CN112646137A - Modified polyester for high-temperature heat-sealing polyester film, production method and production method of heat-sealing polyester film - Google Patents
Modified polyester for high-temperature heat-sealing polyester film, production method and production method of heat-sealing polyester film Download PDFInfo
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- CN112646137A CN112646137A CN201911374516.1A CN201911374516A CN112646137A CN 112646137 A CN112646137 A CN 112646137A CN 201911374516 A CN201911374516 A CN 201911374516A CN 112646137 A CN112646137 A CN 112646137A
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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
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic 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
- C08G63/02—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
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses modified polyester for a high-temperature heat-sealing polyester film, a production method and a production method of the heat-sealing polyester film, and mainly relates to the field of heat-sealing polyester films. The ethylene glycol terephthalate/ethylene glycol composite material is prepared by polymerizing terephthalic acid, ethylene glycol, isophthalic acid, neopentyl glycol and 1, 4-cyclohexanedimethanol, wherein the molar ratio of the terephthalic acid to the ethylene glycol to the isophthalic acid to the neopentyl glycol to the 1, 4-cyclohexanedimethanol is 15-25: 22-32: 2-5: 2-7: 1-3. The invention has the beneficial effects that: solves the problems that the existing heat-sealing film has low unsealing temperature and is not suitable for being used in the high-temperature field of microwave oven and cooking.
Description
Technical Field
The application relates to the field of heat-seal polyester films, in particular to modified polyester for high-temperature heat-seal polyester films, a production method and a production method of the heat-seal polyester films.
Background
The biaxially oriented polyester film (BOPET) has excellent comprehensive properties such as good transparency, low haze, high gloss, high mechanical strength, high elastic modulus, rigidity, scratch resistance, folding resistance, excellent barrier property, easy printing and the like, and is widely applied to the industries of packaging, card protection, metallization, insulating materials and the like. The BOPET film is the application field with the fastest increase of the demand of the BOPET film in the field of commodity packaging with high requirements on air tightness and aroma retention of tea, coffee, milk powder and the like. However, since PET itself is a crystalline polymer, it has a high glass transition temperature (78 ℃ C.), a high melting point (256 ℃ C.), and it does not have a heat-sealing property, and in order to make it have a heat-sealing property, it is modified by copolymerization or blending
The common copolymerization modifying monomer of the heat sealing material of the heat sealing film is one or two of isophthalic acid (IPA) and neopentyl glycol (NPG) which act together, and the melting temperature range of the heat-sealable copolyester can be adjusted according to the content of IPA and NPC in the copolymer. Generally, the seal-initiation temperature of the heat-sealable copolyester film is lower with the increase of the addition amount of the comonomer, so that the content of the comonomer needs to be reduced for increasing the seal-initiation temperature of the heat-sealable film, but the heat-sealing performance of the heat-sealable film is affected by the reduction of the content of the comonomer, so that the heat-sealing initiation temperature of the heat-sealable film of the copolyester modified by IPA and NPG is about 110 ℃ and not more than 130 ℃.
Because the heat-seal starting temperature of BOPET heat-seal films is low, the subsequent use process cannot have too high temperature, and the use of the film in certain fields is limited. If the food is directly packaged by the film and heated in a microwave oven, the existing polyester heat-sealing film has the phenomenon of seal adhesion, and the non-opening part of the bag is also adhered after the food is heated in the microwave oven, so that the food cannot be normally taken out. In addition, the heat-sealing surface is heat-sealed with other materials and then made into a bag, the bag is used in some fields (above 121 ℃) needing high-temperature cooking, and the phenomenon that the heat-sealing strength is reduced in the cooking process due to low seal-starting temperature of a common heat-sealing film.
Disclosure of Invention
The application aims to provide modified polyester for a high-temperature heat-sealing polyester film, a production method and a production method of the heat-sealing polyester film, and solves the problems that the existing heat-sealing film is low in unsealing temperature and is not suitable for being used in the high-temperature field of microwave ovens and cooking.
In order to achieve the purpose, the method is realized by the following technical scheme:
the modified polyester for high-temperature heat sealing of the polyester film is formed by polymerizing terephthalic acid, ethylene glycol, isophthalic acid, neopentyl glycol and 1, 4-cyclohexanedimethanol, wherein the molar ratio of the terephthalic acid to the ethylene glycol to the isophthalic acid to the neopentyl glycol to the 1, 4-cyclohexanedimethanol is 15-25: 22-32: 2-5: 2-7: 1-3.
The production process of modified polyester for high temperature heat sealing polyester film includes the following steps: uniformly stirring terephthalic acid, ethylene glycol, isophthalic acid, neopentyl glycol and 1, 4-cyclohexanedimethanol according to a ratio, controlling the temperature of an esterification kettle to be 250-270 ℃, and adding a blue reagent to perform esterification reaction; feeding the materials after the esterification reaction into a polycondensation kettle, heating to 255-265 ℃, starting to vacuumize the polycondensation kettle, carrying out vacuum polycondensation reaction at 270-290 ℃, carrying out vacuum polycondensation reaction under the stirring condition, wherein the initial stirring condition is 50HZ and 0.6KW, when reaching 2.1KW, reducing the 50HZ to 35HZ for continuous stirring, when reaching 2.0KW, reducing the 35HZ to 25HZ for continuous stirring, and when reaching 1.8KW, stopping stirring; and (3) raising the pressure of the polycondensation kettle to 0.2MPa by using nitrogen, opening a discharge valve to discharge, and performing water cooling, grain cutting and drying to obtain polymer slices.
A heat-seal polyester film production method, the modified polyester material of claim 1 and the crystalline ethylene terephthalate of silicon dioxide are blended, the modified polyester material accounts for more than 90 percent; the three layers are co-extruded, wherein the heat sealing layer is one of the outer layers, the thickness of the heat sealing layer is 10-30 mu m, and the heat sealing layer accounts for 10-20% of the whole film; the temperature of the chilling roller is set to be 25 ℃ for chilling; the transverse-longitudinal stretching ratio is 3.5-4, the preheating section temperature of the longitudinal stretching machine is 60 ℃, 65 ℃, 75 ℃, the stretching section temperature is 79 ℃, 82 ℃, 30 ℃, and the cooling section temperature is 36 ℃ for longitudinal stretching; setting the temperature of a drawing machine of a transverse drawing machine: a preheating section: 96 ℃, 102 ℃ and 104 ℃; stretching: heat setting section at 106 ℃, 110 ℃, 115 ℃ and 119 ℃: 215 ℃, 240 ℃, 238 ℃, 215 ℃; a cooling section: transversely stretching and shaping at 160 deg.C and 40 deg.C.
Compared with the prior art, the beneficial effects of the application lie in:
the existing heat sealing film has low unsealing temperature, and can easily cause the problems of adhesion, strength reduction and the like when being used under the conditions of microwave oven heating, stewing and the like. The method reduces the content of comonomers IPA and NPG, simultaneously adds a modified component CHDM (1, 4-cyclohexanedimethanol) to polymerize with terephthalic acid (PTA) and Ethylene Glycol (EG), adjusts the melting range of the polymerized polyester material to 180-220 ℃, and can be directly used in the environments of microwave oven, cooking and the like, wherein the seal-initiating and heat-sealing temperature of the heat-sealing film produced by the polyester material is at least above 180 ℃.
Detailed Description
The present application is further illustrated with reference to specific examples.
Example 1: 34kg of terephthalic acid, 17.2kg of ethylene glycol, 5.6kg of isophthalic acid, 4.3kg of neopentyl glycol, 2.2kg of 1, 4-cyclohexanedimethanol, TMP15ml and 20g of catalyst are added into a slurry preparation device to be uniformly stirred, blanking is started after the temperature of a pre-esterification reaction kettle is raised to 250 ℃, stirring is started after the temperature is raised, the temperature of the kettle is controlled to be between 250 ℃ and 270 ℃, a blue temperature agent is added, and generated esterification water is slowly discharged. And when the generated esterification water reaches the theoretical amount and is about 3 hours, indicating that the esterification reaction is finished.
Introducing the materials into an esterification kettle through a material guide pipe, entering a polycondensation kettle through the esterification kettle, raising the temperature to 260 ℃, starting to slowly vacuumize, finally carrying out high vacuum polycondensation reaction at 270-290 ℃, setting the starting stirring frequency to be 50HZ, setting the stirring frequency to be 0.6KW, when the stirring frequency reaches 2.10KW, the gear shifting is started, the 50HZ is reduced to 35HZ, the gear shifting is carried out when the stirring frequency reaches 2.0KW, the 35HZ is reduced to 25HZ, when the stirring frequency reaches 1.8KW, stopping stirring, increasing the pressure of the polycondensation reaction kettle to 0.2MPa by using nitrogen, opening a discharge valve to discharge, performing water cooling, granulating and drying to obtain polymer slices, the physical index analysis of the polyester chip shows that the melting range is 180-220 ℃, the glass transition temperature is 75 ℃, the crystallization peak temperature is 167 ℃, the viscosity is 0.76dl/g, the polyester material has a crystallization peak of 167 ℃ and a melting peak of 211 ℃, and the polyester material is a semi-crystalline polyester raw material.
The polyester material and the ethylene terephthalate containing silicon dioxide crystals are blended, and the high-melting-point modified polyester material accounts for more than 90 percent. And three layers are co-extruded, wherein the heat sealing layer is one of the outer layers and is 10% inside the whole film. The film thickness of the heat-sealable film is generally from 10 to 30 μm.
The temperature of a chill roll is set to be 25 ℃ for chilling, the transverse and longitudinal stretching ratio is preferably 3.4, and the temperature of a longitudinal drawing machine is set as follows: a preheating section: 60. 65, 75 (. degree. C.); temperature of the stretching section: 79. 82, 30 (. degree. C.); temperature of the cooling section: longitudinal stretching at 36 (DEG C), and
setting the temperature of the transverse drawing machine: a preheating section: 96. 102, 104 (. degree. C.); stretching: 106. 110, 115, 119 (° c), heat setting section: 215. 240, 238, 215; a cooling section: 160. and (4) longitudinally stretching and shaping at 40 (DEG C) to obtain the high-temperature heat-seal polyester film.
Example 2: 25kg of terephthalic acid, 13.7kg of ethylene glycol, 3.3kg of isophthalic acid, 2kg of neopentyl glycol, 1.4kg of 1, 4-cyclohexanedimethanol, TMP15ml and 20g of catalyst were added to a slurry preparation device, and the subsequent esterification reaction and polycondensation reaction conditions were the same as in example 1.
Example 3: 41.6kg of terephthalic acid, 20kg of ethylene glycol, 8.3kg of isophthalic acid, 7.3kg of neopentyl glycol, 4.3kg of 1, 4-cyclohexanedimethanol, TMP15ml and 20g of catalyst were added to a slurry preparation device, and the subsequent esterification reaction and polycondensation reaction conditions were the same as in example 1.
Comparative example 1: 36.2kg of terephthalic acid, 20.7kg of ethylene glycol, 3.4kg of isophthalic acid, 13g of a catalyst and TMP10ml were added to a slurry preparation vessel, and stirred uniformly, and the conditions of the subsequent esterification reaction and the polycondensation reaction were the same as in example 1.
Comparative example 2: 39.6kg of terephthalic acid, 16.57kg of ethylene glycol, 6.9kg of neopentyl glycol, 20g of a catalyst and TMP15ml were added to a slurry preparation vessel, and stirred uniformly, and the conditions of the subsequent esterification reaction and the polycondensation reaction were the same as in example 1.
Comparative example 3: 33.7kg of terephthalic acid, 17.4kg of ethylene glycol, 5.9kg of isophthalic acid, 5.6kg of neopentyl glycol, 20g of a catalyst and TMP20ml were added to a slurry preparation vessel, and stirred uniformly, and the conditions for the subsequent esterification reaction and the polycondensation reaction were the same as in example 1.
TABLE 1 physical Properties of polyester chips in the present application
TABLE 2 physical Properties of the heat-sealable polyester film produced in example 1 of the present application
As can be seen from tables 1 and 2, the polyester chip provided by the present application belongs to a semi-crystalline polyester raw material, has a high unsealing temperature, and is suitable for use in high temperature environments such as microwave ovens, cooking and the like.
Claims (3)
1. The modified polyester for high-temperature heat-sealing polyester film is characterized by comprising the following components in parts by weight: the ethylene glycol terephthalate is polymerized with terephthalic acid, ethylene glycol, isophthalic acid, neopentyl glycol and 1, 4-cyclohexanedimethanol, wherein the molar ratio of the terephthalic acid to the ethylene glycol to the isophthalic acid to the neopentyl glycol to the 1, 4-cyclohexanedimethanol is 15-25: 22-32: 2-5: 2-7: 1-3.
2. The production method of the modified polyester for the high-temperature heat-sealing polyester film is characterized by comprising the following steps of: the method comprises the following steps:
uniformly stirring terephthalic acid, ethylene glycol, isophthalic acid, neopentyl glycol and 1, 4-cyclohexanedimethanol according to a ratio, controlling the temperature of an esterification kettle to be 250-270 ℃, and adding a blue reagent to perform esterification reaction;
feeding the materials after the esterification reaction into a polycondensation kettle, heating to 255-265 ℃, starting to vacuumize the polycondensation kettle, carrying out vacuum polycondensation reaction at 270-290 ℃, carrying out vacuum polycondensation reaction under the stirring condition, wherein the initial stirring condition is 50HZ and 0.6KW, when reaching 2.1KW, reducing the 50HZ to 35HZ for continuous stirring, when reaching 2.0KW, reducing the 35HZ to 25HZ for continuous stirring, and when reaching 1.8KW, stopping stirring;
and (3) raising the pressure of the polycondensation kettle to 0.2MPa by using nitrogen, opening a discharge valve to discharge, and performing water cooling, grain cutting and drying to obtain polymer slices.
3. The production method of the heat-seal polyester film is characterized by comprising the following steps: blending the modified polyester material of claim 1 with ethylene terephthalate containing silica crystals, wherein the modified polyester material accounts for more than 90%;
the three layers are co-extruded, wherein the heat sealing layer is one of the outer layers, the thickness of the heat sealing layer is 10-30 mu m, and the heat sealing layer accounts for 10-20% of the whole film;
the temperature of the chilling roller is set to be 25 ℃ for chilling;
the transverse-longitudinal stretching ratio is 3.5-4, the preheating section temperature of the longitudinal stretching machine is 60 ℃, 65 ℃, 75 ℃, the stretching section temperature is 79 ℃, 82 ℃, 30 ℃, and the cooling section temperature is 36 ℃ for longitudinal stretching;
setting the temperature of a drawing machine of a transverse drawing machine: a preheating section: 96 ℃, 102 ℃ and 104 ℃; stretching: heat setting section at 106 ℃, 110 ℃, 115 ℃ and 119 ℃: 215 ℃, 240 ℃, 238 ℃, 215 ℃; a cooling section: transversely stretching and shaping at 160 deg.C and 40 deg.C.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911374516.1A CN112646137A (en) | 2019-12-27 | 2019-12-27 | Modified polyester for high-temperature heat-sealing polyester film, production method and production method of heat-sealing polyester film |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911374516.1A CN112646137A (en) | 2019-12-27 | 2019-12-27 | Modified polyester for high-temperature heat-sealing polyester film, production method and production method of heat-sealing polyester film |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101362539A (en) * | 2008-08-30 | 2009-02-11 | 富维薄膜（山东）有限公司 | Polyester film for shrinkable cigarette pack |
| CN101367285A (en) * | 2008-08-30 | 2009-02-18 | 富维薄膜（山东）有限公司 | Polyester film and methods for making same |
| CN102964574A (en) * | 2012-12-07 | 2013-03-13 | 富维薄膜（山东）有限公司 | Modified polyester and preparation method thereof |
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- 2019-12-27 CN CN201911374516.1A patent/CN112646137A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101362539A (en) * | 2008-08-30 | 2009-02-11 | 富维薄膜（山东）有限公司 | Polyester film for shrinkable cigarette pack |
| CN101367285A (en) * | 2008-08-30 | 2009-02-18 | 富维薄膜（山东）有限公司 | Polyester film and methods for making same |
| CN102964574A (en) * | 2012-12-07 | 2013-03-13 | 富维薄膜（山东）有限公司 | Modified polyester and preparation method thereof |
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Application publication date: 20210413 |