CN113372870B - Special adhesive for aluminum plastic film and preparation method thereof - Google Patents
Special adhesive for aluminum plastic film and preparation method thereof Download PDFInfo
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- CN113372870B CN113372870B CN202110580835.9A CN202110580835A CN113372870B CN 113372870 B CN113372870 B CN 113372870B CN 202110580835 A CN202110580835 A CN 202110580835A CN 113372870 B CN113372870 B CN 113372870B
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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
- C09J175/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
- C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids and dialcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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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
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Abstract
The invention belongs to the technical field of new energy, and particularly relates to an adhesive special for an aluminum-plastic film and a preparation method thereof. According to the polyester synthesis scheme provided by the invention, 3-methyl-1, 5-pentanediol is used as a monomer to synthesize polyester adhesive, the water-resistant property of the adhesive is greatly improved, polyester resin with larger molecular weight is synthesized by gradient temperature rise, and meanwhile, groups with different reaction activities at different reaction temperatures are added into the reaction, so that the molecular structure is controlled, and the performance of the polyester adhesive is more excellent. And the obtained polyester intermediate is externally connected with part of polycarbonate, so that the electrolyte resistance of the polyester adhesive is greatly improved, the resistance to damp-heat aging is enhanced, and the excellent resistance to the external environment is obtained.
Description
Technical Field
The invention belongs to the technical field of new energy, and particularly relates to an adhesive special for an aluminum-plastic film and a preparation method thereof.
Background
The soft package lithium battery is generally assembled by wrapping aluminum-plastic films, electrolyte, a diaphragm, positive and negative electrodes and other materials through a certain process, wherein the positive and negative electrodes are soaked in the electrolyte, and lithium ions move between the positive and negative electrodes by taking the electrolyte as a medium to realize the charging and discharging of the battery.
For the inner layer adhesive and the outer layer adhesive of the aluminum-plastic film adhesive, the adhesive strength, the boiling resistance, the stamping resistance and other properties need to be extremely excellent. The adhesive layer is usually selected by using an acid-modified polyolefin, optionally blending an epoxy compound, a cyclic alkane compound, a polyfunctional isocyanate compound, a compatible elastomer, a phosphoric acid-modified compound, etc., and it is a widely used technique to use a composition containing urethane methacrylate, phosphoric acid group methacrylate and epoxy acrylate, or a reaction product of a urethane polyol and a saturated aliphatic and/or alicyclic polyisocyanate, or a combination of an isocyanate compound and saponified ethylene vinyl acetate as the adhesive layer.
At present, japan has absolute technical advantages in the field of flexible-package lithium battery aluminum plastic films, and among them, globally-known aluminum plastic film production enterprises such as japan printing, showa and electrician, and typographic printing corporation have monopoly in the global aluminum plastic film market, and have global advanced patent layouts in the aluminum plastic film field, so that the patent technology output in the aluminum plastic film field in japan is far ahead of other countries and regions. Few enterprises are researched and produced in China, so that the demand for developing a high-performance aluminum plastic film outer layer adhesive capable of replacing an imported adhesive is urgent.
Chinese patent application CN109148740A provides an aluminum plastic film and a lithium battery. The aluminum-plastic film comprises: the aluminum foil heat-resistant adhesive comprises a heat-resistant resin layer, a first adhesive layer, an aluminum foil layer, a second adhesive layer and a heat sealing layer which are sequentially stacked, wherein the first adhesive layer is formed by a polyurethane adhesive, and the polyurethane adhesive contains a polymer formed by the following substances: the aluminum foil comprises polyester polyol, polyisocyanate and epoxy resin, wherein the polyester polyol is generated by the reaction of polybasic acid and polyol, the polybasic acid comprises aromatic polybasic acid and aliphatic polybasic acid, the molar ratio of the aromatic polybasic acid to the aliphatic polybasic acid is 3: 1-6: 1, the outer surface of the aluminum foil layer is provided with a chemical treatment layer, and the chemical treatment layer contains an anhydride functional group.
However, the polyurethane adhesive described in the above patent has a complex preparation method and high cost, and is not beneficial to industrial production, so that there is an urgent need to develop an adhesive special for aluminum plastic films, which has a simple preparation method, excellent properties, and is beneficial to industrial production.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide an adhesive special for an aluminum-plastic film and a preparation method thereof. The special adhesive for the aluminum-plastic film provided by the invention is a special resin with polyurethane as a main component, and has excellent bonding strength, boiling resistance and stamping resistance.
The technical scheme of the invention is as follows:
the special adhesive for the aluminum-plastic film comprises a polyester adhesive and a curing agent, wherein the weight ratio of the polyester adhesive to the curing agent in the special adhesive for the aluminum-plastic film is 100: 10-20 parts of; when in use, the polyester adhesive and the curing agent are uniformly mixed according to the weight ratio.
Further, the preparation method comprises the following steps:
s1, uniformly mixing the glycol mixed solution I and the diacid mixed solution I at normal temperature under the protection of nitrogen, adding a metal catalyst into a reaction kettle for reaction, setting the initial temperature to be 50 ℃, heating at the speed of 1 ℃/min until the temperature reaches 150 ℃, adding the diacid mixed solution II and the glycol mixed solution II, preserving the heat for 1 hour, heating to 180 ℃ at the speed of 1 ℃/min, preserving the heat for 2 hours, then heating to 200 ℃ at the speed of 1 ℃/min, and carrying out vacuum pumping for 30 minutes; cooling and discharging to obtain a polyester intermediate;
s2: uniformly mixing the polyester intermediate obtained in the step S1 with polycarbonate, adding a solvent to dilute until the solid content is 40%, adding 1% of isophorone diisocyanate, heating to 80 ℃ at the speed of 1 ℃/min to react, preserving heat for 2 hours, cooling and discharging to obtain a polyester adhesive;
s3: under the protection of nitrogen, rectifying trihydroxypropane for one hour at 100 ℃, keeping the trihydroxypropane at the bottom of the tower and cooling for later use, adding toluene diisocyanate into a reaction kettle, keeping the temperature at 50 ℃, dripping the treated trihydroxypropane within 4 hours, then heating to 120 ℃ at the speed of 1 ℃/min, refluxing for 2 hours, cooling and discharging to obtain a curing agent; the content of 2, 4-meta configuration in the toluene diisocyanate was 80%.
Further, the weight ratio of the diol mixed solution I to the diacid mixed solution I in the step S1 is 1: 1.15-1.8; the weight ratio of the diol mixed solution II to the diacid mixed solution II is 1: 1.5-2.5; the metal catalyst is 1-3% of the total dosage of the diol mixed solution and the diacid mixed solution.
In addition, the diol mixture I and the diol mixture II in step S1 may be one or more of 3-methyl-1, 5-pentanediol, neopentyl glycol, and 1, 4-butanediol.
Further, the diacid mixture I and the diacid mixture II in step S1 are one or more of adipic acid and terephthalic acid.
The metal catalyst in step S1 is one or more of an organotin compound and an organoplatinum compound.
Furthermore, the metal catalyst organic tin is dibutyltin dilaurate, and the organic platinum is a Kanstedt platinum metal catalyst; further, the concentration of platinum in the kast platinum metal catalyst is 5000 PPM.
Further, the solvent in step S2 is one or more of ethyl acetate, toluene, and xylene.
Further, the weight ratio of the polyester intermediate to the polycarbonate in the step S2 is 100: 5-15.
Further, the temperature reduction refers to temperature reduction by using cold water, and the temperature is reduced to be lower than 40 ℃ at the speed of 2 ℃/min.
Compared with the prior art, the adhesive special for the aluminum-plastic film and the preparation method thereof provided by the invention have the following advantages:
(1) according to the polyester synthesis scheme provided by the invention, 3-methyl-1, 5-pentanediol is used as a monomer to synthesize polyester adhesive, the water resistance of the adhesive is greatly improved, polyester resin with larger molecular weight is synthesized by gradient temperature rise, groups with different reaction activities at different reaction temperatures are added into the reaction, the molecular structure is controlled, and the performance of the polyester adhesive is more excellent.
(2) The obtained polyester intermediate is partially externally connected with polycarbonate, so that the electrolyte resistance of the polyester adhesive is greatly improved, the resistance to damp-heat aging is enhanced, and excellent external environment resistance is obtained.
(3) The trihydroxy propane grafted toluene diisocyanate is used to obtain a matched adhesive curing agent suitable for curing the adhesive, and the value and the stability of the product are improved.
(4) The process of the invention meets the fine production requirement and is easy for industrial production.
Detailed Description
The present invention is further illustrated by the following description of specific embodiments, which are not intended to limit the present invention, and various modifications and improvements can be made by those skilled in the art based on the basic idea of the present invention, but the scope of the present invention is within the scope of the present invention.
Wherein, the reagents used in the invention are all common reagents and can be purchased from common reagent production and sale companies.
Embodiment 1 adhesive special for aluminum plastic film and preparation method thereof
S1: under the protection of nitrogen at normal temperature, uniformly mixing 20 parts of 3-methyl-1, 5-pentanediol and 30 parts of neopentyl glycol with 30 parts of adipic acid and 30 parts of terephthalic acid, adding 2% dibutyltin dilaurate (T12) into a reaction kettle for reaction, setting the initial temperature to be 50 ℃, heating at the speed of 1 ℃/min until the temperature reaches 150 ℃, supplementing 25 parts of adipic acid and 10 parts of 3-methyl-1, 5-pentanediol, keeping the temperature for 1 hour, heating at the speed of 1 ℃/min to 180 ℃, keeping the temperature for 2 hours, then heating at the speed of 1 ℃/min to 200 ℃, and carrying out vacuum pumping for 30 minutes; cooling to 38 ℃, discharging to obtain a polyester intermediate;
s2: uniformly mixing 100 parts of the polyester intermediate obtained in the step S1 with 5 parts of polycarbonate, adding ethyl acetate to dilute until the solid content is 40%, adding 1% of isophorone diisocyanate, heating to 80 ℃ at the speed of 1 ℃/min to react, preserving heat for 2 hours, cooling to 38 ℃, discharging, and obtaining a polyester adhesive;
s3: under the protection of nitrogen, rectifying 80 parts of trihydroxypropane for one hour at 100 ℃, keeping the trihydroxypropane at the bottom of the tower and cooling for later use, adding 60 parts of toluene diisocyanate into a reaction kettle, keeping the temperature at 50 ℃, dripping the treated trihydroxypropane within 4 hours, then heating to 120 ℃ at the speed of 1 ℃/min, refluxing for 2 hours, cooling to 38 ℃, and discharging to obtain a curing agent;
the cooling mode is that cold water is used for cooling, and the temperature is reduced at the speed of 2 ℃/min.
Embodiment 2 adhesive special for aluminum plastic film and preparation method thereof
S1: under the protection of nitrogen at normal temperature, uniformly mixing 30 parts of 3-methyl-1, 5-pentanediol, 5 parts of neopentyl glycol, 40 parts of 1, 4-butanediol, 100 parts of adipic acid and 35 parts of terephthalic acid, adding 2% Kanster platinum metal catalyst (5000PPM) into a reaction kettle for reaction, setting the initial temperature to be 50 ℃, heating at the rate of 1 ℃/min until the temperature reaches 150 ℃, supplementing 20 parts of adipic acid and 12 parts of 3-methyl-1, 5-pentanediol, preserving the heat for 1 hour, subsequently heating at the rate of 1 ℃/min to 180 ℃, preserving the heat for 2 hours, then heating at the rate of 1 ℃/min to 200 ℃, and carrying out vacuum pumping for 30 minutes; cooling to 35 ℃ and discharging to obtain a polyester intermediate;
s2: uniformly mixing 100 parts of the polyester intermediate obtained in the step S1 with 15 parts of polycarbonate, adding ethyl acetate to dilute until the solid content is 40%, adding 1% of isophorone diisocyanate, heating to 80 ℃ at the speed of 1 ℃/min to react, preserving heat for 2 hours, cooling to 35 ℃ and discharging to obtain a polyester adhesive;
s3: under the protection of nitrogen, rectifying 80 parts of trihydroxypropane for one hour at 100 ℃, keeping the trihydroxypropane at the bottom of the tower and cooling for later use, adding 60 parts of toluene diisocyanate into a reaction kettle, keeping the temperature at 50 ℃, dripping the treated trihydroxypropane within 4 hours, then heating to 120 ℃ at the speed of 1 ℃/min, refluxing for 2 hours, cooling to 35 ℃, and discharging to obtain a curing agent;
the cooling mode is that cold water is used for cooling, and the temperature is reduced at the speed of 2 ℃/min.
Embodiment 3 adhesive special for aluminum plastic film and preparation method thereof
S1: under the protection of nitrogen at normal temperature, uniformly mixing 50 parts of 3-methyl-1, 5-pentanediol and 30 parts of neopentyl glycol with 100 parts of adipic acid, adding 2% T12 into a reaction kettle to react, setting the initial temperature to be 50 ℃, heating at the speed of 1 ℃/min until the temperature reaches 150 ℃, supplementing 20 parts of adipic acid and 10 parts of 1, 4-butanediol, preserving heat for 1 hour, then heating to 180 ℃ at the speed of 1 ℃/min, preserving heat for 2 hours, then heating to 200 ℃ at the speed of 1 ℃/min, and carrying out vacuum pumping for 30 minutes; cooling to 32 ℃ and discharging to obtain a polyester intermediate;
s2: uniformly mixing 100 parts of the polyester intermediate obtained in the step S1 with 10 parts of polycarbonate, adding ethyl acetate to dilute until the solid content is 40%, adding 1% of isophorone diisocyanate, heating to 80 ℃ at the speed of 1 ℃/min to react, preserving heat for 2 hours, cooling to 32 ℃, discharging, and obtaining a polyester adhesive;
s3: under the protection of nitrogen, rectifying 80 parts of trihydroxypropane for one hour at 100 ℃, keeping the trihydroxypropane at the bottom of the tower and cooling for later use, adding 60 parts of toluene diisocyanate into a reaction kettle, keeping the temperature at 50 ℃, dripping the treated trihydroxypropane within 4 hours, then heating to 120 ℃ at the speed of 1 ℃/min, refluxing for 2 hours, cooling to 32 ℃, and discharging to obtain a curing agent;
the cooling mode is that cold water is used for cooling, and the temperature is reduced at the speed of 2 ℃/min.
Comparative example 1 adhesive special for aluminum plastic film and preparation method thereof
Comparative example 1 a method for preparing the adhesive special for the aluminum plastic film is similar to that of example 2.
The difference from example 2 is that the temperature increase rate of the gradient temperature increase program set in comparative example 1 is 2 ℃/min.
Comparative example 2 adhesive special for aluminum plastic film and preparation method thereof
In comparison with example 2, comparative example 2 is different in that propylene glycol is used instead of 3-methyl-1, 5-pentanediol, and other parameters and operations are the same as those of example 2.
Comparative example 3 adhesive special for aluminum plastic film and preparation method thereof
In comparison with example 2, comparative example 3 differs in that instead of neopentyl glycol, hexanediol is used, and the other parameters and operations are the same as in example 2.
Comparative example 4 adhesive special for aluminum plastic film and preparation method thereof
In comparison with example 2, comparative example 4 differs in that hexanediol is used instead of 1, 4-butanediol, the other parameters and operation being identical to example 2.
Comparative example 5 adhesive special for aluminum plastic film and preparation method thereof
Comparative example 5 is compared to example 2 with the difference that adipic acid is used instead of terephthalic acid and the other parameters and operations are the same as in example 2.
Comparative example 6 adhesive special for aluminum plastic film and preparation method thereof
In comparison with example 2, comparative example 6 is different in that polycarbonate is not used in step S2 and other parameters and operations are the same as example 2.
Comparative example 7 adhesive special for aluminum plastic film and preparation method thereof
Comparative example 7 is different from example 2 in that the amount of the catalyst used in step S1 is 4%, and other parameters and operations are the same as those of example 2.
Test example Performance detection of adhesive special for aluminum plastic film
1. Test subjects: adhesive special for aluminum plastic film prepared in examples 1-3 and comparative examples 1-7
The polyester adhesives and the curing agents prepared in examples 1 to 3 and comparative examples 1 to 7 were prepared according to the ratio in the table, and coated on an aluminum foil with a thickness of 40um at a coating weight of 4g/m2And baking the mixture for 1 minute by using a 100 ℃ oven, and adhering a PA film with the thickness of 40um at the adhering temperature of 80 ℃ under the adhering pressure of 4kg to obtain the special adhesive for the aluminum plastic film. The formulation of the polyester adhesive and the curing agent corresponding to examples 1 to 3 and comparative examples 1 to 7 is shown in table 1:
TABLE 1 polyester adhesive and curing agent ratio
2. The test method comprises the following steps:
bonding: the peel strength of the special adhesive for the aluminum-plastic films prepared in the embodiments 1-3 and the comparative examples 1-7 is detected according to the national standard GB/T27922014;
boiling resistance: the special adhesive for the aluminum plastic film prepared in the examples 1 to 3 and the comparative examples 1 to 7 is placed in water at 100 ℃ to be boiled for 30 minutes, and appearance changes such as white lines, separation, wrinkles and the like before and after the special adhesive for the aluminum plastic film is boiled are compared;
resistance to wet heat aging: detecting the special adhesive for the aluminum plastic film prepared in the examples 1-3 and the comparative examples 1-7 according to the national standard GB/T17402007;
electrolyte resistance: placing the special adhesive for the aluminum plastic film prepared in the examples 1-3 and the comparative examples 1-7 in electrolyte at 85 ℃, and soaking the special adhesive for the aluminum plastic film in the electrolyte for 24 hours to compare the appearance changes before and after comparison, such as white lines, separation, wrinkles and the like;
anti-stamping; the special adhesive for the aluminum plastic film prepared in the examples 1-3 and the comparative examples 1-7 is used as a material, and a punching machine directly punches a pit with a diameter of 6.5mm, and appearance changes of the material before and after punching, such as white lines, separation, wrinkles and the like, are compared.
3. And (3) test results:
the parameter list of the adhesive special for the aluminum-plastic film prepared in the examples 1 to 3 and the comparative examples 1 to 7 is shown in table 2, and the performance test results of the adhesive special for the aluminum-plastic film prepared in the examples 1 to 3 and the comparative examples 1 to 7 are shown in table 3:
TABLE 2 parameters of examples 1 to 3 and comparative examples 1 to 7
Table 3 Performance test results of adhesives specially used for aluminum plastic films prepared in examples 1-3 and comparative examples 1-7
As shown in the performance test results in Table 3, the number average molecular weights of examples 1 to 3 reach 22000 to 25000, the adhesion (N/mm), the boiling resistance, the stamping resistance, the electrolyte resistance and the resistance to damp-heat aging are all better than those of comparative examples 1 to 7, and at the molecular weight, the polyurethane adhesive can meet the requirement of standard stamping depth of 6mm, but the poor peeling force ratio caused by too large molecular weight and the insufficient tensile strength caused by too small molecular weight can not be caused, and meanwhile, the product tolerance can be improved by the graft modification of polycarbonate, for example, the polycarbonate has extremely good water resistance and boiling resistance.
Based on the test data, example 2 performed best, being the best example of the present invention, and the other two examples also performed better than the other comparative examples.
The adhesive property of the adhesive is more than 7N/mm in the examples 1 to 3, and the adhesive is qualified and has no white line when resistance tests of steaming resistance, stamping resistance, electrolyte resistance and damp-heat aging are carried out.
In comparative example 1, the temperature-increasing rate of the gradient temperature-increasing program was 2 ℃/min, which is different from that of example 2, compared with example 2. Accordingly, the adhesion of comparative example 1 was 6N/mm, which is significantly weaker than that of example 2, and the results of the resistance tests for retort resistance, punching resistance, electrolyte resistance and wet heat aging showed slight white lines or partial lines.
Comparative example 2 differs from example 2 in that propylene glycol is used instead of 3-methyl-1, 5-pentanediol. Accordingly, the adhesion of comparative example 2 was 7N/mm, which is significantly weaker than that of example 2, and the results of the resistance test for retort resistance, punching resistance, electrolyte resistance and wet heat aging showed slight white lines or slight lines.
Comparative example 3 differs from example 2 in that instead of neopentyl glycol, hexanediol is used. Accordingly, the adhesion of comparative example 3 was 6N/mm, which is significantly weaker than that of example 2, and the results of the resistance tests for retort resistance, electrolyte resistance and humid heat aging showed slight white lines or lines, and the result of the impact resistance test showed the appearance of very slight white lines.
Comparative example 4 differs from example 2 in that hexanediol is used instead of 1, 4-butanediol. Accordingly, comparative example 4 had an adhesion of 5N/mm, which was significantly weaker than that of example 2, and the results of the resistance tests for retort resistance, electrolyte resistance and humid heat aging showed slight white lines or lines, and the result of the impact resistance test showed the appearance of very slight white lines.
Comparative example 5 differs from example 2 in that adipic acid is used instead of terephthalic acid. Accordingly, comparative example 5 had an adhesion of 5N/mm, which was significantly weaker than that of example 2, and the results of the resistance test for retort resistance, electrolyte resistance and humid heat aging showed slight white lines or lines, and the result of the impact resistance test showed the appearance of very slight white lines.
Comparative example 6 differs from example 2 in that adipic acid is used instead of terephthalic acid. Accordingly, comparative example 6 had an adhesion of 7.5N/mm, which was significantly weaker than that of example 2, and the results of the resistance tests for retort resistance, electrolyte resistance and humid heat aging showed severe white lines, and the result of the impact resistance test showed the appearance of slight white lines.
Comparative example 7 is different from example 2 in that the amount of the catalyst used in step S1 was 4%, and accordingly, comparative example 7 had an adhesion of 6N/mm and a molecular weight of 28000, but the impact resistance was weakened, and the impact resistance test was conducted with the occurrence of a slight white line.
To sum up, this application embodiment 1 ~ 3 also has better tolerance when having better peel strength, compares 1 ~ 7 and is more suitable for the application of plastic-aluminum membrane.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (7)
1. The special adhesive for the aluminum-plastic film comprises a polyester adhesive and a curing agent, and is characterized in that the weight ratio of the polyester adhesive to the curing agent in the special adhesive for the aluminum-plastic film is 100: 10-20; when in use, the polyester adhesive and the curing agent are uniformly mixed according to the weight part ratio;
the preparation method of the adhesive special for the aluminum-plastic film comprises the following steps:
s1: under the protection of nitrogen at normal temperature, uniformly mixing the glycol solution I and the diacid solution I, adding a metal catalyst into a reaction kettle for reaction, setting the initial temperature to be 50 ℃, heating at the speed of 1 ℃/min until the temperature reaches 150 ℃, supplementing the diacid solution II and the glycol solution II, preserving the heat for 1 hour, subsequently heating to 180 ℃ at the speed of 1 ℃/min, preserving the heat for 2 hours, then heating to 200 ℃ at the speed of 1 ℃/min, and carrying out vacuum pumping for 30 minutes; cooling and discharging to obtain a polyester intermediate;
s2: uniformly mixing the polyester intermediate obtained in the step S1 with polycarbonate, adding a solvent to dilute until the solid content is 40%, adding 1% of isophorone diisocyanate, heating to 80 ℃ at the speed of 1 ℃/min to react, preserving heat for 2 hours, cooling and discharging to obtain a polyester adhesive;
s3: under the protection of nitrogen, rectifying trihydroxypropane for one hour at 100 ℃, keeping the trihydroxypropane at the bottom of the tower and cooling for later use, adding toluene diisocyanate into a reaction kettle, keeping the temperature at 50 ℃, dripping the treated trihydroxypropane within 4 hours, controlling the temperature to be 120 ℃, refluxing for 2 hours, cooling and discharging to obtain a curing agent;
the diol liquid I and the diol liquid II in the step S1 are one or more of 3-methyl-1, 5-pentanediol, neopentyl glycol and 1, 4-butanediol;
the diacid solution I and the diacid solution II in the step S1 are one or more of adipic acid and terephthalic acid.
2. The adhesive special for aluminum-plastic films as claimed in claim 1, wherein the weight ratio of the diol liquid I to the diacid liquid I in the step S1 is 1:1.15 to 1.8; the weight ratio of the glycol liquid II to the diacid liquid II is 1: 1.5-2.5; the metal catalyst accounts for 1-3% of the total consumption of the glycol solution and the diacid solution.
3. The adhesive of claim 1, wherein the metal catalyst in step S1 is one or more of organic tin and organic platinum.
4. The adhesive special for the aluminum-plastic film as recited in claim 3, wherein the metal catalyst organotin is dibutyltin dilaurate and the organic platinum is a platinum catalyst of Kanster.
5. The adhesive special for aluminum-plastic films as claimed in claim 1, wherein the solvent in step S2 is one or more of ethyl acetate, toluene and xylene.
6. The adhesive special for aluminum-plastic films as claimed in claim 1, wherein the weight ratio of the polyester intermediate to the polycarbonate in the step S2 is 100:5 to 15.
7. The adhesive special for the aluminum-plastic film as claimed in claim 1, wherein the temperature reduction is carried out by using cold water to reduce the temperature to less than 40 ℃ at a rate of 2 ℃/min.
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