Production method of acid-resistant composite bag material

Abstract

The invention discloses a production method of an acid-resistant composite bag material. The composite bag material comprises a contact protection layer, an acid resistance shielding layer, a reinforcing layer and an exterior functional layer which are arranged from inside to outside. The contact protection layer is prepared from ETFE-g-MAH, fluorinated ethylene propylene, UHMWPE (Ultra High Molecular Weight Polyethylene), an ethylene-acrylic acid copolymer, organic quaternary ammonium salt modified nano montmorillonite, an antioxidant and a lubricant; the acid resistance shielding layer is prepared from polyvinylidene chloride, PA66, an ethylene-vinyl alcohol copolymer, silane coupling agent modified nano silicon dioxide, hydrotalcite and an antioxidant; the reinforcing layer is prepared from silane coupling agent modified aramid fibers, silane coupling agent modified glass fibers, epoxy resin, polyurethane, carbon nanotubes and carboxyl-terminated nitrile rubber; the exterior functional layer is prepared from polyphenylene sulfide, polyether-ether-ketone, nano zinc oxide, polyethylene glycol fatty acid ester, a sorbitol acetal compound and dilauryl thiodipropionate. The material has the advantages of layered synergistic acid resistance, high barrier, high strength, weather resistance and the like.

Description

Technical Field

[0001] The invention relates to the technical field of packaging materials, in particular to a method for producing an acid-resistant composite bag material. Background Art

[0002] A wide range of industries, including the chemical, food, and pharmaceutical industries, often require the packaging of acidic substances. However, conventional packaging materials are susceptible to corrosion, breakage, and penetration when exposed to acidic substances, leading to leakage of packaged contents. This not only results in product loss but can also pose risks to the environment and personnel safety. While acid-resistant packaging materials currently available on the market can resist acidic corrosion to a certain extent, their performance often falls short of expectations when used for long-term storage or when exposed to strong or special acidic substances. Therefore, the development of high-performance acid-resistant composite bags is of great practical significance. Summary of the Invention

[0003] In view of the above-mentioned defects of the prior art, the object of the present invention is to provide a method for producing an acid-resistant composite bag material.

[0004] To solve the above problems, the technical solution of the present invention is: a method for producing an acid-resistant composite bag material, the composite bag material comprising a contact protection layer, an acid barrier layer, a reinforcement layer, and an exterior functional layer arranged from the inside to the outside;

[0005] The contact protection layer is composed of ETFE-g-MAH, poly(perfluoroethylene propylene), UHMWPE, ethylene-acrylic acid copolymer, organic quaternary ammonium salt modified nano-montmorillonite, antioxidant, and lubricant;

[0006] The acid barrier layer is composed of polyvinylidene chloride, PA66, ethylene-vinyl alcohol copolymer, silane coupling agent modified nano-silica, hydrotalcite, and antioxidant;

[0007] The reinforcement layer is composed of silane coupling agent modified aramid fiber, silane coupling agent modified glass fiber, epoxy resin, polyurethane, carbon nanotubes, and carboxyl-terminated nitrile rubber;

[0008] The exterior functional layer is composed of polyphenylene sulfide, polyetheretherketone, nano zinc oxide, polyethylene glycol fatty acid ester, sorbitol acetal compound, and dilauryl thiodipropionate;

[0009] The production method comprises the following steps:

[0010] (1) The contact protection layer, the acid barrier layer, the reinforcement layer and the exterior functional layer are mixed separately and then sent into respective extruders for melt mixing and plasticization, and the contact protection layer, the acid barrier layer, the reinforcement layer and the exterior functional layer are extruded separately;

[0011] (2) The contact protection layer film, the acid barrier layer film, the reinforcement layer film, and the exterior functional layer are sequentially passed through a laminating machine and compounded using a polyurethane adhesive;

[0012] (3) Prepare the printing coating liquid and evenly apply the prepared printing coating liquid on the surface through a coating machine.

[0013] Furthermore, the preparation method of the printing coating liquid is as follows: acrylic resin, polyurethane resin, silane coupling agent KH-560, polyether modified polysiloxane and benzophenone are added into a high-speed disperser, and fully dispersed and mixed to prepare the printing coating liquid.

[0014] Furthermore, after coating, the composite bag material is passed through an ultraviolet curing device and cured under ultraviolet irradiation for 5 minutes to ensure that the printed coating is firmly attached.

[0015] Furthermore, the components of the contact protection layer are as follows by mass ratio: ETFE-g-MAH 37.7%, polyperfluoroethylene propylene 30%, UHMWPE 20%, ethylene-acrylic acid copolymer 10%, organic quaternary ammonium salt modified nano-montmorillonite 1.5%, antioxidant 0.5%, and lubricant 0.3%;

[0016] The components of the acid barrier layer are as follows by mass ratio: polyvinylidene chloride 45.5%, PA66 28%, ethylene-vinyl alcohol copolymer 20%, silane coupling agent modified nano-silica 4%, hydrotalcite 2%, antioxidant 0.5%;

[0017] The components of the reinforcement layer are as follows by mass ratio: 27% of silane coupling agent modified aramid fiber, 18.5% of silane coupling agent modified glass fiber, 30% of epoxy resin, 20% of polyurethane, 3% of carbon nanotubes, and 1.5% of carboxyl-terminated nitrile rubber.

[0018] The components of the exterior functional layer are as follows by mass: 57% polyphenylene sulfide, 38% polyetheretherketone, 2.5% nano zinc oxide, 1.2% polyethylene glycol fatty acid ester, 0.8% sorbitol acetal compound, and 0.5% dilauryl thiodipropionate.

[0019] The beneficial effects of the present invention are:

[0020] The synergistic effect of various fluorine-containing resins and functional additives in the contact protection layer, the efficient barrier system of the acid barrier layer, and the protection of the mechanical strengthening layer and the exterior functional layer enable the composite bag to effectively resist the erosion of various acidic substances, greatly extending the service life of the packaging;

[0021] The rational selection and matching of materials for each layer, such as the combination of high-strength fiber and high-performance resin in the reinforcement layer, gives the composite bag excellent strength, toughness, wear resistance and impact resistance, and is able to withstand various external forces during packaging, transportation and storage;

[0022] The printing coating adopts acrylic resin and polyurethane resin, combined with other additives, so that the surface of the composite bag has good printability, can meet the requirements of various printing processes, and ensure the quality and durability of the printed pattern. DETAILED DESCRIPTION

[0023] In order to more intuitively and completely understand the technical solution of the present invention, a non-limiting description of the features is now provided as follows:

[0024] A method for producing an acid-resistant composite bag material, the composite bag material comprising a contact protection layer, an acid-resistant shielding layer, a reinforcement layer, and an exterior functional layer arranged from the inside out;

[0025] The contact protection layer is composed of ETFE-g-MAH, polyperfluoroethylene propylene, UHMWPE, ethylene-acrylic acid copolymer, organic quaternary ammonium salt modified nano-montmorillonite, antioxidant, and lubricant, wherein the antioxidant is antioxidant 1010 and the lubricant is zinc stearate;

[0026] The acid barrier layer is composed of polyvinylidene chloride, PA66, ethylene-vinyl alcohol copolymer, silane coupling agent modified nano-silica, hydrotalcite, and antioxidant, wherein the antioxidant is antioxidant 168;

[0027] The reinforcement layer is composed of silane coupling agent modified aramid fiber, silane coupling agent modified glass fiber, epoxy resin, polyurethane, carbon nanotubes, and carboxyl-terminated nitrile rubber;

[0028] The exterior functional layer is composed of polyphenylene sulfide, polyetheretherketone, nano zinc oxide, polyethylene glycol fatty acid ester, sorbitol acetal compounds, and dilauryl thiodipropionate.

[0029] The preparation method of organic quaternary ammonium salt modified nano-montmorillonite is as follows: the nano-montmorillonite and the organic quaternary ammonium salt are stirred and reacted at 80° C. for 12 hours to carry out organic modification.

[0030] The preparation method of silane coupling agent modified nano-silica is as follows: nano-silica and silane coupling agent KH-570 are refluxed in an ethanol solution for 4 hours to perform surface treatment.

[0031] The preparation method of the silane coupling agent modified aramid fiber and the silane coupling agent modified glass fiber is as follows: the aramid fiber and the glass fiber are respectively immersed in an ethanol solution with the silane coupling agent KH-550 for 2 hours, and then dried.

[0032] Nano zinc oxide is surface silanized.

[0033] The production method of the acid-resistant composite bag material comprises the following steps:

[0034] (1) The contact protection layer, the acid barrier layer, the reinforcement layer and the exterior functional layer are mixed separately and then sent into respective extruders for melt mixing and plasticization, and the contact protection layer, the acid barrier layer, the reinforcement layer and the exterior functional layer are extruded separately;

[0035] (2) The contact protection layer film, the acid barrier layer film, the reinforcement layer film, and the exterior functional layer are sequentially passed through a laminating machine and compounded using a polyurethane adhesive;

[0036] (3) Prepare the printing coating liquid, and evenly apply the prepared printing coating liquid on the surface through a coating machine. After coating, pass the composite bag material through an ultraviolet curing device and cure it under ultraviolet light for 5 minutes to ensure that the printed coating is firmly attached.

[0037] The preparation method of the printing coating liquid is as follows: acrylic resin, polyurethane resin, silane coupling agent KH-560, polyether modified polysiloxane and benzophenone are added into a high-speed disperser, and fully dispersed and mixed to prepare the printing coating liquid.

[0038] The components of the contact protection layer are as follows by mass ratio: ETFE-g-MAH 37.7%, polyperfluoroethylene propylene 30%, UHMWPE 20%, ethylene-acrylic acid copolymer 10%, organic quaternary ammonium salt modified nano-montmorillonite 1.5%, antioxidant 0.5%, and lubricant 0.3%. ETFE-g-MAH is grafted with maleic anhydride (MAH) to enhance its compatibility with other components while retaining ETFE's good chemical corrosion resistance. Polyperfluoroethylene propylene has excellent chemical stability and non-stick properties, and can effectively resist the corrosion of acidic substances. UHMWPE provides high strength and wear resistance, enhancing the physical properties of the contact protection layer. Ethylene-acrylic acid copolymer facilitates the processing and molding of composite bags due to its good flexibility and heat sealing properties. After being modified with organic quaternary ammonium salts, the interlayer spacing of nano-montmorillonite is expanded to approximately 4.5nm, which can form a barrier network in the matrix and improve the barrier performance of the contact protection layer against acidic substances. Lubricants are used to improve processing fluidity, making the contact protection layer smoother during extrusion molding.

[0039] The acid barrier layer's components, by mass, are: 45.5% polyvinylidene chloride (PVDC), 28% PA66 (PA66), 20% ethylene-vinyl alcohol (EVA) copolymer (EPA), 4% silane-coupling agent-modified nano-silica (SiO2), 2% hydrotalcite (Hydrotalcite), and 0.5% antioxidant. PVDC, with its extremely low oxygen and water vapor transmission rates, serves as the core barrier component of the acid barrier layer. PA66 provides excellent mechanical strength and toughness, enhancing the overall performance of the acid barrier layer. EVA copolymer offers excellent barrier properties against gases and organic solvents, particularly acidic gases, and synergistically improves the barrier efficiency of the acid barrier layer. Nano-silica, surface-treated with a silane coupling agent, is evenly dispersed within the polymer matrix, enhancing the strength and barrier properties of the acid barrier layer. Hydrotalcite, with its unique layered structure, absorbs acids, further enhancing the layer's protection against them.

[0040] The reinforcement layer's components, by mass, are: 27% silane-coupling agent-modified aramid fiber, 18.5% silane-coupling agent-modified glass fiber, 30% epoxy resin, 20% polyurethane, 3% carbon nanotubes, and 1.5% carboxyl-terminated nitrile rubber. Silane-coupling agent treatment of the aramid and glass fibers improves their bonding with the resin matrix. Aramid fiber offers exceptional strength and modulus, while glass fiber provides excellent heat resistance and dimensional stability. Together, they significantly enhance the overall strength and rigidity of the composite bag. Epoxy resin provides high strength and excellent bonding properties, while polyurethane imparts flexibility and abrasion resistance to the reinforcement layer, making it less susceptible to breakage under significant external forces. Carbon nanotubes, evenly dispersed in the resin matrix, enhance the reinforcement layer's antistatic properties, preventing safety issues caused by static electricity accumulation. Carboxyl-terminated nitrile rubber further improves the reinforcement layer's toughness, enhancing its resistance to impact and tearing.

[0041] The exterior functional layer's components, by weight, are: 57% polyphenylene sulfide, 38% polyetheretherketone, 2.5% nano-zinc oxide, 1.2% polyethylene glycol fatty acid ester, 0.8% sorbitol acetal, and 0.5% dilauryl thiodipropionate. Polyphenylene sulfide offers excellent chemical stability, heat resistance, and flame retardancy, while polyetheretherketone provides excellent mechanical properties, abrasion resistance, and high-temperature stability. The combination of these two gives the exterior functional layer excellent overall performance, making it adaptable to a variety of harsh environmental conditions. Nano-zinc oxide not only absorbs UV rays, enhancing the exterior functional layer's weather resistance, but also possesses antibacterial and mildew-resistant properties, effectively inhibiting microbial growth on the composite bag's surface. Polyethylene glycol fatty acid ester forms a hydrophilic film on the material's surface, reducing surface resistance and preventing static electricity accumulation, which can affect the product's appearance due to dust attraction. Sorbitol acetal promotes polymer crystallization, refines grain size, and improves the exterior functional layer's transparency, rigidity, and heat distortion temperature. Dilauryl thiodipropionate forms a stable structure with polymer molecules, captures free radicals, effectively delays the oxidative aging process of the material, and extends the service life of the composite bag.

[0042] The synergistic effect of the various fluorine-containing resins and functional additives in the contact protection layer of the present invention, the efficient barrier system of the acid barrier layer, and the protection of the mechanical strengthening layer and the exterior functional layer enable the composite bag to effectively resist the erosion of various acidic substances, greatly extending the service life of the packaging;

[0043] The rational selection and matching of materials for each layer, such as the combination of high-strength fiber and high-performance resin in the reinforcement layer, gives the composite bag excellent strength, toughness, wear resistance and impact resistance, and is able to withstand various external forces during packaging, transportation and storage;

[0044] The printing coating adopts acrylic resin and polyurethane resin, combined with other additives, so that the surface of the composite bag has good printability, can meet the requirements of various printing processes, and ensure the quality and durability of the printed pattern.

Claims

1. A method for producing an acid-resistant composite bag material, characterized in that: The composite bag material includes a contact protection layer, an acid barrier layer, a reinforcement layer, and an exterior functional layer arranged from the inside to the outside; The contact protection layer is composed of ETFE-g-MAH, poly(perfluoroethylene propylene), UHMWPE, ethylene-acrylic acid copolymer, organic quaternary ammonium salt modified nano-montmorillonite, antioxidant, and lubricant; The acid barrier layer is composed of polyvinylidene chloride, PA66, ethylene-vinyl alcohol copolymer, silane coupling agent modified nano-silica, hydrotalcite, and antioxidant; The reinforcement layer is composed of silane coupling agent modified aramid fiber, silane coupling agent modified glass fiber, epoxy resin, polyurethane, carbon nanotubes, and carboxyl-terminated nitrile rubber; The exterior functional layer is composed of polyphenylene sulfide, polyetheretherketone, nano zinc oxide, polyethylene glycol fatty acid ester, sorbitol acetal compound, and dilauryl thiodipropionate; The production method comprises the following steps: (1) The contact protection layer, the acid barrier layer, the reinforcement layer and the exterior functional layer are mixed separately and then sent into respective extruders for melt mixing and plasticization, and the contact protection layer, the acid barrier layer, the reinforcement layer and the exterior functional layer are extruded separately; (2) The contact protection layer film, the acid barrier layer film, the reinforcement layer film, and the exterior functional layer are sequentially passed through a laminating machine and compounded using a polyurethane adhesive; (3) Prepare the printing coating liquid and evenly apply the prepared printing coating liquid on the surface through a coating machine.

2. The method for producing an acid-resistant composite bag material according to claim 1, characterized in that The preparation method of the printing coating liquid is as follows: acrylic resin, polyurethane resin, silane coupling agent KH-560, polyether modified polysiloxane and benzophenone are added into a high-speed disperser, and fully dispersed and mixed to prepare the printing coating liquid.

3. The method for producing an acid-resistant composite bag material according to claim 1, characterized in that: After coating, the composite bag material is passed through a UV curing device and cured under UV irradiation for 5 minutes to ensure that the printed coating is firmly attached.

4. The method for producing an acid-resistant composite bag material according to claim 1, characterized in that: The components of the contact protection layer are as follows by mass ratio: ETFE-g-MAH 37.7%, polyperfluoroethylene propylene 30%, UHMWPE 20%, ethylene-acrylic acid copolymer 10%, organic quaternary ammonium salt modified nano-montmorillonite 1.5%, antioxidant 0.5%, and lubricant 0.3%; The components of the acid barrier layer are as follows by mass ratio: polyvinylidene chloride 45.5%, PA66 28%, ethylene-vinyl alcohol copolymer 20%, silane coupling agent modified nano-silica 4%, hydrotalcite 2%, antioxidant 0.5%; The components of the reinforcement layer are as follows by mass ratio: 27% of silane coupling agent modified aramid fiber, 18.5% of silane coupling agent modified glass fiber, 30% of epoxy resin, 20% of polyurethane, 3% of carbon nanotubes, and 1.5% of carboxyl-terminated nitrile rubber. The components of the exterior functional layer are as follows by mass: 57% polyphenylene sulfide, 38% polyetheretherketone, 2.5% nano zinc oxide, 1.2% polyethylene glycol fatty acid ester, 0.8% sorbitol acetal compound, and 0.5% dilauryl thiodipropionate.