An antistatic high-density polyethylene barrel

Abstract

The present invention relates to an antistatic high-density polyethylene barrel, belonging to the technical field of antistatic polyethylene materials. The antistatic high-density polyethylene barrel comprises an outer layer, an intermediate layer, and an inner layer from the outside to the inside; the outer layer is composed of 85 to 90 parts of high-density polyethylene, 3 to 5 parts of halloysite nanotube-modified masterbatch, 2 to 4 parts of ultraviolet absorber, and 3 to 5 parts of modified antistatic agent, wherein the modified antistatic agent is prepared by mixing cinnamamide propyl trimethylammonium chloride, sodium carboxymethyl cellulose, and graphene in a mass ratio of 1:0.5 to 1:0.5 to 1; the intermediate layer is high-density polyethylene, and the inner layer is high-purity high-density polyethylene. The present invention modifies the raw material components in the outer layer, and through the synergistic effect between the various components, the prepared high-density polyethylene barrel has excellent antistatic properties.

Description

Technical Field

[0001] The invention belongs to the technical field of antistatic polyethylene materials and relates to an antistatic high-density polyethylene barrel. Background Art

[0002] The semiconductor industry requires the ability to store high-purity chemicals while maintaining their high purity. Glass containers are inconvenient to transport because they are heavy and can break if dropped. 200L plastic drums made of high-density polyethylene resin are lightweight and less prone to cracking during transport. However, high-purity chemicals used for etching and cleaning in semiconductor manufacturing, such as isopropyl alcohol and isobutyl alcohol, are prone to generating flammable gases when stored. During the transportation and storage of chemical reagents, static electricity can interact with high concentrations of isopropyl alcohol and isobutyl alcohol, potentially creating fire or explosion hazards.

[0003] In the semiconductor manufacturing process, the prevention and control of static electricity is essential. Without this, problems such as particle contamination, semiconductor damage due to electrostatic discharge, and equipment downtime can occur.

[0004] Therefore, how to eliminate the surface static hazards of various plastic products has always been a basic need of the semiconductor plastics industry. How to meet this requirement in a simple and low-cost way has a huge market.

[0005] Common methods for eliminating static electricity in plastic products include the use of conductive fillers, conductive devices, and antistatic agents. There are two methods for eliminating static electricity in plastic products using antistatic agents: external coating and internal addition. Externally coated antistatic agents contain hydrophilic and lipophilic groups. The lipophilic groups are adsorbed on the surface of the plastic, and their hydrophilic groups easily absorb trace moisture in the environment, thereby forming a conductive layer that can release surface charges. Externally coated antistatic agents are also used in some plastics with high processing temperatures, such as polycarbonate, polyethylene terephthalate, polysulfone, etc. The principle of internally adding antistatic agents is that after the product is formed, the polar groups (hydrophilic groups) of the antistatic agent are arranged toward the air side, forming a single-molecule conductive layer, which absorbs moisture in the air to form a uniform conductive layer.

[0006] However, existing antistatic plastics often have poor mechanical properties, so it is necessary to develop a new plastic container that has both good antistatic properties and good mechanical properties. Summary of the Invention

[0007] The object of the present invention is to provide an antistatic high-density polyethylene barrel which maintains good antistatic properties through the synergistic effect between various components.

[0008] The purpose of the present invention can be achieved through the following technical solutions:

[0009] An antistatic high-density polyethylene barrel, comprising an outer layer, a middle layer and an inner layer from the outside to the inside;

[0010] In parts by mass, the outer layer is composed of 85-90 parts of high-density polyethylene, 3-5 parts of halloysite nanotube-modified masterbatch, 2-4 parts of ultraviolet absorber, and 3-5 parts of modified antistatic agent. The middle layer is high-density polyethylene, and the inner layer is high-purity high-density polyethylene, wherein the model of the high-purity high-density polyethylene is Tosoh 8D01A, and the model of the high-density polyethylene is Qatar TR571.

[0011] The preparation method of the halloysite nanotube-modified masterbatch is as follows:

[0012] Halloysite nanotubes are added to anhydrous ethanol and ultrasonically treated for 0.5 h to fully disperse the halloysite nanotubes in the anhydrous ethanol. A silane coupling agent is added thereto in an amount of 3 to 5% by weight of the halloysite nanotubes. The mixture is ultrasonically reacted at 50° C. and 500 W for 2 to 4 h. The resulting dispersion is vacuum filtered and washed until the solution is neutral. The filtered solid is dried to obtain silane-treated halloysite nanotubes.

[0013] The silane-treated halloysite nanotubes and the masterbatch were fully ground and mixed in a ball mill at a rotation speed of 300 r / min for 4 h to prepare the halloysite nanotube-modified masterbatch;

[0014] The preparation method of the modified antistatic agent is as follows:

[0015] The antistatic agent cinnamamide propyl trimethyl ammonium chloride is added to deionized water at a temperature of 75 to 85° C. and stirred to dissolve. After the solution is slowly cooled to room temperature, sodium carboxymethyl cellulose is added and ultrasonically dispersed for 0.5 h. After uniform dispersion, graphene is slowly added in batches. A probe ultrasonic disperser is used to ultrasonically disperse the graphene at an ultrasonic power of 100 W for 1 to 2 h. After the graphene is uniformly dispersed, the deionized water is filtered out and dried to obtain a modified antistatic agent, wherein the solid-liquid mass ratio of cinnamamide propyl trimethyl ammonium chloride, sodium carboxymethyl cellulose, graphene, and deionized water is 1:0.5 to 1:0.5 to 1:10 to 15.

[0016] The antistatic high-density polyethylene barrel is prepared through co-extrusion and blow molding processes.

[0017] As a preferred technical solution of the present invention, the silane coupling agent is one or more of 3-aminopropyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane, and vinyltrimethoxysilane.

[0018] As a preferred technical solution of the present invention, the ultraviolet absorber is one of ultraviolet absorber UV-234 and ultraviolet absorber UV-120.

[0019] As a preferred technical solution of the present invention, in parts by mass, the outer layer is 20 parts, the middle layer is 60 parts, and the inner layer is 20 parts.

[0020] Beneficial effects of the present invention:

[0021] (1) In the present invention, the masterbatch is modified by silane-treated halloysite nanotubes, so that the masterbatch is functionalized. The halloysite nanotubes not only have good antistatic properties, but also can enhance the mechanical properties of polymer materials. Due to their high aspect ratio and excellent mechanical properties, the halloysite nanotubes can effectively improve the strength of polyethylene plastics. When the nanotubes are uniformly dispersed in the plastic matrix, they can act as a reinforcing agent to increase the load-bearing capacity and deformation resistance of the plastic. The halloysite nanotubes have high thermal stability and can significantly improve the thermal stability and heat resistance of the plastic.

[0022] (2) Cinnamamide propyl trimethylammonium chloride is a cationic surfactant and can also be used as an antistatic agent. The addition of sodium carboxymethyl cellulose has good water absorption and water retention properties, which can ensure the durability of the small molecule antistatic agent. At the same time, graphene is added. Graphene has a large specific surface area, extremely high chemical activity and thermal stability, and is highly compatible with polyethylene materials. At the same time, graphene can adhere to the surface of the antistatic agent, further improving the adhesion between the modified antistatic agent and high-density polyethylene, thereby improving the antistatic durability of the high-density polyethylene plastic barrel.

[0023] (3) The good antistatic properties of the material are ensured through the synergistic effect between the components. DETAILED DESCRIPTION

[0024] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined purpose of the invention, the specific implementation methods, structures, features and effects of the present invention are described in detail below in combination with the embodiments.

[0025] Example 1

[0026] Preparation of halloysite nanotube-modified masterbatch:

[0027] Halloysite nanotubes were ultrasonically dispersed in anhydrous ethanol for 0.5 h, 3-aminopropyltriethoxysilane (3% by weight of the halloysite nanotubes) was added thereto, and ultrasonic reaction was carried out at 50° C. and 500 W of ultrasonic power for 2 h. The resulting dispersion was vacuum filtered and washed until the solution was neutral. The filtered solid was dried to obtain silane-treated halloysite nanotubes. The silane-treated halloysite nanotubes and masterbatch at a mass ratio of 0.5:1 were fully ground and mixed in a ball mill at a speed of 300 r / min for 4 h to prepare a halloysite nanotube-modified masterbatch.

[0028] Preparation of modified antistatic agent:

[0029] The antistatic agent cinnamamide propyl trimethyl ammonium chloride was added to deionized water at a temperature of 75°C and stirred to dissolve. After the solution was slowly cooled to room temperature, sodium carboxymethyl cellulose was added and ultrasonically dispersed for 0.5 h. After uniform dispersion, graphene was slowly added in batches and ultrasonically dispersed for 1 h using a probe-type ultrasonic disperser at an ultrasonic power of 100 W. The deionized water was filtered out and dried to obtain a modified antistatic agent, wherein the solid-liquid mass ratio of cinnamamide propyl trimethyl ammonium chloride, sodium carboxymethyl cellulose, graphene, and deionized water was 1:0.5:0.5:10.

[0030] The outer layer is composed of 90 parts by mass of high-density polyethylene, 3 parts by mass of halloysite nanotube-modified masterbatch, 4 parts by mass of ultraviolet absorber UV-120, and 3 parts by mass of modified antistatic agent. 20 parts by mass of outer layer raw materials, 60 parts by mass of high-density polyethylene for the middle layer, and 20 parts by mass of high-purity high-density polyethylene for the inner layer are used to prepare an antistatic high-density polyethylene barrel through a three-layer co-extrusion and blow molding process.

[0031] Example 2

[0032] Preparation of halloysite nanotube-modified masterbatch:

[0033] Halloysite nanotubes were dispersed in anhydrous ethanol by ultrasonication for 0.5 h, γ-glycidyloxypropyltrimethoxysilane (4% by weight of the halloysite nanotubes) was added thereto, and ultrasonication was carried out at 50° C. and 500 W of ultrasonic power for 2 h. The resulting dispersion was vacuum filtered and washed until the solution was neutral. The filtered solid was dried to obtain silane-treated halloysite nanotubes. The silane-treated halloysite nanotubes and masterbatch at a mass ratio of 0.7:1 were fully ground and mixed in a ball mill at a speed of 300 r / min for 4 h to prepare a halloysite nanotube-modified masterbatch.

[0034] Preparation of modified antistatic agent:

[0035] The antistatic agent cinnamamide propyl trimethyl ammonium chloride was added to deionized water at a temperature of 75°C and stirred to dissolve. After the solution was slowly cooled to room temperature, sodium carboxymethyl cellulose was added and ultrasonically dispersed for 0.5 h. After uniform dispersion, graphene was slowly added in batches and ultrasonically dispersed for 1 h using a probe-type ultrasonic disperser at an ultrasonic power of 100 W. The deionized water was filtered out and dried to obtain a modified antistatic agent, wherein the solid-liquid mass ratio of cinnamamide propyl trimethyl ammonium chloride, sodium carboxymethyl cellulose, graphene, and deionized water was 1:0.7:0.7:12.

[0036] The outer layer is composed of 88 parts by mass of high-density polyethylene, 4 parts by mass of halloysite nanotube-modified masterbatch, 4 parts by mass of ultraviolet absorber UV-120, and 4 parts by mass of modified antistatic agent. 20 parts by mass of outer layer raw materials, 60 parts by mass of high-density polyethylene for the middle layer, and 20 parts by mass of high-purity high-density polyethylene for the inner layer are used to prepare an antistatic high-density polyethylene barrel through a three-layer co-extrusion and blow molding process.

[0037] Example 3

[0038] Preparation of halloysite nanotube-modified masterbatch:

[0039] Halloysite nanotubes were dispersed in anhydrous ethanol by ultrasonication for 0.5 h, and vinyltrimethoxysilane (5% by weight of the halloysite nanotubes) was added thereto. The mixture was ultrasonically reacted at 50° C. and 500 W for 2 h. The resulting dispersion was vacuum filtered and washed until the solution was neutral. The filtered solid was dried to obtain silane-treated halloysite nanotubes. The silane-treated halloysite nanotubes and masterbatch were fully ground and mixed in a ball mill at a speed of 300 r / min for 4 h to prepare a halloysite nanotube-modified masterbatch.

[0040] Preparation of modified antistatic agent:

[0041] The antistatic agent cinnamamide propyl trimethyl ammonium chloride was added to deionized water at a temperature of 85°C and stirred to dissolve. After the solution was slowly cooled to room temperature, sodium carboxymethyl cellulose was added and ultrasonically dispersed for 0.5 h. After uniform dispersion, graphene was slowly added in batches and ultrasonically dispersed for 1 h using a probe-type ultrasonic disperser at an ultrasonic power of 100 W. The deionized water was filtered out and dried to obtain a modified antistatic agent, wherein the solid-liquid mass ratio of cinnamamide propyl trimethyl ammonium chloride, sodium carboxymethyl cellulose, graphene and deionized water was 1:1:1:15.

[0042] The outer layer is composed of a mixture of 87 parts by mass of high-density polyethylene, 5 parts by mass of halloysite nanotube-modified masterbatch, 3 parts by mass of ultraviolet absorber UV-120, and 5 parts by mass of modified antistatic agent. 20 parts by mass of the outer layer raw material, 60 parts by mass of the middle layer high-density polyethylene, and 20 parts by mass of the inner layer high-purity high-density polyethylene are used to prepare an antistatic high-density polyethylene barrel through a three-layer co-extrusion and blow molding process.

[0043] Comparative Example 1

[0044] The difference between Comparative Example 1 and Example 1 is that halloysite nanotubes are not added to modify the masterbatch, and the other operations are the same.

[0045] The outer layer is composed of 90 parts by mass of high-density polyethylene, 3 parts by mass of masterbatch, 4 parts by mass of ultraviolet absorber UV-120, and 3 parts by mass of modified antistatic agent. 20 parts by mass of outer layer raw materials, 60 parts by mass of high-density polyethylene for the middle layer, and 20 parts by mass of high-purity high-density polyethylene for the inner layer are mixed to prepare antistatic high-density polyethylene barrels through a three-layer co-extrusion and blow molding process.

[0046] Comparative Example 2

[0047] The difference between Comparative Example 2 and Example 1 is that sodium hydroxymethyl cellulose is not added to the modified antistatic agent, and the other operations are the same.

[0048] Preparation of modified antistatic agent:

[0049] The antistatic agent cinnamamide propyl trimethyl ammonium chloride was added to deionized water at a temperature of 75°C and stirred to dissolve. After the solution was slowly cooled to room temperature, graphene was slowly added in batches after uniform dispersion. Ultrasonic dispersion was carried out for 1 hour using a probe-type ultrasonic disperser at an ultrasonic power of 100 W. The deionized water was filtered out and dried to obtain a modified antistatic agent, wherein the solid-liquid mass ratio of cinnamamide propyl trimethyl ammonium chloride, graphene, and deionized water was 1:0.5:10.

[0050] The outer layer is composed of 90 parts by mass of high-density polyethylene, 3 parts by mass of halloysite nanotube-modified masterbatch, 4 parts by mass of ultraviolet absorber UV-120, and 3 parts by mass of modified antistatic agent. 20 parts by mass of outer layer raw materials, 60 parts by mass of high-density polyethylene for the middle layer, and 20 parts by mass of high-purity high-density polyethylene for the inner layer are used to prepare an antistatic high-density polyethylene barrel through a three-layer co-extrusion and blow molding process.

[0051] Comparative Example 3

[0052] The difference between Comparative Example 3 and Example 1 is that no graphene is added to the modified antistatic agent, and the other operations are the same.

[0053] Preparation of modified antistatic agent:

[0054] The antistatic agent cinnamamide propyl trimethyl ammonium chloride was added to deionized water at a temperature of 75°C and stirred to dissolve. After the solution was slowly cooled to room temperature, sodium carboxymethyl cellulose was added and ultrasonically dispersed for 0.5 h. The deionized water was filtered out and dried to obtain a modified antistatic agent, wherein the solid-liquid mass ratio of cinnamamide propyl trimethyl ammonium chloride, sodium carboxymethyl cellulose and deionized water was 1:0.5:10.

[0055] The outer layer is composed of 90 parts by mass of high-density polyethylene, 3 parts by mass of halloysite nanotube-modified masterbatch, 4 parts by mass of ultraviolet absorber UV-120, and 3 parts by mass of modified antistatic agent. 20 parts by mass of outer layer raw materials, 60 parts by mass of high-density polyethylene for the middle layer, and 20 parts by mass of high-purity high-density polyethylene for the inner layer are used to prepare an antistatic high-density polyethylene barrel through a three-layer co-extrusion and blow molding process.

[0056] Comparative Example 4

[0057] The difference between Comparative Example 4 and Example 1 is that graphene and sodium carboxymethyl cellulose are not added to the modified antistatic agent, and the other operations are the same.

[0058] The outer layer is composed of 90 parts by mass of high-density polyethylene, 3 parts by mass of halloysite nanotube-modified masterbatch, 4 parts by mass of ultraviolet absorber UV-120, and 3 parts by mass of cinnamamide propyltrimethylammonium chloride. 20 parts by mass of the outer layer raw material, 60 parts by mass of the middle layer high-density polyethylene, and 20 parts by mass of the inner layer high-purity high-density polyethylene are used to prepare an antistatic high-density polyethylene barrel through a three-layer co-extrusion and blow molding process.

[0059] Comparative Example 5

[0060] The difference between Comparative Example 5 and Example 1 is that halloysite nanotubes, carboxymethyl cellulose and graphene are not added.

[0061] The outer layer is composed of 90 parts by mass of high-density polyethylene, 3 parts by mass of masterbatch, 4 parts by mass of ultraviolet absorber UV-120, and 3 parts by mass of cinnamamide propyltrimethylammonium chloride. 20 parts by mass of the outer layer raw material, 60 parts by mass of high-density polyethylene for the middle layer, and 20 parts by mass of high-purity high-density polyethylene for the inner layer are used to prepare an antistatic high-density polyethylene barrel through a three-layer co-extrusion and blow molding process.

[0062] The tensile strength was tested according to GB / T1040, the flexural strength was tested according to GB / T9341-2008, the thermal shrinkage was tested after treatment at 120°C for 1 hour, and the surface resistance was tested according to the method in GB / T1410-2006. 2mm thick strips were made and tested at an ambient humidity of 40%. The results are shown in the following table:

[0063]

[0064]

[0065] As shown in the table above, the antistatic high-density polyethylene plastic barrel prepared by the method of the present invention has a large tensile strength, a small reduction in flexural strength, a large reduction in surface resistance, and a low thermal shrinkage rate in the examples, indicating that it has good thermal stability and can maintain good stability even at high temperatures. According to Comparative Examples 1-5, it can be seen that the synergistic effect between different components enables the plastic barrel prepared by the present invention to have good mechanical properties and antistatic properties.

[0066] The above description is merely a preferred embodiment of the present invention and does not constitute any form of limitation to the present invention. Although the present invention has been disclosed as above in terms of a preferred embodiment, it is not intended to limit the present invention. Any person skilled in the art can, without departing from the scope of the technical solution of the present invention, make some changes or modifications to equivalent embodiments using the technical contents disclosed above. However, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. An antistatic high-density polyethylene barrel, characterized in that: The antistatic high-density polyethylene barrel comprises an outer layer, a middle layer and an inner layer from the outside to the inside; In parts by mass, the outer layer is composed of 85-90 parts of high-density polyethylene, 3-5 parts of halloysite nanotube-modified masterbatch, 2-4 parts of ultraviolet absorber, and 3-5 parts of modified antistatic agent. The middle layer is high-density polyethylene, and the inner layer is high-purity high-density polyethylene, wherein the model of the high-purity high-density polyethylene is Tosoh 8D01A, and the model of the high-density polyethylene is Qatar TR571. The preparation method of the halloysite nanotube-modified masterbatch is as follows: Halloysite nanotubes are added to anhydrous ethanol and ultrasonically treated for 0.5 h to fully disperse the halloysite nanotubes in the anhydrous ethanol. A silane coupling agent is added thereto in an amount of 3 to 5% by weight of the halloysite nanotubes. The mixture is ultrasonically reacted at 50° C. and 500 W for 2 to 4 h. The resulting dispersion is vacuum filtered and washed until the solution is neutral. The filtered solid is dried to obtain silane-treated halloysite nanotubes. The silane-treated halloysite nanotubes and the masterbatch were fully ground and mixed in a ball mill at a rotation speed of 300 r / min for 4 h to prepare the halloysite nanotube-modified masterbatch; The preparation method of the modified antistatic agent is as follows: The antistatic agent cinnamamide propyl trimethyl ammonium chloride is added to deionized water at a temperature of 75 to 85° C. and stirred to dissolve. After the solution is slowly cooled to room temperature, sodium carboxymethyl cellulose is added and ultrasonically dispersed for 0.5 h. After uniform dispersion, graphene is slowly added in batches. A probe ultrasonic disperser is used to ultrasonically disperse the graphene at an ultrasonic power of 100 W for 1 to 2 h. After the graphene is uniformly dispersed, the deionized water is filtered out and dried to obtain a modified antistatic agent, wherein the solid-liquid mass ratio of cinnamamide propyl trimethyl ammonium chloride, sodium carboxymethyl cellulose, graphene, and deionized water is 1:0.5 to 1:0.5 to 1:10 to 15. The ultraviolet absorber is one of ultraviolet absorber UV-234 and ultraviolet absorber UV-120; The antistatic high-density polyethylene barrel is prepared through a three-layer co-extrusion and blow molding process.

2. The antistatic high-density polyethylene barrel according to claim 1, characterized in that: The silane coupling agent is one or more of 3-aminopropyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane, and vinyltrimethoxysilane.

3. The antistatic high-density polyethylene barrel according to claim 1, characterized in that: In parts by mass, the outer layer accounts for 20 parts, the middle layer accounts for 60 parts, and the inner layer accounts for 20 parts.

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