CN111116875B - High-toughness stamping-resistant polyester resin for compounding aluminum plastic film of lithium battery - Google Patents
High-toughness stamping-resistant polyester resin for compounding aluminum plastic film of lithium battery Download PDFInfo
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- CN111116875B CN111116875B CN201911367595.3A CN201911367595A CN111116875B CN 111116875 B CN111116875 B CN 111116875B CN 201911367595 A CN201911367595 A CN 201911367595A CN 111116875 B CN111116875 B CN 111116875B
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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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
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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Abstract
The invention discloses a high-toughness stamping-resistant polyester resin for compounding an aluminum plastic film of a lithium battery; when in preparation, 25-35% of dicarboxylic acid or acid ester monomer containing rigid structure, 32-42% of dicarboxylic acid with nine or more linear carbon chains, 31-37% of dihydric alcohol with symmetrical structure and carbon chain number less than or equal to 4 and 1-3% of dihydric alcohol containing more than two asymmetric alkyl groups are put into a reaction container for heating and stirring; adding 0.01 to 0.05 percent of catalyst for heating reaction; when the esterification rate of the materials in the reaction vessel is measured to be more than 94 percent, vacuumizing, and gradually increasing the vacuum degree to the hydroxyl value of the materials in the reaction vessel of 46 +/-4 mgKOH/g; heating to 260 +/-5 ℃, vacuumizing, gradually increasing the vacuum degree to below 300Pa, wherein the hydroxyl value of the material in the reaction container is 4 +/-0.5 mgKOH/g; and (5) obtaining the product. The related indexes of the toughness of the resin have advantages; the impact test yield is higher, and the deep drawing test can reach 15mm at most.
Description
Technical Field
The invention relates to the technical field of adhesive resin, in particular to high-toughness stamping-resistant polyester resin for compounding an aluminum plastic film of a lithium battery.
Background
With the development of the technology, lithium ion batteries are increasingly used by people due to the performance advantages of large energy density, high output voltage, small self-discharge, strong cyclic discharge and the like. The aluminum plastic film has the advantages of light weight, thin thickness, flexible appearance design and the like, and is widely applied to many fields of 3C consumer electronics, power batteries, energy storage and the like. The aluminum plastic film is an important material for packaging the soft package battery, plays a vital role in the quality of the soft package battery, and plays a role in protecting contents. As a key link with the highest barrier in the lithium battery industry chain, the global aluminum plastic film composite adhesive resin market is monopolized by a small number of Japan enterprises all the time and almost occupies more than 70% of the global market share.
The synthesis technology of the aluminum plastic film composite adhesive resin is a link with higher technical difficulty in the field of lithium battery materials at present, and related technologies are mastered in a few Japanese enterprises. For example, most of the resins currently used in lithium battery adhesive products worldwide are from TOYOBO (TOYOBO) corporation of japan, which represents products such as Vylon200, Vylon220, Vylon226, Vylon237, and the like. The common characteristic of the polyester resins is that the glue line formed by compounding the polyester resins as main resins and curing agents has good flexibility, and is particularly suitable for the punching aluminum plastic film industry. However, as the main resin in the lithium battery aluminum plastic film composite adhesive, the products have some problems in the actual production process of relevant enterprises in China, and the main performance is as follows:
1. with the development of the new energy automobile industry, the lithium battery industry is also greatly increased. In consideration of energy consumption, endurance and cost, the demand of lithium batteries for light weight is increasing. The problem directly affects the thickness of the aluminum foil, and the reduction of the thickness of the aluminum foil puts higher requirements on the adhesive layer. The yield of the aluminum-plastic composite film using the prior resin product is obviously reduced.
2. Along with the expansion of the capacity demand, the production machine speed of the actual production line is also obviously improved. Particularly, in the step of stamping the aluminum plastic film, the higher-speed stamping also puts higher requirements on the related performance of the adhesive layer. The existing resins have not been able to meet the continuously increasing impact velocity.
3. With the expansion of market capacity, competition among related enterprises is also more intense. Imported resin represented by Japanese enterprises is high in price, the profit margin of local enterprises in China at the downstream is reduced, and meanwhile, the imported resin is possibly restrained by relevant trade policies.
Therefore, the high-toughness stamping-resistant polyester resin for compounding the lithium battery aluminum plastic film is synthesized, the resin has more advantages in stamping resistance and toughness than the existing imported resin products, and each performance of the resin is more suitable for actual production requirements of related enterprises in China.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide the high-toughness stamping-resistant polyester resin for compounding the aluminum plastic film of the lithium battery.
The purpose of the invention is realized by the following technical scheme:
the invention relates to a high-toughness stamping-resistant polyester resin for compounding an aluminum plastic film of a lithium battery, which comprises the following components in percentage by weight:
the polyester resin is prepared by a method comprising the following steps:
s1, putting the dicarboxylic acid or acid ester monomer containing the rigid structure, dicarboxylic acid with nine or more than nine linear carbon chains, diol with a symmetrical structure and carbon chain number less than or equal to four and diol containing more than two asymmetric alkyl groups into a reaction container, and heating and stirring at 120-140 ℃ until the materials are dissolved and form a slurry state;
s2, adding the catalyst, and gradually heating to 240-260 ℃ for reaction; when the esterification rate of the materials in the reaction vessel is measured to be more than 94 percent, the vacuum pumping is started at the constant temperature of 240 ℃, and the vacuum degree is gradually increased until the hydroxyl value of the materials in the reaction vessel is 46 +/-4 mgKOH/g;
s3, raising the temperature in the reaction container to 260 +/-5 ℃, starting to vacuumize, gradually raising the vacuum degree to below 300Pa, and controlling the hydroxyl value of the materials in the reaction container to be 4 +/-0.5 mgKOH/g; and (4) after the reaction is finished, obtaining the polyester resin.
As an embodiment of the invention, the dicarboxylic acid or acid ester monomer containing a rigid structure refers to one or more of terephthalic acid, dimethyl terephthalate and isophthalic acid. Terephthalic acid and dimethyl terephthalate are generally considered equivalents by the skilled person in the field of polyester synthesis, and they can be substituted for each other. In actual production in the industry, the two are not used together, because the two can be switched to replace each other, and only one of the two is usually used. Preferably wherein the amount of terephthalic acid or dimethyl terephthalate is not less than 50% of the amount of dicarboxylic acid containing rigid structures.
As an embodiment of the present invention, the dicarboxylic acid having nine or more linear carbon chains is one or both of azelaic acid and sebacic acid.
As an embodiment of the invention, the dihydric alcohol having a symmetrical structure and a carbon chain number of less than or equal to four means one or both of ethylene glycol and 1, 4-butanediol.
In one embodiment of the present invention, the diol having two or more asymmetric alkyl groups is one of 2,2, 4-trimethyl-1, 3-pentanediol, 2-methyl-2, 4-pentanediol, and 2-butyl-2-ethyl-1, 3-propanediol.
As an embodiment of the invention, the catalyst comprises one or more of monobutyl triisooctoate tin, dioctyl tin oxide, dibutyl tin oxide, dihydroxy butyl tin chloride, monobutyl tin oxide, zinc oxalate and zinc acetate.
The design principle of the invention is as follows:
the aluminum-plastic film of the lithium battery is a product obtained by compounding an aluminum foil layer and a plastic film layer (PET, nylon and other films) through an adhesive layer. The polyester developed by the invention is used as a glue layer. Since the finished lithium battery has various shapes, the aluminum plastic film is punched by a die in practical application. Although the aluminum foil itself is somewhat ductile, the aluminum foil cannot withstand such instantaneous, high-speed, large deformation stamping without being damaged. Therefore, the adhesive layer needs to be protected, and the adhesive layer has very good toughness, can generate certain deformation along with the aluminum foil in the stamping process, and simultaneously has higher cohesive strength to protect the aluminum foil from being damaged. This requires that the polyester be both "rigid" and "flexible".
The dicarboxylic acid or acid ester monomer containing rigid structure mainly endows the polyester with high cohesive force and rigidity, and the use amount is insufficient, so that the adhesive layer has insufficient strength. Too much dosage, too strong rigidity, brittle glue line, easy fracture and damage together with the aluminum foil. The reason why the amount of terephthalic acid or dimethyl terephthalate is not less than 50% of the amount of dicarboxylic acid having a rigid structure is that the crystallinity of the terephthalic structure is strong and the effect of improving the rigid structure of the polyester is most remarkable, and if the amount of terephthalic acid or dimethyl terephthalate is not sufficient, the lower limit corresponding to the requirement of the whole product for the rigid structure is not reached.
Dicarboxylic acids with nine or more linear carbon chains are used to impart "softness" to the polyester, at too low a level, and the gum layer is "brittle" and easily broken. Too much dosage, too soft adhesive layer, no strength, insufficient composite fastness of the aluminum foil and the plastic film, damage of the aluminum foil after stamping and delamination and falling off of the aluminum plastic film. The reason why nine or more linear carbon chain numbers are defined is that the structural unit can impart stronger flexibility as the carbon chain number increases. Under the premise of ensuring the proportion of rigid structural units, nine or more than nine flexible structures must be selected for obtaining a more balanced flexible structure, otherwise the performance is not enough.
The dihydric alcohol with a symmetrical structure and a carbon chain number less than or equal to four is used for improving the crystallinity of the whole polyester, improving cohesive energy and endowing the polyester with composite strength as an adhesive layer. The number of carbon chains is less than or equal to by limiting the length of the carbon chains so that they do not adversely affect the strength provided by the rigid building blocks.
The dihydric alcohol containing more than two asymmetric alkyl groups is used as a polyester crystallization performance regulator, and the rigidity and flexibility of the polyester can reach the required balance effect through the function of the dihydric alcohol, so that the material has the optimal toughness performance. Slightly more, the polyester shifts to more "soft" and slightly less, the polyester shifts to more "rigid", although the effect is evident at a lesser amount.
Compared with the prior art, the invention has the following beneficial effects:
(1) the product has the advantages of related indexes of resin toughness (tensile yield strength and elongation at break);
(2) the production process is more suitable for the domestic lithium battery aluminum plastic film factories, the impact test yield is higher, and the deep punching test can reach 15mm at most;
(3) the main resin is synthesized independently, and the cost is far lower than that of imported resin;
(4) good compounding fastness.
Detailed Description
The present invention will be described in detail with reference to examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the present invention.
Example 1
The embodiment relates to a high-toughness stamping-resistant polyester resin for compounding an aluminum plastic film of a lithium battery, which comprises the following components in percentage by weight: 16.44 percent of terephthalic acid, 13.15 percent of isophthalic acid, 36.17 percent of sebacic acid, 32.89 percent of ethylene glycol, 1.32 percent of 2,2, 4-trimethyl-1, 3-pentanediol and 0.03 percent of dihydroxy butyl tin chloride.
The specific synthesis comprises the following process steps:
(1) 25Kg of terephthalic acid, 20Kg of isophthalic acid, 55Kg of sebacic acid, 50Kg of ethylene glycol and 2Kg of 2,2, 4-trimethyl-1, 3-pentanediol were put into a reaction kettle and stirred and heated at a temperature of 130 ℃. After the materials are dissolved, 45g of dihydroxy butyl tin chloride is added, and the temperature is gradually increased to 250 ℃ for reaction. When the esterification rate in the kettle is measured to be more than 94 percent, the vacuum pumping is started at the constant temperature of 240 ℃, and the vacuum degree is gradually increased until the hydroxyl value of the materials in the kettle is 46 +/-4 mgKOH/g.
(2) Raising the temperature in the reaction container to 260 +/-5 ℃, starting to vacuumize, gradually raising the vacuum degree to below 300Pa, wherein the hydroxyl value of the materials in the reaction container is 4 +/-0.5 mgKOH/g; the reaction was complete.
(3) Discharging after the reaction is finished.
The composite fastness test method comprises the following steps: 20 parts of the self-synthesized polyester resin, 1 part of the curing agent 3390 and 49 parts of ethyl acetate are mixed, fully stirred and compounded with the aluminum-plastic film, and a 180-degree peeling test is carried out after the glue layer is cured.
Tensile yield strength, elongation at break: ASTM638 test standards were used. 20 parts of the self-synthesized polyester resin of this example and 1 part of the curing agent 3390 were mixed by a hot melt method to prepare a sample piece, and the sample piece was cured for 48 hours and then tested.
The stamping depth test method comprises the following steps: the stamping die is 80mm by 40mm, and the maximum depth is 25 mm. The impact pressure is 0.6 MPa. And continuously punching the shell for 20 times at a certain depth, wherein the edges of all the punched shells have no aluminum foil tearing damage or aluminum-plastic film delamination phenomenon, and the sample is qualified in the test under the punching depth. The maximum acceptable impact depth for each sample was taken and recorded as the penetration depth.
The test results are shown in table 1.
Comparative example 1
The comparative example relates to a high-toughness stamping-resistant polyester resin for compounding an aluminum plastic film of a lithium battery, and the raw materials of the polyester resin comprise the following components in percentage by weight: 11.84 percent of terephthalic acid, 17.75 percent of isophthalic acid, 36.17 percent of sebacic acid, 32.89 percent of ethylene glycol, 1.32 percent of 2,2, 4-trimethyl-1, 3-pentanediol and 0.03 percent of dihydroxy butyl tin chloride.
The specific synthesis comprises the following process steps:
(1) 18Kg of terephthalic acid, 27Kg of isophthalic acid, 55Kg of sebacic acid, 50Kg of ethylene glycol and 2Kg of 2,2, 4-trimethyl-1, 3-pentanediol were put into a reaction kettle and stirred and heated at a temperature of 130 ℃. After the materials are dissolved, 45g of dihydroxy butyl tin chloride is added, and the temperature is gradually increased to 250 ℃ for reaction. When the esterification rate in the kettle is measured to be more than 94 percent, the vacuum pumping is started at the constant temperature of 240 ℃, and the vacuum degree is gradually increased until the hydroxyl value of the materials in the kettle is 46 +/-4 mgKOH/g.
Compared with the embodiment 1, the content of the terephthalic acid is lower than 50 percent of the total content of the rigid structure dibasic acid on the premise of ensuring that the total content of the rigid structure dibasic acid is not changed. Because the rigid structural units mainly provide rigidity and strength for the adhesive layer, the increase of the cohesive force of the adhesive layer is most obvious because of the high symmetry of the terephthalic acid or the dimethyl terephthalate. When the amount is less than 50% of the total amount of the dibasic acid containing the rigid structure, the decrease in crystallinity of the whole structure results in a significant decrease in bond line strength and tensile yield strength, with a corresponding increase in elongation at break.
Comparative example 2
The comparative example relates to a high-toughness stamping-resistant polyester resin for compounding an aluminum plastic film of a lithium battery, and the raw materials of the polyester resin comprise the following components in percentage by weight: 16.44 percent of terephthalic acid, 13.15 percent of phthalic acid, 36.17 percent of sebacic acid, 32.89 percent of ethylene glycol, 1.32 percent of 2,2, 4-trimethyl-1, 3-pentanediol and 0.03 percent of dihydroxy butyl tin chloride.
The specific synthesis comprises the following process steps:
(1) 25Kg of terephthalic acid, 20Kg of phthalic acid, 55Kg of sebacic acid, 50Kg of ethylene glycol and 2Kg of 2,2, 4-trimethyl-1, 3-pentanediol are put into a reaction kettle and stirred and heated at a temperature of 130 ℃. After the materials are dissolved, 45g of dihydroxy butyl tin chloride is added, and the temperature is gradually increased to 250 ℃ for reaction. When the esterification rate in the kettle is measured to be more than 94 percent, the vacuum pumping is started at the constant temperature of 240 ℃, and the vacuum degree is gradually increased until the hydroxyl value of the materials in the kettle is 46 +/-4 mgKOH/g.
The isophthalic acid was replaced by an equal amount of phthalic acid compared to example 1. Although phthalic acid structurally belongs to a dibasic acid monomer containing a rigid structure, due to the high asymmetry and the strong steric hindrance effect of the phthalic structure, the addition of a large amount of phthalic acid can obviously destroy the crystallization property of high molecular chain fracture, reduce the cohesive force and further influence the strength of an adhesive layer.
Comparative example 3
The comparative example relates to a high-toughness stamping-resistant polyester resin for compounding an aluminum plastic film of a lithium battery, and the raw materials of the polyester resin comprise the following components in percentage by weight: 19.36 percent of terephthalic acid, 15.46 percent of isophthalic acid, 24.86 percent of 1, 4-butanedioic acid, 38.71 percent of ethylene glycol, 1.55 percent of 2,2, 4-trimethyl-1, 3-pentanediol and 0.03 percent of dihydroxy butyl tin chloride.
The specific synthesis comprises the following process steps:
(1) 25Kg of terephthalic acid, 20Kg of isophthalic acid, 32.11Kg of 1, 4-succinic acid, 50Kg of ethylene glycol and 2Kg of 2,2, 4-trimethyl-1, 3-pentanediol are put into a reaction kettle and stirred and heated at the temperature of 130 ℃. After the materials are dissolved, 45g of dihydroxy butyl tin chloride is added, and the temperature is gradually increased to 250 ℃ for reaction. When the esterification rate in the kettle is measured to be more than 94 percent, the vacuum pumping is started at the constant temperature of 240 ℃, and the vacuum degree is gradually increased until the hydroxyl value of the materials in the kettle is 46 +/-4 mgKOH/g.
In comparison with example 1, sebacic acid was replaced by equimolar 1, 4-butanedioic acid. Because the role of sebacic acid in the structure is to provide flexibility to the molecular chain through linear long carbon chains. The 1, 4-succinic acid is not enough to provide enough flexibility for the adhesive layer due to the short carbon chain, and finally the adhesive layer is hard overall and the toughness is reduced.
Comparative example 4
The comparative example relates to a high-toughness stamping-resistant polyester resin for compounding an aluminum plastic film of a lithium battery, and the raw materials of the polyester resin comprise the following components in percentage by weight: 12.67% of terephthalic acid, 10.15% of isophthalic acid, 27.88% of sebacic acid, 48.26% of 1, 6-hexanediol, 1.01% of 2,2, 4-trimethyl-1, 3-pentanediol and 0.03% of dihydroxybutyltin chloride.
The specific synthesis comprises the following process steps:
(1) 25Kg of terephthalic acid, 20Kg of isophthalic acid, 55Kg of sebacic acid, 95.19Kg of 1, 6-hexanediol and 2Kg of 2,2, 4-trimethyl-1, 3-pentanediol were put into a reaction vessel and stirred and heated at 130 ℃. After the materials are dissolved, 45g of dihydroxy butyl tin chloride is added, and the temperature is gradually increased to 250 ℃ for reaction. When the esterification rate in the kettle is measured to be more than 94 percent, the vacuum pumping is started at the constant temperature of 240 ℃, and the vacuum degree is gradually increased until the hydroxyl value of the materials in the kettle is 46 +/-4 mgKOH/g.
In comparison with example 1, ethylene glycol was replaced by equimolar amounts of 1, 6-hexanediol. The dihydric alcohol with a symmetrical structure and the carbon chain number less than or equal to four is used for improving the integral crystallinity of the polyester, improving the cohesive energy and endowing the polyester with the composite strength as an adhesive layer. Although 1, 6-hexanediol also has a symmetrical structure, the carbon chain is relatively long, and the rigidity of a part of the rubber layer is reduced, so that the corresponding performance is reduced.
Comparative example 5
The comparative example relates to a high-toughness stamping-resistant polyester resin for compounding an aluminum plastic film of a lithium battery, and the raw materials of the polyester resin comprise the following components in percentage by weight: 16.57% of terephthalic acid, 13.25% of isophthalic acid, 36.45% of sebacic acid, 33.70% of ethylene glycol and 0.03% of dihydroxybutylstannic chloride.
The specific synthesis comprises the following process steps:
(1) 25kg of terephthalic acid, 20kg of isophthalic acid, 55kg of sebacic acid and 50.85kg of ethylene glycol were put into a reaction kettle and stirred and heated at a temperature of 130 ℃. After the materials are dissolved, 45g of dihydroxy butyl tin chloride is added, and the temperature is gradually increased to 250 ℃ for reaction. When the esterification rate in the kettle is measured to be more than 94 percent, the vacuum pumping is started at the constant temperature of 240 ℃, and the vacuum degree is gradually increased until the hydroxyl value of the materials in the kettle is 46 +/-4 mgKOH/g.
In comparison with example 1, instead of using the diol "2, 2, 4-trimethyl-1, 3-pentanediol", which contains more than two asymmetric alkyl groups, an equimolar amount of ethylene glycol is used instead. Because the 2,2, 4-trimethyl-1, 3-pentanediol side chain has an asymmetric methyl structure, the side chain can be used for adjusting the interaction force among molecular chains, so that the molecular chains are easier to move under the action of external force. Particularly, the method has obvious improvement effect on the aspect of dynamic stretching related performance test, and improves the flexibility of the glue layer. If not added, the deep drawing property is remarkably reduced although the adhesive strength is not remarkably affected.
Example 2
The embodiment relates to a high-toughness stamping-resistant polyester resin for compounding an aluminum plastic film of a lithium battery, which comprises the following components in percentage by weight: 13 percent of dimethyl terephthalate, 12 percent of isophthalic acid, 42 percent of azelaic acid, 31 percent of 1, 4-butanediol, 1.99 percent of 2-methyl-2, 4-pentanediol and 0.01 percent of monobutyl triisooctanoic acid tin.
The specific synthesis comprises the following process steps:
(1) 19.5Kg of dimethyl terephthalate, 18Kg of isophthalic acid, 63Kg of azelaic acid, 46.5Kg of 1, 4-butanediol and 2.99Kg of 2-methyl-2, 4-pentanediol are put into a reaction kettle and stirred and heated at the temperature of 120 ℃. After the materials are dissolved, 15g of monobutyl triisooctanoic acid tin is added, and the temperature is gradually increased to 240 ℃ for reaction. When the esterification rate in the kettle is measured to be more than 94 percent, the vacuum pumping is started at the constant temperature of 240 ℃, and the vacuum degree is gradually increased until the hydroxyl value of the materials in the kettle is 46 +/-4 mgKOH/g.
(2) Raising the temperature in the reaction container to 260 +/-5 ℃, starting to vacuumize, gradually raising the vacuum degree to below 300Pa, wherein the hydroxyl value of the materials in the reaction container is 4 +/-0.5 mgKOH/g; the reaction was complete.
(3) Discharging after the reaction is finished.
The complex fastness test, tensile yield strength, elongation at break test and depth of punch test were the same as in example 1, and the test results are shown in table 1.
Example 3
The embodiment relates to a high-toughness stamping-resistant polyester resin for compounding an aluminum plastic film of a lithium battery, which comprises the following components in percentage by weight: 35% of dimethyl terephthalate, 32% of azelaic acid, 31.95% of ethylene glycol, 1% of 2-butyl-2-ethyl-1, 3-propanediol and 0.05% of zinc oxalate.
The specific synthesis comprises the following process steps:
(1) 52.5Kg of dimethyl terephthalate, 48Kg of azelaic acid, 47.93Kg of ethylene glycol and 1.5Kg of 2-butyl-2-ethyl-1, 3-propanediol are put into a reaction kettle and stirred and heated at the temperature of 140 ℃. After the materials are dissolved, 75g of zinc oxalate is added, and the temperature is gradually increased to 260 ℃ for reaction. When the esterification rate in the kettle is measured to be more than 94 percent, the vacuum pumping is started at the constant temperature of 240 ℃, and the vacuum degree is gradually increased until the hydroxyl value of the materials in the kettle is 46 +/-4 mgKOH/g.
(2) Raising the temperature in the reaction container to 260 +/-5 ℃, starting to vacuumize, gradually raising the vacuum degree to below 300Pa, wherein the hydroxyl value of the materials in the reaction container is 4 +/-0.5 mgKOH/g; the reaction was complete.
(3) Discharging after the reaction is finished.
The complex fastness test, tensile yield strength, elongation at break test and depth of punch test were the same as in example 1, and the test results are shown in table 1.
Example 4
The embodiment relates to a high-toughness stamping-resistant polyester resin for compounding an aluminum plastic film of a lithium battery, which comprises the following components in percentage by weight: 18 percent of terephthalic acid, 9.98 percent of isophthalic acid, 32 percent of sebacic acid, 37 percent of 1, 4-butanediol, 3 percent of 2,2, 4-trimethyl-1, 3-pentanediol and 0.02 percent of dioctyl tin oxide.
The specific synthesis comprises the following process steps:
(1) 27Kg of terephthalic acid, 14.97Kg of isophthalic acid, 48Kg of sebacic acid, 55.5Kg of 1, 4-butanediol and 4.5Kg of 2,2, 4-trimethyl-1, 3-pentanediol were put into a reaction vessel and heated at 130 ℃ with stirring. After the materials are dissolved, 30g of dioctyl tin oxide is added, and the temperature is gradually increased to 250 ℃ for reaction. When the esterification rate in the kettle is measured to be more than 94 percent, the vacuum pumping is started at the constant temperature of 240 ℃, and the vacuum degree is gradually increased until the hydroxyl value of the materials in the kettle is 46 +/-4 mgKOH/g.
(2) Raising the temperature in the reaction container to 260 +/-5 ℃, starting to vacuumize, gradually raising the vacuum degree to below 300Pa, wherein the hydroxyl value of the materials in the reaction container is 4 +/-0.5 mgKOH/g; the reaction was complete.
(3) Discharging after the reaction is finished.
The complex fastness test, tensile yield strength, elongation at break test and depth of punch test were the same as in example 1, and the test results are shown in table 1.
TABLE 1
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (5)
1. The high-toughness stamping-resistant polyester resin for compounding the aluminum plastic film of the lithium battery is characterized in that the polyester resin comprises the following components in percentage by weight:
25-35% of dicarboxylic acid or acid ester monomer containing rigid structure;
32-42% of dicarboxylic acid with nine or more than nine linear carbon chains;
31-37% of dihydric alcohol with a symmetrical structure and a carbon chain number less than or equal to four;
1-3% of dihydric alcohol containing more than two asymmetric alkyl groups;
0.01 to 0.05 percent of catalyst;
the dicarboxylic acid or acid ester monomer containing the rigid structure refers to one or more of terephthalic acid, dimethyl terephthalate and isophthalic acid; the using ratio of terephthalic acid or dimethyl terephthalate in the dicarboxylic acid or acid ester monomer containing the rigid structure is more than or equal to 50 percent;
the polyester resin is prepared by a method comprising the following steps:
s1, putting the dicarboxylic acid or acid ester monomer containing the rigid structure, dicarboxylic acid with nine or more than nine linear carbon chains, diol with a symmetrical structure and carbon chain number less than or equal to four and diol containing more than two asymmetric alkyl groups into a reaction container, and heating and stirring at 120-140 ℃ until the materials are dissolved and form a slurry state;
s2, adding the catalyst, and gradually heating to 240-260 ℃ for reaction; when the esterification rate of the materials in the reaction vessel is measured to be more than 94 percent, the vacuum pumping is started at the constant temperature of 240 ℃, and the vacuum degree is gradually increased until the hydroxyl value of the materials in the reaction vessel is 46 +/-4 mgKOH/g;
s3, raising the temperature in the reaction container to 260 +/-5 ℃, starting to vacuumize, gradually raising the vacuum degree to below 300Pa, and controlling the hydroxyl value of the materials in the reaction container to be 4 +/-0.5 mgKOH/g; and (4) after the reaction is finished, obtaining the polyester resin.
2. The high-toughness impact-resistant polyester resin for aluminum plastic film composite of lithium batteries as claimed in claim 1, wherein said dicarboxylic acid having nine or more linear carbon chains is one or both of azelaic acid and sebacic acid.
3. The high-toughness impact-resistant polyester resin for aluminum plastic film composite of lithium batteries as claimed in claim 1, wherein said diol having a symmetrical structure and a carbon chain number of less than or equal to four is one or two of ethylene glycol and 1, 4-butanediol.
4. The high-toughness impact-resistant polyester resin for aluminum plastic film composite of lithium battery as claimed in claim 1, wherein said diol containing two or more asymmetric alkyl groups is one of 2,2, 4-trimethyl-1, 3-pentanediol and 2-butyl-2-ethyl-1, 3-propanediol.
5. The high-toughness impact-resistant polyester resin for the aluminum plastic film composite of the lithium battery as claimed in claim 1, wherein the catalyst comprises one or more of monobutyl triisooctanoic acid tin, dioctyl tin oxide, dibutyl tin oxide, dihydroxy butyl tin chloride, monobutyl tin oxide, zinc oxalate and zinc acetate.
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| CN102675609B (en) * | 2012-06-07 | 2013-09-18 | 昆山天洋热熔胶有限公司 | Rapid crystallization type nanometer composite polyester hot melt adhesive and preparing process thereof |
| US9416290B2 (en) * | 2012-12-28 | 2016-08-16 | Nthdegree Technologies Worldwide Inc. | Nickel inks and oxidation resistant and conductive coatings |
| JP6101548B2 (en) * | 2013-04-12 | 2017-03-22 | アイカ工業株式会社 | Hot melt adhesive composition |
| WO2017104639A1 (en) * | 2015-12-17 | 2017-06-22 | Dic株式会社 | Gas barrier adhesive, film and gas barrier film |
| IT201600078950A1 (en) * | 2016-07-27 | 2018-01-27 | Versalis Spa | Regioselective synthesis method of polyesters from asymmetric diols. |
| WO2019100058A1 (en) * | 2017-11-20 | 2019-05-23 | Resinate Materials Group, Inc. | Polyol compositions from thermoplastic polyesters and their use in hot-melt adhesives and binders |
| CN109148740A (en) * | 2018-07-20 | 2019-01-04 | 乐凯胶片股份有限公司 | Aluminum plastic film and lithium battery |
| CN109293906B (en) * | 2018-09-26 | 2021-09-03 | 上海维凯光电新材料有限公司 | High-weather-resistance polyester for bonding multilayer films of solar back plates and synthesis method thereof |
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