Plastic-loaded graphene copper oxide light-color and strong-color antibacterial master batch and manufacturing method thereof

Abstract

The invention relates to the technical field of plastic antibacterial additives, and particularly discloses a plastic loaded graphene copper oxide light-color-concentration antibacterial master batch and a manufacturing method thereof.The light-color-concentration antibacterial master batch is prepared from, by mass, 63.5%-81% of plastic, 3%-10% of graphene copper oxide, 15%-20% of titanium dioxide, 0.5%-1% of a KH550 coupling agent, 1%-2% of a PP or PE-g-MAH compatilizer and 0.5% of a 1010 antioxidant. According to the invention, the graphene copper oxide antibacterial agent which is originally light black is converted into the light-color antibacterial master batch, so that the limitation of color on the application of the antibacterial agent is thoroughly broken, the chroma of titanium dioxide and the formula ratio are determined, and the requirements of white and light-color plastic products are met; the graphene copper oxide antibacterial agent can be widely applied to the fields with strict requirements on colors, such as household appliance shells, food contact plastics, daily necessities and the like, and the application scene of the graphene copper oxide antibacterial agent is obviously expanded.

Description

Technical Field

[0001] This invention belongs to the field of plastic antibacterial additives technology, specifically relating to a plastic-supported graphene copper oxide light-colored concentrated antibacterial masterbatch and its manufacturing method. Background Technology

[0002] As one of the world's fastest-growing industries, the plastics industry has seen continuous expansion in both output and application scope. By 2020, global plastic production had climbed to 300 million tons. As a major global producer and consumer of plastics, my country's plastic production reached over 76.0322 million tons during the same period. Plastic products have permeated numerous fields such as home appliances, daily necessities, building materials, and medical supplies, becoming an indispensable basic material in modern industry and daily life.

[0003] As the application scenarios for plastic products continue to expand, consumers are increasingly demanding higher levels of functionality and safety. Antibacterial properties have become a key indicator for products that come into frequent contact with the human body, such as home appliances. To regulate market order and protect consumer health, the series of national standards for "Antibacterial, Sterilizing, and Purifying Functions of Household and Similar Electrical Appliances" officially came into effect in 2011. These standards set forth strict technical requirements for the antibacterial and antifungal properties and safety of home appliances, clarifying the application threshold for antibacterial plastics in the home appliance field and further promoting the research and development and industrialization of related technologies.

[0004] Currently, graphene copper oxide antibacterial agents, which are widely researched and applied, are yellowish-brown to black solid powders. Antibacterial powders formulated from these agents also appear light black. This color characteristic severely limits their application range. Light black antibacterial agents cannot be added to white or light-colored plastic products, otherwise it would significantly alter the product's appearance and disrupt the visual design requirements of white or light-colored plastic products. This makes it difficult to promote such high-performance antibacterial agents in fields with strict color requirements, such as appliance casings and food contact plastics.

[0005] Meanwhile, existing antibacterial masterbatch products generally have high selling prices. To control costs, manufacturers of antibacterial plastic products urgently hope to achieve antibacterial function by adding a low proportion of antibacterial masterbatch. However, when the addition exceeds 3%, it still significantly affects the color of white plastic products. Furthermore, graphene-copper oxide composite antibacterial agents, due to their extremely large specific surface area, are significantly more difficult to disperse in the plastic matrix than conventional powder materials. When using traditional plastic particle composite processes, nano-scale antibacterial agents are prone to agglomeration, forming visible black particles. These agglomerated particles not only damage the uniformity of the appearance of white plastic products but also lead to a decrease in the mechanical properties of the product, seriously affecting the final product quality. Summary of the Invention

[0006] The purpose of this invention is to provide a plastic-supported graphene copper oxide light-colored concentrated antibacterial masterbatch and its manufacturing method, in order to solve the problems mentioned in the background art, such as the inability to add light-black antibacterial agents to white and light-colored plastic products, the confusion caused by adding more than 3% of light-colored antibacterial masterbatch to white plastic products, and the easy agglomeration of nano-sized antibacterial agents when using traditional plastic particle composite processes, which damages the appearance uniformity and reduces the mechanical properties of white plastic products.

[0007] To achieve the above objectives, the present invention provides the following technical solution:

[0008] A light-colored, concentrated antibacterial masterbatch of copper oxide supported on plastic and its manufacturing method include the following steps:

[0009] The light-colored concentrated antibacterial masterbatch is composed of the following components by weight percentage: 63.5-81% plastic, 3-10% graphene copper oxide, 15-20% titanium dioxide, 0.5-1% KH550 coupling agent, 1-2% PP or PE-g-MAH compatibilizer, and 0.5% 1010 antioxidant.

[0010] The amount of graphene copper oxide added is greater than 3% to achieve concentrated antibacterial properties; the titanium dioxide is used to cover the dark color of graphene copper oxide, so that the masterbatch is light-colored or white.

[0011] The plastic has a particle size of 60-100 mesh, which is used to optimize the coating effect of graphene copper oxide; the antibacterial masterbatch is added to the plastic product at an addition ratio of not less than 2%, so that the graphene copper oxide content in the product is not less than 0.6%, which is used to achieve a long-term antibacterial effect with an antibacterial rate of ≥99.9%.

[0012] Preferably, the plastic is polypropylene or polyethylene, and the graphene copper oxide is an ultrafine powder with a moisture content of less than 0.1% and a particle size passing through an 800-mesh sieve after drying.

[0013] A method for manufacturing a plastic-supported graphene-copper oxide light-colored antibacterial masterbatch, characterized by comprising the following steps:

[0014] The graphene copper oxide solid was stirred and sprayed in an aqueous solvent at a pressure of 1-2 MPa; the dispersed graphene copper oxide solid was collected in a powder-solid separation dryer; after collection, it was dried at 100-120°C to remove surface water.

[0015] After removing the surface water, the graphene copper oxide powder was dried at 120°C for 4 hours in a dehumidifying desiccant chamber to remove the internal structural water, so that its water content was less than 0.1%.

[0016] The dried graphene copper oxide powder was microwaved and passed through an 800-mesh sieve to obtain ultrafine dried graphene copper oxide powder.

[0017] Grind the plastic granules into 60-100 mesh plastic powder; stir the titanium dioxide in a V-type low-speed mixer for 20 minutes to disperse it; add the ultrafine dry graphene copper oxide powder in batches and stir for 20 minutes; add the KH550 coupling agent in batches and stir for 20 minutes to fully impregnate the graphene copper oxide and titanium dioxide.

[0018] Add plastic powder, PP-g-MAH or PE-g-MAH compatibilizer, and 1010 antioxidant, and stir for 30 minutes to obtain a mixture. Extrude the mixture into granules using a twin-screw extruder with a 300-1000 mesh filter screen at the die head and the screw temperature controlled at 170-210℃ to finally obtain a plastic-supported graphene copper oxide light-colored antibacterial masterbatch.

[0019] Compared with the prior art, the beneficial effects of the present invention are:

[0020] This invention transforms the originally light black graphene copper oxide antibacterial agent into a light-colored antibacterial masterbatch, completely breaking the limitation of color on the application of this type of antibacterial agent. It determines the color and formula ratio of titanium dioxide, adapting to the needs of white and light-colored plastic products. It can be widely used in fields with strict color requirements such as household appliance shells, food contact plastics, and daily necessities, significantly expanding the application scenarios of graphene copper oxide antibacterial agent.

[0021] The antibacterial masterbatch prepared by this invention is a concentrated antibacterial masterbatch, achieving efficient dispersion and high concentration loading of the antibacterial agent. This significantly reduces the proportion of masterbatch added during production, directly reducing the cost of purchasing antibacterial masterbatch for enterprises. Even at low addition ratios, the light-colored concentrated antibacterial masterbatch of this invention maintains both the appearance purity and antibacterial properties of white plastics.

[0022] Meanwhile, this invention solves the agglomeration problem of graphene copper oxide antibacterial agents from the source by combining a pretreatment process of jet blowing, graded drying, and microwave vibration sieving. By breaking the original agglomerated structure of the antibacterial agent, removing adsorbed water on the material surface and internal structural water, and sieving through an 800-mesh sieve using microwave vibration to obtain ultrafine dried powder, the graphene copper oxide is ensured to enter the subsequent mixing process in a nanoscale dispersed state. In the melt granulation process of the twin-screw extruder, a 300-1000-mesh filter screen is set to remove individual agglomerated particles larger than 120 mesh, solving the problem of black particle formation in nano antibacterial masterbatch in traditional processes. The 60-100 mesh plastic powder provides sufficient specific surface area and interfacial contact area, allowing the antibacterial agent particles to adhere evenly to the surface of the plastic powder, greatly improving the compatibility between the two and avoiding fluctuations in antibacterial performance caused by local agglomeration of the antibacterial agent. Detailed Implementation

[0023] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0024] Example 1:

[0025] A light-colored, concentrated antibacterial masterbatch of plastic-supported graphene copper oxide, wherein the raw material components of the concentrated antibacterial masterbatch are in the following mass percentages: 81% polypropylene (PP) powder, 3% graphene copper oxide powder, 15% titanium dioxide, 0.5% KH550 coupling agent, 0.5% PP-g-MAH compatibilizer, and 0.5% 1010 antioxidant.

[0026] The manufacturing method includes the following steps:

[0027] 3.0 kg of graphene copper oxide solid aqueous solvent was stirred evenly and sprayed at a pressure of 1 MPa. The dispersed solid was collected in a powder solid separation dryer. After collection, it was placed in a drying device at 100℃ to remove surface water, and then transferred to a desiccant chamber and dried at 120℃ for 4 hours. The moisture content was measured to be 0.08% (<0.1%). Finally, it was microwave-vibrated and passed through an 800-mesh sieve to obtain ultrafine dried graphene copper oxide powder.

[0028] Add 15.0 kg of titanium dioxide to a V-type low-speed mixer (30 r / min) and stir for 20 minutes until evenly dispersed; add the pretreated graphene copper oxide powder in 3 batches and stir for 20 minutes each time to ensure that the two are evenly mixed.

[0029] Add a total of 0.5 kg of KH550 coupling agent in two batches, stirring for 20 minutes after each addition, until the coupling agent fully wets the powder without clumping; then add 81.0 kg of PP powder, 0.5 kg of PP-g-MAH compatibilizer, and 0.5 kg of 1010 antioxidant, and stir for 30 minutes to obtain a uniform mixture.

[0030] The mixture is fed into a twin-screw extruder, the screw temperature is set to 170-190℃, and a 300-mesh filter screen is installed at the die head; after extrusion, it is granulated by a pelletizer to obtain light beige antibacterial masterbatch.

[0031] Example 2:

[0032] A light-colored, concentrated antibacterial masterbatch of plastic-supported graphene copper oxide, wherein the raw material components of the concentrated antibacterial masterbatch are in the following mass percentages: 74% polyethylene powder, 6% graphene copper oxide powder, 18% titanium dioxide, 0.8% KH550 coupling agent, 1.0% PE-g-MAH compatibilizer, and 0.5% 1010 antioxidant.

[0033] The manufacturing method includes the following steps:

[0034] 6.0 kg of graphene copper oxide solid aqueous solvent was sprayed and dispersed under 1.5 MPa pressure. After collection, it was dried at 110°C to remove surface water, and then transferred to a dehumidifying desiccant chamber at 120°C for 4 hours. The moisture content was measured to be 0.06%. It was then microwaved and passed through an 800-mesh sieve for later use.

[0035] 18.0 kg of titanium dioxide was pre-mixed for 20 minutes in a V-type low-speed mixer (35 r / min); graphene copper oxide powder was added in 4 batches, and the mixture was stirred for 20 minutes each time; a total of 0.8 kg of KH550 coupling agent was added in 3 batches, and the mixture was stirred for 20 minutes each time; 74.0 kg of PE powder, 1.0 kg of PE-g-MAH compatibilizer, and 0.5 kg of 1010 antioxidant were added, and the mixture was stirred for 30 minutes until there were no lumps in the mixture.

[0036] By setting the temperature of a twin-screw extruder to 180-200℃ and installing a 500-mesh filter screen at the die head, light-colored antibacterial masterbatch is obtained after extrusion and pelletizing.

[0037] It should be understood that numerous specific implementation decisions can be made during the development of any practical implementation, such as in any engineering or design project. Such development efforts may be complex and time-consuming, but for those skilled in the art who benefit from this disclosure, the development effort will be a routine work of design, manufacturing, and production without requiring much experimentation.

[0038] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.

Claims

1. A plastic-supported graphene-copper oxide light-colored antibacterial masterbatch, characterized in that, The light-colored concentrated antibacterial masterbatch is composed of the following components by weight percentage: 63.5-81% plastic, 3-10% graphene copper oxide, 15-20% titanium dioxide, 0.5-1% KH550 coupling agent, 1-2% PP or PE-g-MAH compatibilizer, and 0.5% 1010 antioxidant. The amount of graphene copper oxide added is greater than 3% to achieve concentrated antibacterial properties; the titanium dioxide is used to cover the dark color of graphene copper oxide, so that the masterbatch is light-colored or white. The plastic has a particle size of 60-100 mesh, which is used to optimize the coating effect of graphene copper oxide; the antibacterial masterbatch is added to the plastic product at an addition ratio of not less than 2%, so that the graphene copper oxide content in the product is not less than 0.6%.

2. The light-colored, concentrated antibacterial masterbatch of plastic-supported graphene copper oxide according to claim 1, characterized in that: The plastic is PP, PE, PVC, or ABS, and the graphene copper oxide is an ultrafine powder with a moisture content of less than 0.1% and a particle size that passes through an 800-mesh sieve after drying.

3. A method for manufacturing a plastic-supported graphene copper oxide light-colored antibacterial masterbatch according to any one of claims 1-2, characterized in that: Includes the following steps: The graphene copper oxide solid was stirred and sprayed in an aqueous solvent at a pressure of 1-2 MPa; the dispersed graphene copper oxide solid was collected in a powder-solid separation dryer; after collection, it was dried at 100-120°C to remove surface water. After removing the surface water, the graphene copper oxide powder was dried at 120°C for 4 hours in a dehumidifying desiccant chamber to remove the internal structural water, so that its water content was less than 0.1%. The dried graphene copper oxide powder was microwaved and passed through an 800-mesh sieve to obtain ultrafine dried graphene copper oxide powder. Grind the plastic granules into 60-100 mesh plastic powder; stir the titanium dioxide in a V-type low-speed mixer for 20 minutes to disperse it; add the ultrafine dry graphene copper oxide powder in batches and stir for 20 minutes; add the KH550 coupling agent in batches and stir for 20 minutes to fully impregnate the graphene copper oxide and titanium dioxide. Add plastic powder, PP-g-MAH or PE-g-MAH compatibilizer, and 1010 antioxidant, stir for 30 minutes to obtain the mixture; The mixture is extruded and granulated using a twin-screw extruder. The die head is equipped with a 300-1000 mesh filter screen, and the screw temperature is controlled at 170-210℃. Finally, a light-colored, concentrated antibacterial masterbatch of graphene-copper oxide loaded on plastic is prepared.