Manufacturing method of alloyed high-barrier polyethylene / polyamide membrane material, product and application of alloyed high-barrier polyethylene / polyamide membrane material

Abstract

The invention discloses a manufacturing method of an alloyed high-barrier polyethylene / polyamide membrane material, a product and application, and belongs to the technical field of high-barrier membranes. The preparation method comprises the following steps: carrying out melt blending and extrusion granulation on a polyethylene / polyamide raw material mixture precursor, preheating a polyethylene / polyamide mixture master batch obtained by granulation to 180-200 DEG C, carrying out pulse type high-pressure compression molding, and cooling to obtain the alloyed high-barrier polyethylene / polyamide membrane material. According to the manufacturing method disclosed by the invention, the polyamide phase can be uniformly dispersed in the polyethylene matrix phase and is converted from a spherical dispersion state to a layered dispersion state, so that a barrier wall effect is formed in the polyethylene / polyamide membrane material, and the gas barrier property of the polyethylene / polyamide membrane material is effectively improved.

Description

Technical Field

[0001] The present application belongs to the technical field of high barrier films, and in particular relates to a method for manufacturing an alloyed high barrier polyethylene / polyamide film material, a product and an application thereof. Background Art

[0002] As one of the five general-purpose synthetic resins, polyethylene has the advantages of low price, excellent processing performance and good water vapor barrier performance, which makes it show great application value in the fields of food, medicine / chemical packaging, electrical device packaging, etc. However, polyethylene has poor barrier performance to non-polar gases, which limits the application of polyethylene film in packaging with the need for freshness and quality preservation. Therefore, it is very important to improve the gas barrier performance of polyethylene film materials.

[0003] At present, the common technical routes for improving the gas barrier performance of polyethylene film are multi-layer composite and surface coating, etc. Among them, the multi-layer composite technology is to use high barrier resin and polyethylene film to form a multi-layer structure, thereby improving the barrier performance by extending the permeation path; surface coating is to deposit metal oxide or nitride coating on the surface of polyethylene film by vapor deposition, atomic layer deposition, molecular layer deposition, layer-by-layer self-assembly or magnetron sputtering deposition, so as to block gas penetration through a dense surface coating.

[0004] However, the common technical routes have obvious deficiencies and defects in actual production. For example, the multi-layer composite technical route will increase the thickness of the polyethylene film and easily cause problems such as bubbles or cracks; while surface coating can maintain a thinner film thickness and prevent problems such as bubbles or cracks, but surface coating has high requirements on the flatness and smoothness of the polyethylene film, the substrate cost is relatively high, and it is more likely to cause problems such as warping or coating scratches / peeling during service, thereby affecting the gas barrier performance. At the same time, the amount of coating used during production is difficult to determine, and the coating process is complicated and the operability is poor. Summary of the invention

[0005] The present application discloses a manufacturing method, product and application of an alloyed high-barrier polyethylene / polyamide film material, which effectively solves the technical problems of complex preparation process, high substrate cost, difficult operation and easy scratches, warping or coating shedding in the service process of the surface coating technology route.

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

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

[0008] Providing a polyethylene / polyamide raw material mixture precursor;

[0009] Melt-blending the polyethylene / polyamide raw material mixture precursor and extruding and granulating to obtain polyethylene / polyamide mixture masterbatch;

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

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

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

[0013] 1-2 parts by weight of antioxidant; 1-3 parts by weight of lubricant; 1-5 parts by weight of compatibilizer;

[0014] The total weight of each raw material is 100 parts.

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

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

[0017] 2 parts by mass of antioxidant; 2 parts by mass of lubricant; 5 parts by mass of extender.

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

[0019] In a possible embodiment, the polyamide resin includes polyamide 6, polyamide 66, polyamide 6T, polyamide 10T, polyamide 12T, polyamide 1010 and combinations thereof.

[0020] In a possible implementation scheme, the polyethylene / polyamide raw material mixture precursor is melt blended and extruded into pellets through a twin-screw extruder, and the temperature of zone 1 of the twin-screw extruder is 50-80°C, the temperature of zone 2 is 150-200°C, and the temperature of zones 3 to 8 are all 250-280°C.

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

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

[0023] The second aspect of the present application provides an alloyed high barrier polyethylene / polyamide film material, which is made by the manufacturing method described in the present application.

[0024] The second aspect of the present application provides the use 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 the present application at least include:

[0026] The manufacturing method provided in the present application makes the polyethylene / polyamide raw material mixture precursor undergo melt blending, preheating before molding and pulse high-pressure molding in sequence, so that the polyamide phase is evenly dispersed in the polyethylene matrix phase and transformed from a spherical dispersion state to a layered dispersion state. On the one hand, it can form a "barrier wall effect" in the polyethylene / polyamide film, effectively improving the gas barrier property of the polyethylene / polyamide film; on the other hand, it can enhance the dispersion stability of the polyamide phase in the polyethylene matrix phase, effectively solving the problem of warping or coating scratches / peeling off when the surface is coated; thirdly, in the preparation process, it is only necessary to control the condition parameters to achieve the regulation of the gas barrier performance. The preparation process is simple, easy to operate and can reduce costs, which is suitable for large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following briefly introduces the drawings required for use in the description of the embodiments. Obviously, the drawings described below are only some embodiments recorded in the present application, and for ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0028] Figure 1 The oxygen permeability curve of the alloyed polyethylene / polyamide film material provided in the embodiment of the present application as a function of the polyamide resin doping amount;

[0029] Figure 2 The oxygen permeability curve of the alloyed polyethylene / polyamide film material provided in the embodiment of the present application as a function of the pulse frequency;

[0030] Figure 3 This is a curve showing the change in oxygen permeability of the alloyed polyethylene / polyamide film material as a function of molding pressure provided in an embodiment of the present application. DETAILED DESCRIPTION

[0031] The technical solutions in the embodiments of the present application will be described clearly and completely below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work 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 association relationship of associated objects, indicating that there may be three relationships. For example, A and / or B can represent: A exists alone, B exists alone, and A and B exist at the same time. Among them, 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" refers to one or more, and "plurality" refers to two or more. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of single items or plural items. For example, "at least one of A, B or C", or "at least one of A, B and C" can represent any one of A, B, C, or A+B, or A+C, or B+C, or A+B+C, where A, B, C can be single or multiple, respectively.

[0034] In the following description of this embodiment, the order of serial numbers does not mean the order of execution. Some or all of the steps can 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 the present embodiment, the numerical range should be understood to also specifically disclose each intermediate value between the upper and lower limits of the range. Any intermediate value in the stated value or stated range and any other stated value or each smaller range between the intermediate values ​​in the range are also included in the present embodiment, and the upper and lower limits of the smaller range can be independently included or excluded in the range.

[0036] Unless otherwise stated, the technical / scientific terms used in the present embodiment have the same meanings as those of ordinary skill in the art to which the application belongs. Although the present application only describes preferred methods and materials, any similar or equivalent methods and materials may also be used in the implementation or testing of the present application. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to the documents. When conflicting with any incorporated document, the content of this specification shall prevail.

[0037] In a first aspect, the present application provides a method for manufacturing an alloyed high barrier polyethylene / polyamide film material, the manufacturing method preferably comprising the following steps:

[0038] S1: providing a polyethylene / polyamide raw material mixture precursor;

[0039] S2: melt-blending the polyethylene / polyamide raw material mixture precursor and extruding and granulating to obtain a polyethylene / polyamide mixture masterbatch;

[0040] S3: preheating the polyethylene / polyamide mixture masterbatch to 180-200° C., then performing pulse high-pressure compression molding and cooling to obtain an 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, and the raw materials contained are all obtained through commercial channels; the pulse high-pressure molding refers to high-pressure molding that is cyclically reciprocated at a certain frequency.

[0042] The manufacturing method provided in the embodiment of the present application makes the polyethylene / polyamide raw material mixture precursor undergo melt blending, preheating before molding and pulse high-pressure molding in sequence, so that the polyamide phase is evenly dispersed in the polyethylene matrix phase and transformed from a spherical dispersion state to a layered dispersion state. On the one hand, it can form a "barrier wall effect" in the polyethylene / polyamide film, effectively improving the gas barrier property of the polyethylene / polyamide film; on the other hand, it can enhance the dispersion stability of the polyamide phase in the polyethylene matrix phase, effectively solving the problem of warping or coating scratches / peeling off when the surface is coated; thirdly, in the preparation process, it is only necessary to control the condition parameters to achieve the regulation of the gas barrier performance. The preparation process is simple, easy to operate and can reduce costs, and is suitable for large-scale production.

[0043] In the embodiment of the present application, the raw material composition of the polyethylene / polyamide raw material mixture precursor may illustratively include:

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

[0045] 1-2 parts by weight of antioxidant; 1-3 parts by weight of lubricant; 1-5 parts by weight of compatibilizer;

[0046] The total weight of each raw material is 100 parts.

[0047] Among them, the embodiments of the present application do not specifically limit the specific material types of the antioxidant, lubricant and compatibilizer. The antioxidants, lubricants and compatibilizers commonly used in polyethylene and polyamide composite materials can be used. For example, the antioxidant 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.; the lubricant can be polyethylene wax, ethylene bisstearamide, etc.; the compatibilizer can be maleic anhydride grafted polyethylene (PE-g-MAH), acrylic acid grafted polyethylene (PE-g-GMA), etc.

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

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

[0050] 2 parts by mass of antioxidant; 2 parts by mass of lubricant; 5 parts by mass of extender.

[0051] Among them, the embodiment of the present application selects the polyethylene / polyamide raw material mixture precursor with the above-mentioned mass ratio, so as to effectively increase the distribution ratio of the polyamide layered dispersed form in the polyethylene matrix phase, so that the "barrier wall effect" is significantly improved, thereby achieving the improvement of the gas barrier properties of the polyethylene / polyamide film.

[0052] In the embodiments of the present application, 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). In the embodiments of the present application, there is no special limitation on the molecular weight, particle size and brand of the high-density polyethylene and low-density polyethylene, and they can be common commercially available high-density polyethylene and low-density polyethylene resin particles; at the same time, when a combination of high-density polyethylene and low-density polyethylene is used, there is no special limitation on the ratio of the combination of the two in the embodiments of the present application, and those skilled in the art can reasonably select according to needs.

[0053] In the embodiment of the present application, the polyamide resin preferably includes polyamide 6, polyamide 66, polyamide 6T, polyamide 10T, polyamide 12T, polyamide 1010 and combinations thereof. For example, any one of the polyamide resins of the above grades can be used, or a combination of several of the polyamide resins of the above grades can be used. When a combination of polyamide resins of different grades is used, the embodiment of the present application does not specifically limit the amount of each polyamide resin added, and can be reasonably selected according to demand; at the same time, the embodiment of the present application does not specifically limit the particle size of the polyamide resin, and can be any common commercially available polyamide resin.

[0054] In an embodiment of the present application, the polyethylene / polyamide raw material mixture precursor is melt-blended and extruded into granules in a twin-screw extruder, and the parameter settings of the twin-screw extruder are preferably: screw speed 100-200r / min, zone 1 temperature 50-80°C, zone 2 temperature 150-200°C, and zone 3 to zone 8 temperature 250-280°C.

[0055] In the embodiment of the present application, when the pulse high pressure molding is performed, the pulse frequency is preferably 10-50 Hz, the molding pressure is preferably 50-120 MPa, and the molding time is 1-3 min. Among them, the embodiment of the present application controls the molding parameters to increase the conversion rate of the polyamide phase from the spherical dispersion state to the lamellar dispersion state in the polyethylene matrix phase, thereby preparing a polyethylene / polyamide film with excellent oxygen barrier properties.

[0056] In the embodiment of the present application, when the pulse high-pressure compression molding is performed, the pulse frequency is more preferably 20-40 Hz, the compression pressure is more preferably 100-120 MPa, and the molding time is 1-3 min. In particular, the embodiment of the present application controls the molding parameters to prepare a polyethylene / polyamide film with excellent oxygen barrier properties, while effectively reducing the performance requirements of the molding equipment in production, saving costs, and improving commercial prospects.

[0057] In the second aspect, the embodiments of the present application provide an alloyed high barrier polyethylene / polyamide film material made by the manufacturing method of the present application. Among them, based on the manufacturing method of the present application, a "barrier wall effect" can be formed in the polyethylene / polyamide film material, and the problem of warping or coating scratches / peeling caused by surface coating can be effectively avoided. Therefore, the alloyed high barrier polyethylene / polyamide film material prepared by the manufacturing method has excellent and long-lasting gas barrier performance.

[0058] In the third aspect, based on the excellent gas barrier properties of the alloyed high barrier polyethylene / polyamide film material described in the present application, the present application embodiment also provides the application of the alloyed high barrier polyethylene / polyamide film material described in the present application, specifically the application of the alloyed high barrier polyethylene / polyamide film material described in the present application for manufacturing high barrier packaging films. Among them, since the alloyed high barrier polyethylene / polyamide film material has excellent and long-lasting gas barrier properties, when used to manufacture high barrier packaging materials, it can effectively increase the shelf life and shelf life of packaged food, medicine, chemicals, etc.

[0059] The technical solution of the present application will be further described below in conjunction with specific embodiments.

[0060] Example 1

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

[0062] S11: 51 parts by mass of polyethylene resin (HDPE 5000S), 40 parts by mass of polyamide resin (PA61013B), 2 parts by mass of butylated hydroxytoluene, 2 parts by mass of polyethylene wax and 5 parts by mass of maleic anhydride grafted polyethylene were put into a high-speed mixer and mixed for 15 minutes to obtain a polyethylene / polyamide raw material mixture precursor:

[0063] S12: setting the temperature of the first zone of the twin-screw extruder to 50° C., the temperature of the second zone to 150° C., the temperature of the third to eighth zones to 260° C., and the screw speed to 200 r / min, then putting 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 placed in a high-pressure molding machine with a temperature of 180° C. and a mold design thickness of 100 μm, and preheated for 10 minutes. Then, pulse pressing is performed at a pressure of 100 MPa and a frequency of 20 Hz for 3 minutes, and the mixture is transferred to a cooling end for cooling to obtain an alloyed polyethylene / polyamide film material.

[0065] Example 2

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

[0067] S21: 71 parts by mass of polyethylene resin (HDPE 5000S), 20 parts by mass of polyamide resin (PA61013B), 2 parts by mass of butylated hydroxytoluene, 2 parts by mass of polyethylene wax and 5 parts by mass of maleic anhydride grafted polyethylene were put into a high-speed mixer and mixed for 15 minutes to obtain a polyethylene / polyamide raw material mixture precursor:

[0068] S22: setting the temperature of the first zone of the twin-screw extruder to 50° C., the temperature of the second zone to 150° C., the temperature of the third to eighth zones to 260° C., and the screw speed to 200 r / min, and then putting the polyethylene / polyamide raw material mixture precursor into the twin-screw extruder for melt blending and extrusion granulation to obtain a polyethylene / polyamide mixture masterbatch;

[0069] S23: The polyethylene / polyamide mixture masterbatch is placed in a high-pressure molding machine with a temperature of 180° C. and a mold design thickness of 100 μm, and preheated for 10 minutes. Then, pulse pressing is performed at a pressure of 100 MPa and a frequency of 20 Hz for 3 minutes, and the mixture is transferred to a cooling end for cooling to obtain an alloyed polyethylene / polyamide film material.

[0070] Example 3

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

[0072] S31: 81 parts by mass of polyethylene resin (HDPE 5000S), 10 parts by mass of polyamide resin (PA61013B), 2 parts by mass of butylated hydroxytoluene, 2 parts by mass of polyethylene wax and 5 parts by mass of maleic anhydride grafted polyethylene were put into a high-speed mixer and mixed for 15 minutes to obtain a polyethylene / polyamide raw material mixture precursor:

[0073] S32: setting the temperature of the first zone of the twin-screw extruder to 50° C., the temperature of the second zone to 150° C., the temperature of the third to eighth zones to 260° C., and the screw speed to 200 r / min, and then putting 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 placed in a high-pressure molding machine with a temperature of 180° C. and a mold design thickness of 100 μm, and preheated for 10 minutes. Then, pulse pressing is performed at a pressure of 100 MPa and a frequency of 20 Hz for 3 minutes, and the mixture is transferred to a cooling end for cooling to obtain an alloyed polyethylene / polyamide film material.

[0075] Example 4

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

[0077] S41: 51 parts by mass of polyethylene resin (HDPE 5000S), 40 parts by mass of polyamide resin (PA61013B), 2 parts by mass of butylated hydroxytoluene, 2 parts by mass of polyethylene wax and 5 parts by mass of maleic anhydride grafted polyethylene were put into a high-speed mixer and mixed for 15 minutes to obtain a polyethylene / polyamide raw material mixture precursor:

[0078] S42: setting the temperature of the first zone of the twin-screw extruder to 50° C., the temperature of the second zone to 150° C., the temperature of the third to eighth zones to 260° C., and the screw speed to 200 r / min, and then putting 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 placed in a high-pressure molding machine with a temperature of 200° C. and a mold design thickness of 100 μm, preheated for 10 minutes, and then pulse-pressed for 3 minutes at a pressure of 100 MPa and a frequency of 20 Hz. The mixture is transferred to a cooling end for cooling to obtain an alloyed polyethylene / polyamide film material.

[0080] Example 5

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

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

[0083] S52: setting the temperature of the first zone of the twin-screw extruder to 80° C., the temperature of the second zone to 200° C., the temperature of the third to eighth zones to 280° C., and the screw speed to 200 r / min, then putting 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 placed in a high-pressure molding machine with a temperature of 180° C. and a mold design thickness of 100 μm, and preheated for 10 minutes. Then, pulse pressing is performed at a pressure of 100 MPa and a frequency of 20 Hz for 3 minutes, and the mixture is transferred to a cooling end for cooling to obtain an alloyed polyethylene / polyamide film material.

[0085] Performance test case

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

[0087] 1.2 Oxygen permeability: Oxygen permeability is tested according to the method specified in the national standard GB / T 19789-2005.

[0088] According to the above test method, the gas barrier performance of the alloyed polyethylene / polyamide film materials manufactured in Examples 1-5 was tested. The test results are shown in Table 1.

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

[0090]

[0091] In order to illustrate the technical effects of various setting parameters in the manufacturing process of the embodiment of the present application, this article provides comparative examples 1-3, and uses gas barrier performance as the evaluation standard to test the technical effects of the molding parameters through single factor experiments, specifically including:

[0092] Test Example 1

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

[0094] S61: Based on 100 parts by mass of the polyethylene / polyamide raw material mixture precursor, 2 parts by mass of butylated hydroxytoluene, 2 parts by mass of polyethylene wax, 5 parts by mass of maleic anhydride grafted polyethylene and the remaining resin material are put into a high-speed mixer and mixed for 15 minutes to prepare a 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 0wt%, 5wt%, 10wt%, 20wt%, 30wt%, 40wt% and 50wt% of the weight of the polyethylene / polyamide raw material mixture precursor respectively;

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

[0096] S63: The polyethylene / polyamide mixture masterbatch is placed in a high-pressure molding machine with a temperature of 180°C and a mold design thickness of 100μm, and preheated for 10 minutes. It is then pulse-pressed at a pressure of 100MPa and a frequency of 20Hz for 3 minutes, and transferred to a cooling end for cooling to prepare alloyed polyethylene / polyamide film materials with polyurethane doping amounts of 0wt%, 5wt%, 10wt%, 20wt%, 30wt%, 40wt% and 50wt%, 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. The results are as follows: Figure 1 As shown. Among them, Figure 1 This is the curve of oxygen permeability of alloyed polyethylene / polyamide film material changing with the doping amount of polyamide resin.

[0098] according to Figure 1It can be seen that the oxygen permeability of the alloyed polyethylene / polyamide film material shows a downward trend with the increase of the doping amount of the polyurethane resin, wherein when the polyurethane doping amount is less than 10wt%, the oxygen permeability of the alloyed polyethylene / polyamide film increases slowly with the increase of the doping amount of the polyurethane resin; when the polyurethane doping amount is greater than or equal to 10wt%, the oxygen permeability of the alloyed polyethylene / polyamide film increases rapidly with the increase of the doping amount of the polyurethane resin, so the polyurethane content in the polyethylene / polyamide raw material mixture precursor is preferably 10-50wt%, but after the polyurethane doping amount reaches 40wt%, the increasing trend of the oxygen permeability of the alloyed polyethylene / polyamide film material slows down, so considering the comprehensive cost, the polyurethane content in the polyethylene / polyamide raw material mixture precursor is more preferably 10-40wt%, and most preferably 40wt%.

[0099] Test Example 2

[0100] This embodiment provides the manufacture of alloyed polyethylene / polyamide film material, which is different from embodiment 1 in that during the pulse high pressure molding process, the pulse molding frequency is set to 0 Hz, 10 Hz, 20 Hz, 30 Hz, 40 Hz and 50 Hz, respectively, in order to explore the influence of the pulse molding frequency on the oxygen barrier property of the alloyed polyethylene / polyamide film material. The specific steps include:

[0101] S71: 51 parts by mass of polyethylene resin (HDPE 5000S), 40 parts by mass of polyamide resin (PA61013B), 2 parts by mass of butylated hydroxytoluene, 2 parts by mass of polyethylene wax and 5 parts by mass of maleic anhydride grafted polyethylene were put into a high-speed mixer and mixed for 15 minutes to obtain a polyethylene / polyamide raw material mixture precursor:

[0102] S72: setting the temperature of the first zone of the twin-screw extruder to 50° C., the temperature of the second zone to 150° C., the temperature of the third to eighth zones to 260° C., and the screw speed to 200 r / min, and then putting 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 placed in a high-pressure molding machine with a temperature of 180° C. and a mold design thickness of 100 μm, and preheated for 10 minutes. Then, pulse pressing is performed at a pressure of 100 MPa and different pulse frequencies for 3 minutes, and the mixture is transferred to a 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. The results are as follows: Figure 2As shown. Among them, Figure 2 This is the curve of oxygen permeability of alloyed polyethylene / polyamide membrane material changing with pulse frequency.

[0105] according to Figure 2 It can be seen that the oxygen permeability of the alloyed polyethylene / polyamide film material shows a downward trend with the increase of the pulse molding frequency, wherein, 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 oxygen permeability of the alloyed polyethylene / polyamide film material shows a decreasing trend with the increase of the pulse molding frequency, especially 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, but when the pulse molding frequency reaches above 30 Hz, the oxygen permeability of the alloyed polyethylene / polyamide film material decreases slightly and then remains basically stable, so 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 manufacture of alloyed polyethylene / polyamide film materials, which differs from embodiment 1 in that during the pulse high-pressure molding process, the molding pressures are set to 0 MPa, 25 MPa, 50 MPa, 75 MPa, 100 MPa, 125 MPa, and 150 MPa, respectively, in order to explore the effect of the molding pressure on the oxygen barrier properties of the alloyed polyethylene / polyamide film. The specific steps include:

[0108] The specific steps include:

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

[0110] S2: setting the temperature of the first zone of the twin-screw extruder to 50° C., the temperature of the second zone to 150° C., the temperature of the third to eighth zones to 260° C., and the screw speed to 200 r / min, then putting 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 was placed in a high-pressure molding machine with a temperature of 180°C and a mold design thickness of 100 μm for preheating for 10 minutes, and then pulse-pressed for 3 minutes at different molding pressures and a frequency of 20 Hz, and then transferred to a cooling end for cooling to prepare alloyed polyethylene / polyamide film materials.

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

[0113] according to Figure 3 It can be seen that the oxygen permeability of the alloyed polyethylene / polyamide film material shows a downward trend with the increase of the molding pressure, wherein, when the molding pressure is less than 50MPa, the oxygen permeability of the alloyed polyethylene / polyamide film material decreases rapidly with the increase of the molding pressure; when the molding pressure is between 50-120MPa, the oxygen permeability of the alloyed polyethylene / polyamide film material decreases significantly with the increase of the molding pressure, so the molding pressure is preferably 50-120MPa; after the molding pressure reaches 100MPa, the oxygen barrier rate of the alloyed polyethylene / polyamide film approaches a stable state, so considering comprehensively, the molding pressure is more preferably 100-120MPa.

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

[0115] The above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit the present application. Although the present application has been described in detail with reference to the aforementioned embodiments, a person of ordinary skill in the art should understand that the technical solutions recorded in the aforementioned embodiments may still be modified, or some or all of the technical features therein may be replaced by equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the present application.

Claims

1. A method for producing an alloyed high barrier polyethylene / polyamide film material, characterized in that: The steps include: Providing a polyethylene / polyamide raw material mixture precursor; Melt-blending the polyethylene / polyamide raw material mixture precursor and extruding and granulating to obtain polyethylene / polyamide mixture masterbatch; The polyethylene / polyamide mixture masterbatch is preheated to 180-200° C., then pulse high-pressure compression molding is performed and the mixture is cooled to obtain an alloyed high-barrier polyethylene / polyamide film material.

2. The manufacturing method according to claim 1, characterized in that: The raw material composition of the polyethylene / polyamide raw material mixture precursor is: 50-85 parts by mass of polyethylene resin; 10-40 parts by mass of polyamide resin; 1-2 parts by weight of antioxidant; 1-3 parts by weight of lubricant; 1-5 parts by weight of compatibilizer; The total weight of each raw material is 100 parts.

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

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

5. The manufacturing method according to claim 2 or 3, characterized in that: The polyamide resin includes polyamide 6, polyamide 66, polyamide 6T, polyamide 10T, polyamide 12T, polyamide 1010 and combinations thereof.

6. The manufacturing method according to claim 1, characterized in that: The polyethylene / polyamide raw material mixture precursor is melt-blended and extruded into granules through a twin-screw extruder, and 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 temperature of the third to eighth zones are all 250-280°C.

7. The manufacturing method according to claim 1, characterized in that: When the pulse high-pressure compression molding is performed, the pulse frequency is 10-50 Hz, the compression pressure is 50-120 MPa, and the molding time is 1-3 min.

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

9. An alloyed high barrier polyethylene / polyamide film material, characterized in that: The method is manufactured by any one of claims 1 to 8.

10. Use of the alloyed high barrier polyethylene / polyamide film material according to claim 9 in the manufacture of high barrier packaging films.

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