An antibacterial polypropylene material and a method for preparing the same

Abstract

This invention discloses an antibacterial polypropylene material and its preparation method. The antibacterial polypropylene material is prepared by weight proportioning 75.3-98.7 parts polypropylene, 0-20 parts inorganic filler, 0.5-3 parts hydrated calcium silicate, 0.2-0.5 parts antibacterial agent, 0.1-0.3 parts nucleating agent, 0.3-0.5 parts antioxidant, and 0.2-0.4 parts dispersant. This invention adds a small amount of hydrated calcium silicate to the traditional antibacterial modified polypropylene material formulation, which promotes the dispersion of the composite inorganic Ag ion antibacterial agent, and the hydrated calcium silicate itself has a synergistic antibacterial effect. Better antibacterial effect is achieved with a lower amount of antibacterial agent added. Therefore, a modified polypropylene material with superior antibacterial properties can be prepared, offering a more competitive price advantage.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to an antibacterial polypropylene material and its preparation method. Background Technology

[0002] Polypropylene is one of the most common general-purpose plastics, widely used in home appliances, automobiles, and electronics due to its excellent mechanical and aging properties. Polypropylene components, commonly used in kitchen appliances, bathroom fixtures, personal care products, and even automotive interior parts, all require antibacterial properties. Therefore, the development of highly efficient, long-lasting, and inexpensive antibacterial polypropylene materials has become an important research topic. Summary of the Invention

[0003] In view of the above, the present invention provides an antibacterial polypropylene material and its preparation method to solve the problems mentioned in the background art, and can obtain better antibacterial effect with the same or lower amount of antibacterial agent added.

[0004] To achieve the above objectives, the present invention provides the following technical solution:

[0005] An antibacterial polypropylene material is prepared by weight of 75.3-98.7 parts polypropylene, 0-20 parts inorganic filler, 0.5-3 parts hydrated calcium silicate, 0.2-0.5 parts antibacterial agent, 0.1-0.3 parts nucleating agent, 0.3-0.5 parts antioxidant, and 0.2-0.4 parts dispersant.

[0006] In a further embodiment, the polypropylene is at least one of copolymer polypropylene and homopolymer polypropylene.

[0007] In a further embodiment, the inorganic filler is at least one of talc, calcium carbonate, and barium sulfate;

[0008] In a further embodiment, the hydrated calcium silicate is a commercially available product with a white powder (CAS number 13983-17-0) and a purity greater than 99%.

[0009] In a further embodiment, the antibacterial agent is a composite inorganic Ag ion antibacterial agent.

[0010] In a further embodiment, the nucleating agent is either an α-nucleating agent or a β-nucleating agent for polypropylene;

[0011] In a further embodiment, the antioxidant is a compound of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and tris[2,4-di-tert-butylphenyl]phosphite.

[0012] In a further embodiment, the dispersant is a silicone-based lubricant, a stearate-based lubricant, or an erucic acid-based lubricant.

[0013] Another object of the present invention is to provide a method for preparing the above-described antibacterial polypropylene material, comprising the following steps:

[0014] After thoroughly mixing polypropylene, inorganic filler, hydrated calcium silicate, antibacterial agent, nucleating agent, antioxidant, and dispersant according to the weight parts, a homogeneous mixture is obtained.

[0015] The homogeneous mixture is added to a twin-screw extruder for melt extrusion granulation to obtain antibacterial polypropylene material;

[0016] The temperature of the twin-screw extruder is 180-200℃ in zone one, 190-210℃ in zone two, 190-210℃ in zone three, 200-220℃ in zone four, and 210-230℃ in zone five.

[0017] Compared with the prior art, the beneficial effects of the present invention are:

[0018] (1) The main antibacterial principle of composite inorganic Ag ion antibacterial agents is to utilize Ag ions for antibacterial action. Silver ions can kill bacteria without harming normal cells because most pathogens are single-celled microorganisms that rely on proteases to maintain metabolism and thus reproduce, affecting normal cells. Among these proteases is an oxygen metabolism enzyme. When silver encounters this oxygen metabolism enzyme, the enzyme's activity steals an electron from the silver atom, turning it into a positively charged silver ion. The silver ion then attracts the specific binding of the negatively charged thiol group (-SH) in the protease, effectively penetrating the cell wall and cell membrane surface. This further causes bacterial cells to denature due to protein denaturation, preventing respiration, metabolism, and reproduction, ultimately leading to bacterial death and achieving sterilization without harming normal cells. The above composite inorganic Ag ion antibacterial agents are added in small quantities during modification formulation and are prone to aggregation, making it difficult to obtain polypropylene materials with good antibacterial properties at lower addition levels. Hydrated calcium silicate has a large number of negatively charged sites on its surface and a large number of Si-OH hydroxyl groups on its surface, which can have a good affinity and adsorption effect with antibacterial agents during mixing and melt granulation. The addition amount of hydrated calcium silicate is relatively high and it is easy to disperse, thereby improving the dispersion effect of antibacterial agents in the formulation. Better antibacterial effect can be obtained with a lower amount of antibacterial agent added.

[0019] (2) Other active groups such as carboxyl groups exist on the surface of hydrated calcium silicate, which can react with water in the air or microbial cells to produce a series of free radicals that are harmful to bacteria, such as hydroxyl radicals. These free radicals have oxidizing properties and can destroy the biomolecular structure in bacterial cells, inhibit the survival of bacteria, and thus obtain antibacterial effects.

[0020] (3) In this invention, hydrated calcium silicate and composite inorganic Ag ion antibacterial agent exert antibacterial effects simultaneously and complement each other in terms of formation mechanism, so that the modified polypropylene prepared in the end can obtain better comprehensive antibacterial effect.

[0021] (4) This invention only makes adjustments to the formula, and the raw materials used are all commercially available chemical raw materials. The production process is simple and pollution-free, easy to promote, and has a lower cost advantage when obtaining the same antibacterial effect, thus having a good market prospect.

[0022] (5) In this invention, a nucleating agent is added to the formula to refine the crystallization region. Since the density of the crystalline region and the amorphous region are different, the dispersibility of the antibacterial agent will be different. The addition of the nucleating agent can improve the uniformity of the antibacterial agent dispersion. Detailed Implementation

[0023] To facilitate understanding of the present invention, a more comprehensive description will be given below with reference to specific embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of the present invention.

[0024] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0025] Example 1

[0026] A method for preparing an antibacterial polypropylene material includes the following steps:

[0027] 96.8 parts of polypropylene PP K9829H (Yanshan Petrochemical), 2 parts of hydrated calcium silicate (Jiangxi Dishi Mineral Fiber Technology Co., Ltd.), 0.3 parts of antibacterial agent HX-R102 (Ishizuka Glass), 0.2 parts of nucleating agent NA-11 (Japan Adico), 0.2 parts of antioxidant pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 0.2 parts of antioxidant tris[2,4-di-tert-butylphenyl] phosphite, and 0.3 parts of dispersant silicone lubricant E525 (Evonik Chemicals, Germany) were added to a high-speed mixer and dry-mixed for 5 minutes. The homogeneous mixture was then added to a twin-screw extruder for melt extrusion granulation to obtain antibacterial polypropylene material. The temperatures of the twin-screw extruder were 190℃ in zone 1, 200℃ in zone 2, 200℃ in zone 3, 210℃ in zone 4, and 220℃ in zone 5.

[0028] Example 2

[0029] A method for preparing an antibacterial polypropylene material includes the following steps:

[0030] 82.4 parts of polypropylene PP S700 (Sinopec Yangzi Petrochemical) and 15 parts of inorganic filler talc powder AH were mixed. 51210 (Liaoning Aihai), 1.5 parts hydrated calcium silicate (Qingdao Zhongfuxing Trading Co., Ltd.), 0.4 parts antibacterial agent-HX-R102 (Ishizuka Glass), 0.1 parts nucleating agent TMB-5 (Shaanxi Provincial Chemical Research Institute), 0.1 parts antioxidant pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 0.2 parts antioxidant tris[2,4-di-tert-butylphenyl] phosphite, and 0.3 parts dispersant calcium stearate were added to a high-speed mixer and dry-mixed for 8 minutes. The uniform mixture was then added to a twin-screw extruder for melt extrusion granulation to obtain antibacterial polypropylene material. The temperatures of the twin-screw extruder were 190℃ in zone 1, 190℃ in zone 2, 200℃ in zone 3, 210℃ in zone 4, and 210℃ in zone 5.

[0031] Example 3

[0032] A method for preparing an antibacterial polypropylene material includes the following steps:

[0033] 92.6 parts of polypropylene PP S2040 (Shanghai SECCO), 5 parts of inorganic filler calcium carbonate LD-1000C (Lida Ultramicro), 1 part of hydrated calcium silicate (Jiangxi Dishi Mineral Fiber Technology Co., Ltd.), 0.4 parts of antibacterial agent JP-928 (Shanghai Yikelin Technology Co., Ltd.), 0.2 parts of nucleating agent NA-11 (Japan Adico), 0.2 parts of antioxidant pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 0.2 parts of antioxidant tris[2,4-di-tert-butylphenyl] phosphite, and 0.4 parts of dispersant erucamide were added to a high-speed mixer and dry-mixed for 10 minutes. The homogeneous mixture was then melt-extruded and granulated in a twin-screw extruder to obtain antibacterial polypropylene material. The temperatures of the twin-screw extruder were 180℃ in zone 1, 190℃ in zone 2, 200℃ in zone 3, 210℃ in zone 4, and 220℃ in zone 5.

[0034] Example 4

[0035] A method for preparing an antibacterial polypropylene material includes the following steps:

[0036] 98.7 parts of polypropylene PP K7926 (Shanghai SECCO), 0.5 parts of hydrated calcium silicate (Qingdao Zhongfuxing Trading Co., Ltd.), 0.2 parts of antibacterial agent JP-928 (Shanghai Yikelin Technology Co., Ltd.), 0.1 parts of nucleating agent NA-11 (Japan Aidi Ke), 0.1 parts of antioxidant pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 0.2 parts of antioxidant tris[2,4-di-tert-butylphenyl] phosphite, and 0.2 parts of dispersant silicone lubricant E525 (Evonik Chemicals, Germany) were added to a high-speed mixer and dry-mixed for 3 minutes. The homogeneous mixture was then added to a twin-screw extruder for melt extrusion granulation to obtain antibacterial polypropylene material. The temperatures of the twin-screw extruder were 180℃ in zone 1, 190℃ in zone 2, 190℃ in zone 3, 200℃ in zone 4, and 210℃ in zone 5.

[0037] Example 5

[0038] A method for preparing an antibacterial polypropylene material includes the following steps:

[0039] 75.3 parts of polypropylene PP BX3800 (SK Korea), 20 parts of inorganic filler barium sulfate BSM-M (Guangzhou Jimei), 3 parts of hydrated calcium silicate (Jiangxi Dishi Mineral Fiber Technology Co., Ltd.), 0.5 parts of antibacterial agent JP-928 (Shanghai Yikelin Technology Co., Ltd.), 0.3 parts of nucleating agent TMB-5 (Shaanxi Provincial Chemical Research Institute), 0.3 parts of antioxidant pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 0.2 parts of antioxidant tris[2,4-di-tert-butylphenyl] phosphite, and 0.4 parts of dispersant erucamide were added to a high-speed mixer and dry-mixed for 15 minutes. The uniform mixture was then added to a twin-screw extruder for melt extrusion granulation to obtain antibacterial polypropylene material. The temperature of the twin-screw extruder was 200℃ in zone 1, 210℃ in zone 2, 210℃ in zone 3, 200-220℃ in zone 4, and 230℃ in zone 5.

[0040] Comparative Example 1

[0041] A method for preparing an antibacterial polypropylene material includes the following steps:

[0042] 98.8 parts of polypropylene PP K9829H (Yanshan Petrochemical), 0.3 parts of antibacterial agent HX-R102 (Ishizuka Glass), 0.2 parts of nucleating agent NA-11 (Japan Adico), 0.2 parts of antioxidant pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 0.2 parts of antioxidant tris[2,4-di-tert-butylphenyl] phosphite, and 0.3 parts of dispersant silicone lubricant E525 (Evonik Chemicals, Germany) were added to a high-speed mixer and dry-mixed for 5 minutes. The homogeneous mixture was then added to a twin-screw extruder for melt extrusion granulation to obtain antibacterial polypropylene material. The temperatures of the twin-screw extruder were 190℃ in zone 1, 200℃ in zone 2, 200℃ in zone 3, 210℃ in zone 4, and 220℃ in zone 5.

[0043] Comparative Example 2

[0044] A method for preparing an antibacterial polypropylene material includes the following steps:

[0045] 97.0 parts of polypropylene PP K9829H (Yanshan Petrochemical), 2 parts of hydrated calcium silicate (Jiangxi Dishi Mineral Fiber Technology Co., Ltd.), 0.3 parts of antibacterial agent HX-R102 (Ishizuka Glass), 0.2 parts of antioxidant pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 0.2 parts of antioxidant tris[2,4-di-tert-butylphenyl] phosphite, and 0.3 parts of dispersant silicone lubricant E525 (Evonik Chemicals, Germany) were added to a high-speed mixer and dry-mixed for 5 minutes. The homogeneous mixture was then added to a twin-screw extruder for melt extrusion granulation to obtain antibacterial polypropylene material. The temperatures of the twin-screw extruder were 190℃ in zone 1, 200℃ in zone 2, 200℃ in zone 3, 210℃ in zone 4, and 220℃ in zone 5.

[0046] Comparative Example 3

[0047] A method for preparing an antibacterial polypropylene material includes the following steps:

[0048] 99.0 parts of polypropylene PP K9829H (Yanshan Petrochemical), 0.3 parts of antibacterial agent HX-R102 (Ishizuka Glass), 0.2 parts of antioxidant pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 0.2 parts of antioxidant tris[2,4-di-tert-butylphenyl] phosphite, and 0.3 parts of dispersant silicone lubricant E525 (Evonik Chemicals, Germany) were added to a high-speed mixer and dry-mixed for 5 minutes. The homogeneous mixture was then added to a twin-screw extruder for melt extrusion granulation to obtain antibacterial polypropylene material. The temperatures of the twin-screw extruder were 190℃ in zone 1, 200℃ in zone 2, 200℃ in zone 3, 210℃ in zone 4, and 220℃ in zone 5.

[0049] Comparative Example 4:

[0050] A method for preparing an antibacterial polypropylene material includes the following steps:

[0051] 98.6 parts of polypropylene PP K9829H (Yanshan Petrochemical), 0.7 parts of antibacterial agent HX-R102 (Ishizuka Glass), 0.2 parts of antioxidant pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 0.2 parts of antioxidant tris[2,4-di-tert-butylphenyl] phosphite, and 0.3 parts of dispersant silicone lubricant E525 (Evonik Chemicals, Germany) were added to a high-speed mixer and dry-mixed for 5 minutes. The homogeneous mixture was then added to a twin-screw extruder for melt extrusion granulation to obtain antibacterial polypropylene material. The temperatures of the twin-screw extruder were 190℃ in zone 1, 200℃ in zone 2, 200℃ in zone 3, 210℃ in zone 4, and 220℃ in zone 5.

[0052] The antibacterial properties of the obtained antibacterial polypropylene material were tested according to standard GB / T 31402-2015, and the results are shown in Table 1.

[0053] Table 1. Antimicrobial properties of antimicrobial polypropylene materials in the examples and comparative examples.

[0054]

[0055] As can be seen from the test results in Table 1, the modified polypropylene material prepared by this invention has excellent antibacterial properties.

[0056] It is understood that the above-mentioned raw materials and reagents are merely examples of some specific embodiments of the present invention, making the technical solution of the present invention clearer, and do not mean that the present invention can only use the above-mentioned reagents. The specific scope shall be determined by the claims. In addition, unless otherwise specified, "parts" in the examples and comparative examples refer to parts by weight.

[0057] Any range described in this invention includes the endpoint, any value between the endpoints, and any subrange consisting of the endpoint or any value between the endpoints.

[0058] Although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

[0059] Therefore, the above description is only a preferred embodiment of this application and is not intended to limit the scope of this application; that is, all equivalent modifications made in accordance with the scope of the claims of this application shall be within the protection scope of the claims of this application.

Claims

1. An antibacterial polypropylene material, characterized in that, It is prepared by weight of 75.3-98.7 parts polypropylene, 0-20 parts inorganic filler, 0.5-3 parts hydrated calcium silicate, 0.2-0.5 parts antibacterial agent, 0.1-0.3 parts nucleating agent, 0.3-0.5 parts antioxidant, and 0.2-0.4 parts dispersant.

2. The antibacterial polypropylene material according to claim 1, characterized in that, The polypropylene is at least one of copolymer polypropylene and homopolymer polypropylene.

3. The antibacterial polypropylene material according to claim 1, characterized in that, The inorganic filler is at least one of talc, calcium carbonate, and barium sulfate.

4. The antibacterial polypropylene material according to claim 1, characterized in that, The antibacterial agent is a composite inorganic Ag ion antibacterial agent.

5. The antibacterial polypropylene material according to claim 1, characterized in that, The nucleating agent is either an α-nucleating agent or a β-nucleating agent for polypropylene.

6. The antibacterial polypropylene material according to claim 1, characterized in that, The antioxidant is a compound of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and tris[2,4-di-tert-butylphenyl]phosphite.

7. The antibacterial polypropylene material according to claim 1, characterized in that, The dispersant is a silicone lubricant, a stearate lubricant, or an erucic acid lubricant.

8. The method for preparing the antibacterial polypropylene material according to any one of claims 1-7, characterized in that, Includes the following steps: After thoroughly mixing polypropylene, inorganic filler, hydrated calcium silicate, antibacterial agent, nucleating agent, antioxidant, and dispersant according to the weight parts, a homogeneous mixture is obtained. The homogeneous mixture is added to a twin-screw extruder for melt extrusion granulation to obtain antibacterial polypropylene material.

9. The method for preparing the antibacterial polypropylene material according to claim 8, characterized in that, The temperature of the twin-screw extruder is 180-200℃ in zone one, 190-210℃ in zone two, 190-210℃ in zone three, 200-220℃ in zone four, and 210-230℃ in zone five.

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