CN117402421A - Temperature-resistant polyolefin material and application thereof - Google Patents
Temperature-resistant polyolefin material and application thereof Download PDFInfo
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- CN117402421A CN117402421A CN202311373146.6A CN202311373146A CN117402421A CN 117402421 A CN117402421 A CN 117402421A CN 202311373146 A CN202311373146 A CN 202311373146A CN 117402421 A CN117402421 A CN 117402421A
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- 239000000463 material Substances 0.000 title claims abstract description 60
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 57
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 52
- 229920001470 polyketone Polymers 0.000 claims abstract description 52
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 40
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 36
- 239000000155 melt Substances 0.000 claims abstract description 36
- -1 polyethylene Polymers 0.000 claims abstract description 16
- 239000004698 Polyethylene Substances 0.000 claims abstract description 12
- 229920000573 polyethylene Polymers 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 40
- 239000003963 antioxidant agent Substances 0.000 claims description 33
- 230000003078 antioxidant effect Effects 0.000 claims description 33
- 230000009477 glass transition Effects 0.000 claims description 32
- 239000000377 silicon dioxide Substances 0.000 claims description 20
- 229920001903 high density polyethylene Polymers 0.000 claims description 14
- 239000004700 high-density polyethylene Substances 0.000 claims description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims description 14
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 8
- HCILJBJJZALOAL-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n'-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]propanehydrazide Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 HCILJBJJZALOAL-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000010025 steaming Methods 0.000 abstract description 17
- 238000007789 sealing Methods 0.000 abstract description 6
- 230000001954 sterilising effect Effects 0.000 abstract description 4
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 4
- 238000001125 extrusion Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 13
- 238000005469 granulation Methods 0.000 description 12
- 230000003179 granulation Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010411 cooking Methods 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- 230000032683 aging Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 101000742062 Bos taurus Protein phosphatase 1G Proteins 0.000 description 1
- 239000004822 Hot adhesive Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920006284 nylon film Polymers 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- 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
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- 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
- C08J2473/00—Characterised by the use of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08J2459/00 - C08J2471/00; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
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Abstract
The invention discloses a temperature-resistant polyolefin material and application thereof, wherein the temperature-resistant polyolefin material comprises the following raw materials in parts by weight: 80-90 parts of polyethylene, 5-10 parts of aliphatic polyketone and 3-5 parts of ethylene-vinyl acetate copolymer, wherein the aliphatic polyketone is selected from a combination of aliphatic polyketone with a melt flow rate of not less than 60g/10min at 240 ℃ and 2.16kg and aliphatic polyketone with a melt flow rate of 2-10 g/10min at 240 ℃ and 2.16 kg; the heat-resistant polyolefin material not only maintains the steaming resistance of the heat-resistant steaming film, but also has low-temperature toughness, can meet the requirements of high-temperature steaming sterilization (121 ℃/30 min), has high heat sealing strength and hot adhesion strength, and is suitable for the production of lightweight steaming films.
Description
Technical Field
The invention belongs to the field of functional polymer materials, and particularly relates to a temperature-resistant polyolefin material and application thereof.
Background
The film is a flexible sheet with the thickness less than 0.25mm, can be used singly, can also be used for preparing a composite film by using a plurality of layers of plastic films with different materials, and is widely applied to the fields of food, medicines, chemical industry and the like, and common plastic films include polyethylene films, polypropylene films, nylon films, polyester films and the like.
Polypropylene (PP) films produced by a casting extrusion process can be classified into general CPP (abbreviated as GCPP) films, aluminized grade CPP (abbreviated as MCPP) films, retort grade CPP (abbreviated as RCPP) films, and the like according to the use. The substrate of the cooking-grade CPP film is a PP substrate, and a cooking film which can resist the medium temperature of 121 ℃ and has the cooking sterilization condition below 30 minutes is generally produced in China and is called a semi-cooking film (namely a low-temperature cooking film). The boiling-grade CPP is widely applied to the market due to the advantages of unstretched, good flatness, easy heat sealing, high transparency, low cost and the like, but along with the continuous abundance of consumption demands, the limitation of the application of the CPP is continuously revealed, on one hand, the boiling-grade CPP film has poor low temperature resistance and is easy to crack under the low temperature condition, and the boiling-resistant film made of the PP substrate cannot meet the use of the low temperature environment; on the other hand, PP substrates have low heat seal strength, poor toughness, and are prone to breaking in low temperature storage environments, and generally require the use of relatively thick PP films to make retort pouches.
The polyethylene has excellent low-temperature toughness and low heat sealing temperature, can effectively solve the technical problems of the cooking grade CPP, but the single polyethylene material cooking film has poor high temperature resistance, is difficult to meet the requirements of high-temperature cooking sterilization (121 ℃/30 min), is easy to soften and deform in high-temperature cooking, has high air permeability and has poor processing performance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the temperature-resistant polyolefin material which not only maintains the steaming resistance of the temperature-resistant steaming film, but also has low-temperature toughness, can meet the requirements of high-temperature steaming sterilization (121 ℃/30 min), has high heat sealing strength and hot adhesive strength, and is suitable for the production of lightweight steaming films.
The invention aims to provide a temperature-resistant polyolefin material which comprises the following raw materials in parts by weight: 80-90 parts of polyethylene, 5-10 parts of aliphatic polyketone and 3-5 parts of ethylene-vinyl acetate copolymer, wherein the aliphatic polyketone is selected from a combination of aliphatic polyketone with a melt flow rate of not less than 60g/10min at 240 ℃ and 2.16kg and aliphatic polyketone with a melt flow rate of 2-10 g/10min at 240 ℃ and 2.16 kg.
According to the invention, researches show that the aliphatic polyketone with a specific structure is added into the temperature-resistant polyolefin material, so that the flexibility, low-temperature toughness and impact resistance of the temperature-resistant polyolefin material can be effectively improved; meanwhile, the aliphatic polyketone is a high-crystallinity polymer, has good permeation barrier property, can prevent oxygen permeation, reduces oxygen diffusion into the temperature-resistant polyolefin material, and has good chemical resistance and high temperature resistance, and polyethylene has certain compatibility, so that the thermal-oxidative aging resistance of the composition can be obviously improved. And the addition of the ethylene-vinyl acetate copolymer can enhance the heat sealing strength and the hot adhesion strength of the temperature-resistant polyolefin material.
Preferably, the weight ratio of the aliphatic polyketone with the melt flow rate of not less than 60g/10min at 240 ℃ and 2.16kg to the aliphatic polyketone with the melt flow rate of 2-10 g/10min at 240 ℃ and 2.16kg is 8-10: 1.
more preferably, the weight ratio of the aliphatic polyketone having a melt flow rate of not less than 60g/10min at 240 ℃ and 2.16kg to the aliphatic polyketone having a melt flow rate of 2 to 10g/10min at 240 ℃ and 2.16kg is 9:1.
preferably, the polyethylene comprises high density polyethylene.
Preferably, the high density polyethylene has a density of 0.94kg/m 3 The above.
Preferably, the ethylene-vinyl acetate copolymer is selected from the group consisting of ethylene-vinyl acetate copolymers having a glass transition temperature Tg of 10 to 15 ℃ or higher and ethylene-vinyl acetate copolymers having a glass transition temperature Tg of 0 to-10 ℃ or lower.
More preferably, the weight ratio of the ethylene-vinyl acetate copolymer with the glass transition temperature Tg of more than 10-15 ℃ to the ethylene-vinyl acetate copolymer with the glass transition temperature Tg of less than 0-minus 10 ℃ is 5-8: 1.
more preferably, the weight ratio of the ethylene-vinyl acetate copolymer with the glass transition temperature Tg of more than 10-15 ℃ to the ethylene-vinyl acetate copolymer with the glass transition temperature Tg of less than 0-minus 10 ℃ is 6:1.
preferably, the temperature-resistant polyolefin material further comprises 0.5 to 2 parts by weight of dendritic silica.
Although aliphatic polyketones are effective in improving the flexibility, low-temperature toughness and impact resistance of a temperature-resistant polyolefin material, aliphatic polyketones are high crystalline polymers, and have a high crystallization rate, resulting in difficulty in obtaining transparent film products, and therefore, in the production of transparent films, in order to obtain high transparency, it is common technical means to add particulate silica as a transparency agent, but for transparent films, it is still difficult to add particulate silica to obtain a film material having sufficient transparency. The inventor finds that the addition of the dendritic silicon dioxide can effectively improve the transparency of the film prepared from the temperature-resistant polyolefin material in the experimental process. Meanwhile, as the carbonyl groups which are regularly arranged on the main chain of the aliphatic polyketone are photodegradable chromophore groups, the main chain of the aliphatic polyketone is broken after sunlight exposure to degrade, and the degradation resistance of the aliphatic polyketone can be effectively improved by adding the dendritic silicon dioxide.
Preferably, the temperature-resistant polyolefin material further comprises 1 to 2.5 parts by weight of an antioxidant, wherein the antioxidant is selected from the group consisting of an antioxidant 1024, an antioxidant 1010 and an antioxidant 3114.
The aliphatic polyketone has low thermal stability, and is easy to degrade under the action of high shear, so that the mechanical property of the temperature-resistant polyolefin material is reduced, and the combination of the antioxidant 1024, the antioxidant 1010 and the antioxidant 3114 can effectively improve the heat aging resistance of the temperature-resistant polyolefin material.
More preferably, the weight ratio of the antioxidant 1024, the antioxidant 1010 and the antioxidant 3114 is 1:4 to 6:2 to 3.
More preferably, the weight ratio of the antioxidant 1024, the antioxidant 1010 and the antioxidant 3114 is 1:5:2.5.
the invention also aims at providing a preparation method of the temperature-resistant polyolefin material, which comprises the following steps:
mixing polyethylene, aliphatic polyketone, ethylene-vinyl acetate copolymer, optional dendritic silicon dioxide and optional antioxidant, extruding and granulating to obtain the temperature-resistant polyolefin material.
Preferably, the extrusion granulation filter screen is 300-500 meshes.
Preferably, the extrusion granulation screen is 500 mesh.
Preferably, the mixing takes 5 to 10 minutes.
More preferably, the mixing is for 8 minutes.
Preferably, the extrusion temperature is 160-230 ℃.
More preferably, the temperature of the extrusion is 200 ℃.
The invention also aims to provide a temperature-resistant steaming film which is prepared from the temperature-resistant polyolefin material.
Detailed Description
In order to better understand the technical solutions of the present invention, the following description will clearly and completely describe the technical solutions of the embodiments of the present invention in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
An aliphatic polyketone having a melt flow rate of 2 to 10g/10min at 240℃and 2.16kg is a copolymer of ethylene, propylene and a carbon oxide manufactured by the company Xiaozhike M630A.
An aliphatic polyketone having a melt flow rate of 60g/10min at 240℃and 2.16kg was a copolymer of ethylene, propylene and carbon oxide manufactured by the company Xiaozhike, which was designated as Xiaozhike M330A.
Example 1: and (3) preparing the temperature-resistant polyolefin material.
The density is 0.940-0.970 g/cm 3 80 parts by weight of a high-density polyethylene, 9 parts by weight of an aliphatic polyketone having a melt flow rate of 60g/10min at 240 ℃ and 2.16kg, 1 part by weight of an aliphatic polyketone having a melt flow rate of 2 to 10g/10min at 240 ℃ and 2.16kg, and a glass transition temperature Tg of 10 to 15 ℃ to4.3 parts by weight of the ethylene-vinyl acetate copolymer, 0.7 part by weight of the ethylene-vinyl acetate copolymer with the glass transition temperature Tg below 0 to minus 10 ℃,2 parts by weight of dendritic silicon dioxide, 10240.3 parts by weight of antioxidant, 1010.5 parts by weight of antioxidant and 3114.7 parts by weight are mixed for 8 minutes, extruded and granulated at 200 ℃, and a filter screen for extrusion and granulation is 500 meshes, so that the temperature-resistant polyolefin material is obtained.
Example 2: and (3) preparing the temperature-resistant polyolefin material.
The density is 0.940-0.970 g/cm 3 90 parts by weight of high-density polyethylene, 4.5 parts by weight of aliphatic polyketone with a melt flow rate of 60g/10min at 240 ℃ and 2.16kg, 0.5 part by weight of aliphatic polyketone with a melt flow rate of 2-10 g/10min at 240 ℃ and 2.16kg, 2.6 parts by weight of ethylene-vinyl acetate copolymer with a glass transition temperature Tg of more than 10-15 ℃, 0.4 part by weight of ethylene-vinyl acetate copolymer with a glass transition temperature Tg of less than 0-10 ℃, 0.5 part by weight of dendritic silica, 1024.1 parts by weight of antioxidant, 0.6 part by weight of antioxidant 1010 and 0.3 part by weight of antioxidant 3114 are mixed for 8 minutes, extruded and pelletized at 200 ℃, and the extruded and pelletized filter screen is 500 meshes, thereby obtaining the temperature-resistant polyolefin material.
Example 3: and (3) preparing the temperature-resistant polyolefin material.
The density is 0.940-0.970 g/cm 3 The high-density polyethylene 85 weight portions, aliphatic polyketone 7.2 weight portions with a melt flow rate of 60g/10min at 240 ℃ and 2.16kg, aliphatic polyketone 0.8 weight portions with a melt flow rate of 2-10 g/10min at 240 ℃ and 2.16kg, ethylene-vinyl acetate copolymer 3.4 weight portions with a glass transition temperature Tg of more than 10-15 ℃, ethylene-vinyl acetate copolymer 0.6 weight portions with a glass transition temperature Tg of less than 0-10 ℃, dendritic silicon dioxide 1 weight portions, antioxidant 10240.2 weight portions, antioxidant 1010.9 weight portions and antioxidant 3114.4 weight portions are mixed for 8 minutes, extruded and granulated at 200 ℃, and a filter screen for extrusion and granulation is 500 meshes, so that the temperature-resistant polyolefin material is obtained.
Example 4: and (3) preparing the temperature-resistant polyolefin material.
The density is 0.940-0.970 g/cm 3 High density of (3)85 parts by weight of polyethylene, 7.2 parts by weight of aliphatic polyketone with a melt flow rate of 60g/10min at 240 ℃ and 2.16kg, 0.8 part by weight of aliphatic polyketone with a melt flow rate of 2-10 g/10min at 240 ℃ and 2.16kg, 4 parts by weight of ethylene-vinyl acetate copolymer with a glass transition temperature Tg of more than 10-15 ℃, 1 part by weight of dendritic silicon dioxide, 1024.2 parts by weight of antioxidant, 0.9 part by weight of antioxidant 1010 and 0.4 part by weight of antioxidant 3114 are mixed for 8 minutes, extruded and granulated at 200 ℃, and a filter screen for extrusion and granulation is 500 meshes, so that the temperature-resistant polyolefin material is obtained.
Example 5: and (3) preparing the temperature-resistant polyolefin material.
The density is 0.940-0.970 g/cm 3 85 parts by weight of high-density polyethylene, 7.2 parts by weight of aliphatic polyketone with a melt flow rate of 60g/10min at 240 ℃ and 2.16kg, 0.8 part by weight of aliphatic polyketone with a melt flow rate of 2-10 g/10min at 240 ℃ and 2.16kg, 4 parts by weight of ethylene-vinyl acetate copolymer with a glass transition temperature Tg of less than 0-minus 10 ℃, 1 part by weight of dendritic silicon dioxide, 1024.2 parts by weight of antioxidant, 1010.9 parts by weight of antioxidant and 3114.4 parts by weight of antioxidant are mixed for 8 minutes, extruded and granulated at 200 ℃, and a filter screen for extrusion and granulation is 500 meshes, thereby obtaining the temperature-resistant polyolefin material.
Comparative example 1: and (3) preparing the temperature-resistant polyolefin material.
The density is 0.940-0.970 g/cm 3 85 parts by weight of high-density polyethylene, 8 parts by weight of aliphatic polyketone with a melt flow rate of 60g/10min at 240 ℃ and 2.16kg, 3.4 parts by weight of ethylene-vinyl acetate copolymer with a glass transition temperature Tg of more than 10-15 ℃, 0.6 part by weight of ethylene-vinyl acetate copolymer with a glass transition temperature Tg of less than 0-10 ℃, 1 part by weight of dendritic silicon dioxide, 10240.2 parts by weight of antioxidant, 1010.9 parts by weight of antioxidant and 3114.4 parts by weight, mixing for 8 minutes, extruding and granulating at 200 ℃, and extruding and granulating a filter screen of 500 meshes to obtain the temperature-resistant polyolefin material.
Comparative example 2: and (3) preparing the temperature-resistant polyolefin material.
The density is 0.940-0.970 g/cm 3 85 parts by weight of a high-density polyethylene at 240℃,8 parts of aliphatic polyketone with a melt flow rate of 2-10 g/10min under 2.16kg, 3.4 parts of ethylene-vinyl acetate copolymer with a glass transition temperature Tg of more than 10-15 ℃, 0.6 part of ethylene-vinyl acetate copolymer with a glass transition temperature Tg of less than 0-10 ℃, 1 part of dendritic silicon dioxide, 10240.2 parts of antioxidant, 1010.9 parts of antioxidant and 3114.4 parts of antioxidant are mixed for 8 minutes, extruded and granulated at 200 ℃, and a filter screen for extrusion and granulation is 500 meshes, so that the temperature-resistant polyolefin material is obtained.
Comparative example 3: and (3) preparing the temperature-resistant polyolefin material.
The density is 0.940-0.970 g/cm 3 The high-density polyethylene 85 weight portions, aliphatic polyketone 7.2 weight portions with a melt flow rate of 60g/10min at 240 ℃ and 2.16kg, aliphatic polyketone 0.8 weight portions with a melt flow rate of 2-10 g/10min at 240 ℃ and 2.16kg, ethylene-vinyl acetate copolymer 3.4 weight portions with a glass transition temperature Tg of more than 10-15 ℃, ethylene-vinyl acetate copolymer 0.6 weight portions with a glass transition temperature Tg of less than 0-10 ℃, 1 weight portion of granular silicon dioxide, 10240.2 weight portions of antioxidant 1010.9 weight portions and 3114.4 weight portions are mixed for 8 minutes, extruded and granulated at 200 ℃, and a filter screen for extrusion and granulation is 500 meshes, thus obtaining the temperature-resistant polyolefin material.
Comparative example 4: and (3) preparing the temperature-resistant polyolefin material.
The density is 0.940-0.970 g/cm 3 The high-density polyethylene 85 weight portions, aliphatic polyketone 7.2 weight portions with a melt flow rate of 60g/10min at 240 ℃ and 2.16kg, aliphatic polyketone 0.8 weight portions with a melt flow rate of 2-10 g/10min at 240 ℃ and 2.16kg, ethylene-vinyl acetate copolymer 3.4 weight portions with a glass transition temperature Tg of more than 10-15 ℃, ethylene-vinyl acetate copolymer 0.6 weight portions with a glass transition temperature Tg of less than 0-10 ℃, dendritic silicon dioxide 1 weight portions, antioxidant 10980.2 weight portions, antioxidant 1010.9 weight portions and antioxidant 3114.4 weight portions are mixed for 8 minutes, extruded and granulated at 200 ℃, and a filter screen for extrusion and granulation is 500 meshes, so that the temperature-resistant polyolefin material is obtained.
Comparative example 5: and (3) preparing the temperature-resistant polyolefin material.
The density is 0.940-0.970 g/cm 3 85 parts by weight of high-density polyethylene, 7.2 parts by weight of aliphatic polyketone with a melt flow rate of 60g/10min at 240 ℃ and 2.16kg, 0.8 part by weight of aliphatic polyketone with a melt flow rate of 2-10 g/10min at 240 ℃ and 2.16kg, 3.4 parts by weight of ethylene-vinyl acetate copolymer with a glass transition temperature Tg of more than 10-15 ℃, 0.6 part by weight of ethylene-vinyl acetate copolymer with a glass transition temperature Tg of less than 0-minus 10 ℃ and 1 part by weight of dendritic silicon dioxide and 10241.5 parts by weight are mixed for 8 minutes, extruded and granulated at 200 ℃, and a filter screen for extrusion and granulation is 500 meshes, thereby obtaining the temperature-resistant polyolefin material.
Comparative example 6: and (3) preparing the temperature-resistant polyolefin material.
The density is 0.940-0.970 g/cm 3 85 parts by weight of high-density polyethylene, 7.2 parts by weight of aliphatic polyketone with a melt flow rate of 60g/10min at 240 ℃ and 2.16kg, 0.8 part by weight of aliphatic polyketone with a melt flow rate of 2-10 g/10min at 240 ℃ and 2.16kg, 3.4 parts by weight of ethylene-vinyl acetate copolymer with a glass transition temperature Tg of more than 10-15 ℃, 0.6 part by weight of ethylene-vinyl acetate copolymer with a glass transition temperature Tg of less than 0-minus 10 ℃ and 1 part by weight of dendritic silicon dioxide and 10101.5 parts by weight are mixed for 8 minutes, extruded and granulated at 200 ℃, and a filter screen for extrusion and granulation is 500 meshes, thereby obtaining the temperature-resistant polyolefin material.
Comparative example 7: and (3) preparing the temperature-resistant polyolefin material.
The density is 0.940-0.970 g/cm 3 85 parts by weight of high-density polyethylene, 7.2 parts by weight of aliphatic polyketone with a melt flow rate of 60g/10min at 240 ℃ and 2.16kg, 0.8 part by weight of aliphatic polyketone with a melt flow rate of 2-10 g/10min at 240 ℃ and 2.16kg, 3.4 parts by weight of ethylene-vinyl acetate copolymer with a glass transition temperature Tg of more than 10-15 ℃, 0.6 part by weight of ethylene-vinyl acetate copolymer with a glass transition temperature Tg of less than 0-minus 10 ℃, 1 part by weight of dendritic silica and 31141.5 parts by weight of antioxidant are mixed for 8 minutes, extruded and granulated at 200 ℃, and a filter screen for extrusion and granulation is 500 meshes to obtain the temperature-resistant polyolefin materialAnd (5) material.
The heat-resistant polyolefin materials of examples 1 to 5 and comparative examples 1 to 7 were respectively prepared into heat-resistant retort films of examples 6 to 10 and comparative examples 8 to 14 of 50. Mu.m, and the results are shown in Table 1.
Low temperature tensile strength and low temperature elongation at break test: the film was put in a freezer at-10℃for 24 hours and then taken out, and the low temperature toughness was expressed as the performance results of low temperature tensile strength and low temperature elongation at break, as measured in accordance with GB/T1040.3-2006 measurement of Plastic tensile Properties.
Heat seal strength test: the test was performed according to QBT 2358-1998.
Hot tack strength test: the test was performed according to GB/T34445-2017.
Haze test: the test was performed with reference to GB/T2410-2008.
Thermal oxidative aging resistance test: and (3) testing by adopting a thermogravimetric analyzer under the conditions of 25-800 ℃ and the temperature rising rate of 10 ℃/min, and testing the initial degradation temperature in an air atmosphere.
Table 1. Results of the heat-resistant retort film performance test of examples 6 to 10 and comparative examples 8 to 14.
As can be seen from Table 1, the heat-resistant steaming and boiling film prepared by the invention has the advantages of good low-temperature toughness, high heat sealing strength and hot adhesion strength, high transparency, good heat-resistant and oxygen aging resistance and the like.
Preparing a temperature-resistant steaming bag: uniformly coating a double-component polyurethane composite adhesive on the surfaces of the heat-resistant steaming films of examples 6-10 respectively, compositing a PA-6 film on the heat-resistant steaming film coated with the double-component polyurethane composite adhesive, cutting after the double-component polyurethane composite adhesive is solidified, and making bags to obtain the heat-resistant steaming bags of examples 11-15 respectively.
And (3) testing the performance of the temperature-resistant steaming bag: 100 heat-resistant steaming bags of the examples 11-15 are respectively taken and placed in the same environment, the heat-resistant steaming bags of the examples 11-15 are respectively heated by taking silicone oil as a medium, the bag breaking rates at different temperatures are recorded, and the test results are shown in Table 2.
Table 2. High temperature retort pouch resistance test results.
As can be seen from Table 2, the temperature-resistant retort pouch prepared by the present invention has good high temperature-resistant retort properties.
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the above-mentioned embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made to the specific embodiments of the present invention after reading the present specification, and these modifications and variations do not depart from the scope of the invention as claimed in the pending claims.
Claims (10)
1. The heat-resistant polyolefin material is characterized by comprising the following raw materials in parts by weight: 80-90 parts of polyethylene, 5-10 parts of aliphatic polyketone and 3-5 parts of ethylene-vinyl acetate copolymer, wherein the aliphatic polyketone is selected from a combination of aliphatic polyketone with a melt flow rate of not less than 60g/10min at 240 ℃ and 2.16kg and aliphatic polyketone with a melt flow rate of 2-10 g/10min at 240 ℃ and 2.16 kg.
2. The temperature-resistant polyolefin material according to claim 1, wherein the weight ratio of the aliphatic polyketone having a melt flow rate of not less than 60g/10min at 240 ℃ and 2.16kg to the aliphatic polyketone having a melt flow rate of 2 to 10g/10min at 240 ℃ is 8 to 10:1.
3. the temperature-resistant polyolefin material of claim 1, wherein the polyethylene comprises a high density polyethylene having a density of 0.94kg/m 3 The above.
4. The temperature-resistant polyolefin material according to claim 1, wherein the ethylene-vinyl acetate copolymer is selected from the group consisting of ethylene-vinyl acetate copolymers having a glass transition temperature Tg of 10 to 15 ℃ or higher and ethylene-vinyl acetate copolymers having a glass transition temperature Tg of 0 to-10 ℃ or lower.
5. The heat-resistant polyolefin material according to claim 4, wherein the weight ratio of the ethylene-vinyl acetate copolymer having a glass transition temperature Tg of 10 to 15 ℃ or higher to the ethylene-vinyl acetate copolymer having a glass transition temperature Tg of 0 to-10 ℃ or lower is 5 to 8:1.
6. the temperature-resistant polyolefin material according to claim 1, further comprising 0.5 to 2 parts by weight of dendritic silica.
7. The temperature-resistant polyolefin material according to claim 1, further comprising 1 to 2.5 parts by weight of an antioxidant selected from the group consisting of antioxidant 1024, antioxidant 1010 and antioxidant 3114.
8. The temperature resistant polyolefin material of claim 7, wherein the antioxidant 1024, the antioxidant 1010, and the antioxidant 3114 are present in a weight ratio of 1:4 to 6:2 to 3.
9. The method for producing a temperature-resistant polyolefin material according to any one of claims 1 to 8, comprising the steps of:
mixing polyethylene, aliphatic polyketone, ethylene-vinyl acetate copolymer, optional dendritic silicon dioxide and optional antioxidant, extruding and granulating to obtain the temperature-resistant polyolefin material.
10. A temperature-resistant retort film prepared from the temperature-resistant polyolefin material according to any one of claims 1 to 8.
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