A method of making, and products and uses of, an alloyed high barrier polyethylene / polyamide film material

Abstract

The application discloses a manufacturing method, product and application of an alloyed high-barrier polyethylene / polyamide film material, and belongs to the technical field of high-barrier film. The manufacturing method comprises the following steps: melt blending and extruding granulation are performed on a polyethylene / polyamide raw material mixture precursor, and then, after the polyethylene / polyamide mixture master batch obtained through the granulation is preheated to 180-200 DEG C, pulse high-pressure mold forming and cooling are performed, so that the alloyed high-barrier polyethylene / polyamide film material is obtained. The manufacturing method can make the polyamide phase uniformly dispersed in the polyethylene matrix phase and transformed from a spherical dispersion state into a lamellar dispersion state, so that a "barrier wall effect" is formed in the polyethylene / polyamide film material, and the gas barrier property of the polyethylene / polyamide film material is effectively improved.

Description

Technical Field

[0001] This application belongs to the field of high-barrier membrane technology, and specifically relates to a manufacturing method, product, and application of an alloyed high-barrier polyethylene / polyamide membrane material. Background Technology

[0002] Polyethylene, as one of the five major general-purpose synthetic resins, boasts advantages such as low price, excellent processing performance, and good water vapor barrier properties, making it highly valuable in food, pharmaceutical / chemical packaging, and electronic device encapsulation. However, polyethylene suffers from poor barrier properties against non-polar gases, thus limiting the application of polyethylene films in packaging applications requiring freshness and quality preservation. Therefore, improving the gas barrier properties of polyethylene film materials is crucial.

[0003] Currently, common technical approaches to improving the gas barrier performance of polyethylene membranes include multilayer composites and surface coatings. Multilayer composite technology utilizes high-barrier resins to create a multilayer structure with the polyethylene membrane, thereby enhancing barrier performance by extending the permeation path. Surface coatings employ techniques such as vapor deposition, atomic layer deposition, molecular layer deposition, layer-by-layer self-assembly, or magnetron sputtering deposition to deposit metal oxide or nitride coatings on the surface of the polyethylene membrane, thus creating a dense surface coating that blocks gas permeation.

[0004] However, the common technical routes mentioned above have obvious shortcomings and defects in actual production. For example, the multilayer composite technical route increases the thickness of the polyethylene film and is prone to problems such as bubbles or cracking. Surface coating can maintain a thinner film thickness and prevent bubbles or cracking, but surface coating has high requirements for the flatness and smoothness of the polyethylene film, the substrate cost is relatively high, and it is more prone to problems such as edge lifting or coating scratches / peeling during service, which affect the gas barrier performance. At the same time, the amount of coating material used during production is not easy to determine, the coating process is complicated and has poor operability. Summary of the Invention

[0005] This application discloses a manufacturing method, product, and application of alloyed high-barrier polyethylene / polyamide film material, which effectively solves the technical problems of complex preparation process, high substrate cost, difficulty in operation, and easy occurrence of scratches, curling edges, or coating peeling during service of the surface coating technology route.

[0006] To achieve the above objectives, the technical solution adopted in this application is:

[0007] The first aspect of this application provides a method for manufacturing an alloyed high-barrier polyethylene / polyamide film material, the steps of which include:

[0008] Provide polyethylene / polyamide feedstock mixture precursors;

[0009] The polyethylene / polyamide raw material mixture precursor is melt-blended and extruded into granules to obtain polyethylene / polyamide mixture masterbatch.

[0010] The polyethylene / polyamide mixture is preheated to 180-200°C, then subjected to pulsed high-pressure molding and cooled to obtain an alloyed high-barrier polyethylene / polyamide film material.

[0011] In a possible implementation, the raw material composition of the polyethylene / polyamide raw material mixture precursor is as follows:

[0012] 50-85 parts by weight of polyethylene resin; 10-40 parts by weight of polyamide resin;

[0013] Antioxidant 1-2 parts by weight; Lubricant 1-3 parts by weight; Compatibilizer 1-5 parts by weight;

[0014] The total mass of all raw materials is 100 parts.

[0015] In a possible implementation, the raw material composition of the polyethylene / polyamide raw material mixture precursor is as follows:

[0016] 51 parts by weight of polyethylene resin; 40 parts by weight of polyamide resin;

[0017] Antioxidant 2 parts by weight; Lubricant 2 parts by weight; Compatibilizer 5 parts by weight.

[0018] In a possible implementation, the polyethylene resin is high-density polyethylene and / or low-density polyethylene.

[0019] In possible implementations, the polyamide resin comprises polyamide 6, polyamide 66, polyamide 6T, polyamide 10T, polyamide 12T, polyamide 1010, and combinations thereof.

[0020] In a possible implementation, the polyethylene / polyamide raw material mixture precursor is melt-blended and extruded into granules using a twin-screw extruder, wherein the temperature of the first zone of the twin-screw extruder is 50-80°C, the temperature of the second zone is 150-200°C, and the temperatures of the third to eighth zones are all 250-280°C.

[0021] In a possible implementation, when performing the pulsed high-pressure molding, the pulse frequency is 10-50Hz, the molding pressure is 50-120MPa, and the molding time is 1-3min.

[0022] In a possible implementation, when performing the pulsed high-pressure molding, the pulse frequency is 20-40Hz, the molding pressure is 100-120MPa, and the molding time is 1-3min.

[0023] A second aspect of this application provides an alloyed high-barrier polyethylene / polyamide film material, which is manufactured by the manufacturing method described in this application.

[0024] A second aspect of this application provides the application of the alloyed high-barrier polyethylene / polyamide film material in the manufacture of high-barrier packaging films.

[0025] Compared with the prior art, the advantages or beneficial effects of the embodiments of this application include at least the following:

[0026] The manufacturing method provided in this application involves sequentially subjecting the polyethylene / polyamide raw material mixture precursor to a molding process of melt blending, preheating before molding, and pulsed high-pressure molding. This process ensures that the polyamide phase is uniformly dispersed within the polyethylene matrix phase and transforms from a spherical dispersion to a layered dispersion. On one hand, this creates a "barrier wall effect" within the polyethylene / polyamide film, effectively improving its gas barrier properties. On the other hand, it enhances the dispersion stability of the polyamide phase within the polyethylene matrix phase, effectively solving the problem of edge lifting or coating scratches / peeling during surface coating. Thirdly, the gas barrier performance can be controlled simply by adjusting the condition parameters during the preparation process. The preparation process is simple, easy to operate, and cost-effective, making it suitable for large-scale production. Attached Figure Description

[0027] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments recorded in this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0028] Figure 1 The curve showing the variation of oxygen permeability of the alloyed polyethylene / polyamide membrane material with polyamide resin doping amount provided in the embodiments of this application;

[0029] Figure 2 The oxygen permeability of the alloyed polyethylene / polyamide membrane material provided in the embodiments of this application varies with pulse frequency.

[0030] Figure 3 The curve showing the change in oxygen permeability of the alloyed polyethylene / polyamide membrane material as a function of molding pressure, as provided in the embodiments of this application. Detailed Implementation

[0031] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of this application. All other embodiments obtained by those skilled in the art based on the embodiments of this application without creative effort are within the scope of protection of this application.

[0032] In the following description of this embodiment, the term "and / or" is used to describe the relationship between associated objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, B existing alone, and A and B existing simultaneously. Here, A and B can be singular or plural; the single symbol " / " means "or".

[0033] In the following description of this embodiment, the term "at least one" means one or more, and "more than one" means two or more. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of A, B, or C", or "at least one of A, B, and C", can mean any one of A, B, and C, or A+B, or A+C, or B+C, or A+B+C, where A, B, and C can be single or multiple.

[0034] In the following description of this embodiment, the sequence of numbers does not imply the order of execution. Some or all steps may be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of this embodiment.

[0035] In the following description of this embodiment, the numerical range should be understood to also specifically disclose each intermediate value between the upper and lower limits of the range. Any stated value or intermediate value within the stated range, as well as each smaller range between any other stated value or intermediate value within the stated range, are also included in this embodiment, and the upper and lower limits of the smaller ranges may be independently included or excluded from the range.

[0036] Unless otherwise stated, the technical / scientific terms used in this embodiment have the same meanings as commonly understood by one of ordinary skill in the art to which this application pertains. While this application describes only preferred methods and materials, any similar or equivalent methods and materials may be used in the implementation or testing of this application. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0037] In a first aspect, embodiments of this application provide a method for manufacturing an alloyed high-barrier polyethylene / polyamide film material, which preferably includes the following steps:

[0038] S1: Provides a precursor for polyethylene / polyamide raw material mixtures;

[0039] S2: The polyethylene / polyamide raw material mixture precursor is melt-blended and extruded into granules to obtain polyethylene / polyamide mixture masterbatch;

[0040] S3: Preheat the polyethylene / polyamide mixture masterbatch to 180-200℃, then perform pulse high-pressure molding and cooling to obtain alloyed high-barrier polyethylene / polyamide film material.

[0041] The polyethylene / polyamide raw material mixture precursor refers to a raw material mixture containing polyethylene and polyamide, all of which are obtained through commercial channels; the pulsed high-pressure molding refers to high-pressure molding performed in a cyclic manner at a certain frequency.

[0042] The manufacturing method provided in this application involves sequentially subjecting the polyethylene / polyamide raw material mixture precursor to a molding process of melt blending, preheating before molding, and pulsed high-pressure molding. This process ensures that the polyamide phase is uniformly dispersed within the polyethylene matrix phase and transforms from a spherical dispersion to a layered dispersion. On one hand, this creates a "barrier wall effect" within the polyethylene / polyamide film, effectively improving its gas barrier properties. On the other hand, it enhances the dispersion stability of the polyamide phase within the polyethylene matrix phase, effectively solving the problem of edge lifting or coating scratches / peeling during surface coating. Thirdly, the gas barrier performance can be controlled simply by adjusting the condition parameters during the preparation process. The preparation process is simple, easy to operate, and cost-effective, making it suitable for large-scale production.

[0043] In this embodiment of the application, the raw material composition of the polyethylene / polyamide raw material mixture precursor may include, for example, the following:

[0044] 50-85 parts by weight of polyethylene resin; 10-40 parts by weight of polyamide resin;

[0045] Antioxidant 1-2 parts by weight; Lubricant 1-3 parts by weight; Compatibilizer 1-5 parts by weight;

[0046] The total mass of all raw materials is 100 parts.

[0047] In this application, there is no special limitation on the specific types of antioxidants, lubricants, and compatibilizers mentioned. Antioxidants, lubricants, and compatibilizers commonly used in polyethylene and polyamide composites can be used. For example, antioxidants can be pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (ST-1010), tris[2,4-di-tert-butylphenyl] phosphite (ST-168), butylated hydroxytoluene (BHT), etc.; lubricants can be polyethylene wax, ethylene bis-stearamide, etc.; and compatibilizers can be maleic anhydride-grafted polyethylene (PE-g-MAH), acrylic acid-grafted polyethylene (PE-g-GMA), etc.

[0048] In this embodiment of the application, the preferred raw material composition of the polyethylene / polyamide raw material mixture precursor is:

[0049] 51 parts by weight of polyethylene resin; 40 parts by weight of polyamide resin;

[0050] Antioxidant 2 parts by weight; Lubricant 2 parts by weight; Compatibilizer 5 parts by weight.

[0051] In this embodiment, by selecting the polyethylene / polyamide raw material mixture precursor with the above-mentioned mass ratio, the distribution ratio of the polyamide layered dispersion in the polyethylene matrix phase can be effectively increased, thereby significantly enhancing the "barrier wall effect" and improving the gas barrier properties of the polyethylene / polyamide film.

[0052] In this embodiment, the polyethylene resin is preferably high-density polyethylene (HDPE) and / or low-density polyethylene (LDPE), and the low-density polyethylene can also be linear low-density polyethylene (LLDPE). This embodiment does not specifically limit the molecular weight, particle size, or grade of the high-density and low-density polyethylene; common commercially available high-density and low-density polyethylene resin granules can be used. Furthermore, when using a combination of high-density and low-density polyethylene, this embodiment does not specifically limit the ratio of the two; those skilled in the art can choose appropriately according to their needs.

[0053] In this embodiment, the polyamide resin preferably comprises polyamide 6, polyamide 66, polyamide 6T, polyamide 10T, polyamide 12T, polyamide 1010, and combinations thereof. For example, any one of the polyamide resins of these grades can be used, or a combination of several of them can be used. When using combinations of different polyamide resins, this embodiment does not have a special limitation on the amount of each polyamide resin added, and can be selected reasonably according to needs. At the same time, this embodiment does not have a special limitation on the particle size of the polyamide resin, and can use common commercially available polyamide resins of various grades.

[0054] In this embodiment, the polyethylene / polyamide raw material mixture precursor is melt-blended and extruded and granulated in a twin-screw extruder. The preferred parameter settings of the twin-screw extruder are: screw speed 100-200 r / min, zone 1 temperature 50-80℃, zone 2 temperature 150-200℃, and zone 3 to 8 temperature 250-280℃.

[0055] In this embodiment, during the pulsed high-pressure molding, the pulse frequency is preferably 10-50Hz, the molding pressure is preferably 50-120MPa, and the molding time is 1-3min. Specifically, by controlling the molding parameters, this embodiment increases the transformation rate of the polyamide phase from a spherical dispersion to a layered dispersion within the polyethylene matrix, thus preparing a polyethylene / polyamide film with excellent oxygen barrier properties.

[0056] In this embodiment, during the pulsed high-pressure molding, the pulse frequency is more preferably 20-40Hz, the molding pressure is more preferably 100-120MPa, and the molding time is 1-3min. By controlling these molding parameters, this embodiment can produce polyethylene / polyamide films with excellent oxygen barrier properties while effectively reducing the performance requirements of the molding equipment and saving costs, thus improving commercial prospects.

[0057] Secondly, embodiments of this application provide alloyed high-barrier polyethylene / polyamide film materials manufactured using the method described in this application. Because the manufacturing method of this application can form a "barrier wall effect" within the polyethylene / polyamide film material and effectively avoids problems such as edge lifting or coating scratches / peeling during surface coating, the alloyed high-barrier polyethylene / polyamide film material prepared by this manufacturing method possesses excellent and long-lasting gas barrier properties.

[0058] Thirdly, based on the excellent gas barrier properties of the alloyed high-barrier polyethylene / polyamide film material described in this application, the embodiments of this application also provide applications of the alloyed high-barrier polyethylene / polyamide film material, specifically its use in the manufacture of high-barrier packaging films. Because of the excellent and long-lasting gas barrier properties of this alloyed high-barrier polyethylene / polyamide film material, when used in the manufacture of high-barrier packaging materials, it can effectively improve the shelf life and expiration time of packaged food, medicine, and chemicals.

[0059] The technical solution of this application will be further described below with reference to specific embodiments.

[0060] Example 1

[0061] This embodiment provides a method for manufacturing an alloyed polyethylene / polyamide film material, the specific steps of which include:

[0062] S11: 51 parts by weight of polyethylene resin (HDPE 5000S), 40 parts by weight of polyamide resin (PA61013B), 2 parts by weight of dibutylhydroxytoluene, 2 parts by weight of polyethylene wax, and 5 parts by weight of maleic anhydride-grafted polyethylene are added to a high-speed mixer and mixed for 15 minutes to obtain a polyethylene / polyamide raw material mixture precursor.

[0063] S12: Set the temperature of the first zone of the twin-screw extruder to 50℃, the temperature of the second zone to 150℃, and the temperatures of the third to eighth zones to 260℃, and the screw speed to 200r / min. Then, feed the polyethylene / polyamide raw material mixture precursor into the twin-screw extruder for melt blending and extrusion granulation to obtain polyethylene / polyamide mixture masterbatch.

[0064] S13: The polyethylene / polyamide mixture masterbatch is put into a high-pressure molding machine with a temperature of 180℃ and a mold design thickness of 100μm for preheating for 10 minutes, and then pulse-pressed for 3 minutes under a pressure of 100MPa and a frequency of 20Hz to obtain alloyed polyethylene / polyamide film material.

[0065] Example 2

[0066] This embodiment provides a method for manufacturing an alloyed polyethylene / polyamide film material, the specific steps of which include:

[0067] S21: 71 parts by weight of polyethylene resin (HDPE 5000S), 20 parts by weight of polyamide resin (PA61013B), 2 parts by weight of dibutylhydroxytoluene, 2 parts by weight of polyethylene wax, and 5 parts by weight of maleic anhydride-grafted polyethylene are added to a high-speed mixer and mixed for 15 minutes to obtain a polyethylene / polyamide raw material mixture precursor.

[0068] S22: Set the temperature of the first zone of the twin-screw extruder to 50℃, the temperature of the second zone to 150℃, and the temperatures of the third to eighth zones to 260℃, and the screw speed to 200r / min. Then, feed the polyethylene / polyamide raw material mixture precursor into the twin-screw extruder for melt blending and extrusion granulation to obtain polyethylene / polyamide mixture masterbatch.

[0069] S23: The polyethylene / polyamide mixture masterbatch is put into a high-pressure molding machine with a temperature of 180℃ and a mold design thickness of 100μm for preheating for 10 minutes, and then pulse-pressed for 3 minutes under a pressure of 100MPa and a frequency of 20Hz to obtain alloyed polyethylene / polyamide film material.

[0070] Example 3

[0071] This embodiment provides a method for manufacturing an alloyed polyethylene / polyamide film material, the specific steps of which include:

[0072] S31: 81 parts by weight of polyethylene resin (HDPE 5000S), 10 parts by weight of polyamide resin (PA61013B), 2 parts by weight of dibutylhydroxytoluene, 2 parts by weight of polyethylene wax, and 5 parts by weight of maleic anhydride-grafted polyethylene are added to a high-speed mixer and mixed for 15 minutes to obtain a polyethylene / polyamide raw material mixture precursor.

[0073] S32: Set the temperature of the first zone of the twin-screw extruder to 50℃, the temperature of the second zone to 150℃, and the temperatures of the third to eighth zones to 260℃, and the screw speed to 200r / min. Then, feed the polyethylene / polyamide raw material mixture precursor into the twin-screw extruder for melt blending and extrusion granulation to obtain polyethylene / polyamide mixture masterbatch.

[0074] S33: The polyethylene / polyamide mixture masterbatch is put into a high-pressure molding machine with a temperature of 180℃ and a mold design thickness of 100μm for preheating for 10 minutes, and then pulse-pressed for 3 minutes under a pressure of 100MPa and a frequency of 20Hz to obtain alloyed polyethylene / polyamide film material.

[0075] Example 4

[0076] This embodiment provides a method for manufacturing an alloyed polyethylene / polyamide film material, the specific steps of which include:

[0077] S41: 51 parts by weight of polyethylene resin (HDPE 5000S), 40 parts by weight of polyamide resin (PA61013B), 2 parts by weight of dibutylhydroxytoluene, 2 parts by weight of polyethylene wax, and 5 parts by weight of maleic anhydride-grafted polyethylene are added to a high-speed mixer and mixed for 15 minutes to obtain a polyethylene / polyamide raw material mixture precursor.

[0078] S42: Set the temperature of the first zone of the twin-screw extruder to 50℃, the temperature of the second zone to 150℃, and the temperatures of the third to eighth zones to 260℃, and the screw speed to 200r / min. Then, feed the polyethylene / polyamide raw material mixture precursor into the twin-screw extruder for melt blending and extrusion granulation to obtain polyethylene / polyamide mixture masterbatch.

[0079] S43: The polyethylene / polyamide mixture masterbatch is put into a high-pressure molding machine with a temperature of 200℃ and a mold design thickness of 100μm for preheating for 10 minutes, and then pulse-pressed at a pressure of 100MPa and a frequency of 20Hz for 3 minutes. It is then transferred to the cooling end for cooling to obtain alloyed polyethylene / polyamide film material.

[0080] Example 5

[0081] This embodiment provides a method for manufacturing an alloyed polyethylene / polyamide film material, the specific steps of which include:

[0082] S51: 51 parts by weight of polyethylene resin (HDPE 5000S), 40 parts by weight of polyamide resin (PA61013B), 2 parts by weight of butylated hydroxytoluene, 2 parts by weight of polyethylene wax, and 5 parts by weight of maleic anhydride-grafted polyethylene are added to a high-speed mixer and mixed for 15 minutes to obtain a polyethylene / polyamide raw material mixture precursor.

[0083] S52: Set the temperature of the first zone of the twin-screw extruder to 80℃, the temperature of the second zone to 200℃, and the temperatures of the third to eighth zones to 280℃, and the screw speed to 200r / min. Then, feed the polyethylene / polyamide raw material mixture precursor into the twin-screw extruder for melt blending and extrusion granulation to obtain polyethylene / polyamide mixture masterbatch.

[0084] S53: The polyethylene / polyamide mixture masterbatch is put into a high-pressure molding machine with a temperature of 180℃ and a mold design thickness of 100μm for preheating for 10 minutes, and then pulse-pressed at a pressure of 100MPa and a frequency of 20Hz for 3 minutes. It is then transferred to the cooling end for cooling to obtain alloyed polyethylene / polyamide film material.

[0085] Performance test examples

[0086] 1.1 Water vapor permeability coefficient: The water vapor permeability was tested according to the inverted cup method specified in standard ASTM E96;

[0087] 1.2 Oxygen transmission rate: The oxygen transmission rate was tested according to the method specified in the national standard GB / T 19789-2005.

[0088] Based on the above test methods, the gas barrier properties of the alloyed polyethylene / polyamide film materials manufactured in Examples 1-5 were tested, and the test results are shown in Table 1.

[0089] Table 1: Gas barrier performance test results of alloyed polyethylene / polyamide membrane materials in the examples

[0090]

[0091] To illustrate the technical effects of the various settings parameters during the manufacturing process of the embodiments of this application, comparative examples 1-3 are provided. Using gas barrier performance as the evaluation criterion, the technical effects of the molding parameters were tested through single-factor experiments, specifically including:

[0092] Test Example 1

[0093] This test case investigated the effect of polyamide resin doping on the oxygen barrier properties of alloyed polyethylene / polyamide film materials, specifically including:

[0094] S61: Based on 100 parts by weight of the polyethylene / polyamide raw material mixture precursor, 2 parts by weight of dibutylhydroxytoluene, 2 parts by weight of polyethylene wax, 5 parts by weight of maleic anhydride-grafted polyethylene, and the remaining resin material are added to a high-speed mixer and mixed for 15 minutes to prepare the polyethylene / polyamide raw material mixture precursor. The resin material is a combination of polyethylene resin (HDPE 5000S) and polyamide resin (PA61013B), and the polyamide resin (PA61013B) accounts for 0 wt%, 5 wt%, 10 wt%, 20 wt%, 30 wt%, 40 wt%, and 50 wt% of the polyethylene / polyamide raw material mixture precursor, respectively.

[0095] S62: Set the temperature of the first zone of the twin-screw extruder to 50°C, the temperature of the second zone to 150°C, and the temperatures of the third to eighth zones to 260°C, and the screw speed to 200 r / min. Then, feed the polyethylene raw material mixture precursor into the twin-screw extruder for melt blending and extrusion granulation to obtain polyethylene / polyamide mixture masterbatch.

[0096] S63: The polyethylene / polyamide mixture masterbatch is preheated for 10 minutes in a high-pressure molding machine with a temperature of 180℃ and a mold design thickness of 100μm. Then, it is pulse-pressed for 3 minutes under a pressure of 100MPa and a frequency of 20Hz. After cooling, alloyed polyethylene / polyamide film materials with polyurethane doping amounts of 0wt%, 5wt%, 10wt%, 20wt%, 30wt%, 40wt%, and 50wt% are prepared respectively.

[0097] The oxygen barrier properties of the alloyed polyethylene / polyamide films prepared in this test example were tested according to the national standard GB / T 19789-2005, and the results were as follows: Figure 1 As shown. Among them, Figure 1 The curve showing the change in oxygen permeability of alloyed polyethylene / polyamide membrane material with polyamide resin doping amount.

[0098] according to Figure 1It is known that the oxygen permeability of alloyed polyethylene / polyamide film materials decreases with the increase of polyurethane resin doping. Specifically, when the polyurethane doping is less than 10 wt%, the oxygen permeability of alloyed polyethylene / polyamide film increases slowly with the increase of polyurethane resin doping; when the polyurethane doping is greater than or equal to 10 wt%, the oxygen permeability of alloyed polyethylene / polyamide film increases rapidly with the increase of polyurethane resin doping. Therefore, the polyurethane content in the polyethylene / polyamide raw material mixture precursor is preferably 10-50 wt%. However, after the polyurethane doping reaches 40 wt%, the increasing trend of oxygen permeability of alloyed polyethylene / polyamide film materials slows down. Therefore, considering the overall cost, the polyurethane content in the polyethylene / polyamide raw material mixture precursor is more preferably 10-40 wt%, and most preferably 40 wt%.

[0099] Test Example 2

[0100] This embodiment provides the manufacturing of alloyed polyethylene / polyamide film material. The difference from Embodiment 1 is that during the pulse high-pressure molding process, the pulse molding frequency is set to 0Hz, 10Hz, 20Hz, 30Hz, 40Hz, and 50Hz respectively, to investigate the effect of the pulse molding frequency on the oxygen barrier properties of the alloyed polyethylene / polyamide film material. Specific steps include:

[0101] S71: 51 parts by weight of polyethylene resin (HDPE 5000S), 40 parts by weight of polyamide resin (PA61013B), 2 parts by weight of dibutylhydroxytoluene, 2 parts by weight of polyethylene wax, and 5 parts by weight of maleic anhydride-grafted polyethylene are added to a high-speed mixer and mixed for 15 minutes to obtain a polyethylene / polyamide raw material mixture precursor.

[0102] S72: Set the temperature of the first zone of the twin-screw extruder to 50℃, the temperature of the second zone to 150℃, and the temperatures of the third to eighth zones to 260℃, and the screw speed to 200r / min. Then, feed the polyethylene / polyamide raw material mixture precursor into the twin-screw extruder for melt blending and extrusion granulation to obtain polyethylene / polyamide mixture masterbatch.

[0103] S73: The polyethylene / polyamide mixture masterbatch is put into a high-pressure molding machine with a temperature of 180℃ and a mold design thickness of 100μm for preheating for 10 minutes, and then pulse-pressed for 3 minutes under a pressure of 100MPa and different pulse frequencies. It is then transferred to the cooling end for cooling to prepare alloyed polyethylene / polyamide films.

[0104] The oxygen barrier properties of the alloyed polyethylene / polyamide films prepared in this test example were tested according to the national standard GB / T 19789-2005, and the results were as follows: Figure 2As shown. Among them, Figure 2 The curve showing the change in oxygen permeability of alloyed polyethylene / polyamide membrane material with pulse frequency.

[0105] according to Figure 2 It is known that the oxygen permeability of the alloyed polyethylene / polyamide film material decreases with the increase of the pulse molding frequency. Specifically, when the pulse molding frequency is less than 10 Hz, the oxygen permeability of the alloyed polyethylene / polyamide film material decreases rapidly with the increase of the pulse molding frequency. When the pulse molding frequency is greater than or equal to 10 Hz, the decrease in oxygen permeability of the alloyed polyethylene / polyamide film material slows down with the increase of the pulse molding frequency. In particular, when the pulse molding frequency is in the range of 20-30 Hz, the oxygen permeability of the alloyed polyethylene / polyamide film material remains stable. However, when the pulse molding frequency reaches 30 Hz or above, the oxygen permeability of the alloyed polyethylene / polyamide film material decreases slightly and then remains basically stable. Therefore, the pulse molding frequency is preferably 10-50 Hz, more preferably 20-40 Hz, and most preferably 20 Hz.

[0106] Test Example 3

[0107] This embodiment provides the manufacturing of alloyed polyethylene / polyamide film material. The difference from Embodiment 1 is that during the pulsed high-pressure molding process, the molding pressure is set to 0 MPa, 25 MPa, 50 MPa, 75 MPa, 100 MPa, 125 MPa, and 150 MPa respectively, to investigate the effect of molding pressure on the oxygen barrier properties of the alloyed polyethylene / polyamide film. Specific steps include:

[0108] The specific steps include:

[0109] S1: 51 parts by weight of polyethylene resin, 40 parts by weight of polyamide resin, 2 parts by weight of antioxidant, 2 parts by weight of lubricant, and 5 parts by weight of compatibilizer are added to a high-speed mixer and mixed for 15 minutes to obtain a polyethylene / polyamide raw material mixture precursor.

[0110] S2: Set the temperature of the first zone of the twin-screw extruder to 50℃, the temperature of the second zone to 150℃, and the temperatures of the third to eighth zones to 260℃, and the screw speed to 200r / min. Then, feed the polyethylene / polyamide raw material mixture precursor into the twin-screw extruder for melt blending and extrusion granulation to obtain polyethylene / polyamide mixture masterbatch.

[0111] S3: The polyethylene / polyamide mixture masterbatch is put into a high-pressure molding machine with a temperature of 180℃ and a mold design thickness of 100μm for 10 minutes for preheating. Then, it is pulse-pressed for 3 minutes under different molding pressures and a frequency of 20Hz. The mixture is then transferred to a cooling end for cooling to prepare alloyed polyethylene / polyamide film materials.

[0112] The oxygen barrier properties of each alloyed polyethylene / polyamide film material prepared in this test example were tested according to the national standard GB / T 19789-2005, and the results are as follows: Figure 3 As shown. Among them, Figure 3 The curve showing the change in air permeability of alloyed polyethylene / polyamide membrane material with molding pressure.

[0113] according to Figure 3 It is known that the oxygen permeability of alloyed polyethylene / polyamide film material decreases with increasing molding pressure. Specifically, when the molding pressure is less than 50 MPa, the oxygen permeability of alloyed polyethylene / polyamide film material decreases rapidly with increasing molding pressure. When the molding pressure is between 50-120 MPa, the oxygen permeability of alloyed polyethylene / polyamide film material decreases significantly with increasing molding pressure. Therefore, the molding pressure is preferably 50-120 MPa. When the molding pressure reaches 100 MPa, the oxygen barrier properties of alloyed polyethylene / polyamide film tend to stabilize. Therefore, considering all factors, the molding pressure is more preferably 100-120 MPa.

[0114] The various embodiments in this specification are described in a progressive manner. The same or similar parts between the various embodiments can be referred to each other. Each embodiment focuses on describing the differences from other embodiments.

[0115] The above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit this application. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of this application.

Claims

1. A method for manufacturing an alloyed high-barrier polyethylene / polyamide film material, characterized in that, The steps include: A polyethylene / polyamide raw material mixture precursor is provided, wherein the raw material composition of the polyethylene / polyamide raw material mixture precursor is: 50-85 parts by weight of polyethylene resin, 10-40 parts by weight of polyamide resin, 1-2 parts by weight of antioxidant, 1-3 parts by weight of lubricant, and 1-5 parts by weight of compatibilizer, and the sum of the parts by weight of each raw material is 100 parts. The polyethylene / polyamide raw material mixture precursor is melt-blended and extruded into granules to obtain polyethylene / polyamide mixture masterbatch. The polyethylene / polyamide mixture masterbatch is preheated to 180-200℃, then subjected to pulse-type high-pressure molding and cooled to obtain alloyed high-barrier polyethylene / polyamide film material. The pulse frequency is 10-50Hz, the molding pressure is 50-120MPa, and the molding time is 1-3min.

2. The manufacturing method according to claim 1, characterized in that, The raw material composition of the polyethylene / polyamide raw material mixture precursor is as follows: 51 parts by weight of polyethylene resin; 40 parts by weight of polyamide resin; Antioxidant 2 parts by weight; lubricant 2 parts by weight; compatibilizer 5 parts by weight.

3. The manufacturing method according to claim 1 or 2, characterized in that, The polyethylene resin comprises high-density polyethylene and / or low-density polyethylene.

4. The manufacturing method according to claim 1 or 2, characterized in that, The polyamide resin includes polyamide 6, polyamide 66, polyamide 6T, polyamide 10T, polyamide 12T, polyamide 1010, and combinations thereof.

5. The manufacturing method according to claim 1, characterized in that, The polyethylene / polyamide raw material mixture precursor is melt-blended and extruded into granules using a twin-screw extruder, with the temperature of zone one of the twin-screw extruder being 50-80℃, zone two being 150-200℃, and zones three through eight being 250-280℃.

6. The manufacturing method according to claim 1, characterized in that, When performing the pulsed high-pressure molding, the pulse frequency is 20-40Hz, the molding pressure is 100-120MPa, and the molding time is 1-3min.

7. An alloyed high-barrier polyethylene / polyamide film material, characterized in that, Made by any of the manufacturing methods described in claims 1-6.

8. The application of the alloyed high-barrier polyethylene / polyamide film material according to claim 7 in the manufacture of high-barrier packaging films.

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