Wear-resistant antibacterial thermoplastic resin composite and method for preparing the same

Abstract

This invention discloses a wear-resistant and antibacterial thermoplastic resin composite material and its preparation method, comprising the following components by weight: 90-110 parts thermoplastic resin, 10-16 parts functional filler, and 0.1-0.5 parts antioxidant. This invention also discloses the preparation method of the thermoplastic resin composite material. The thermoplastic resin composite material prepared by this invention exhibits excellent wear resistance and antibacterial properties, and can be used in the automotive and home appliance materials fields, showing excellent application prospects.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials, specifically relating to a wear-resistant and antibacterial thermoplastic resin composite material and its preparation method. Background Technology

[0002] Thermoplastic resin is a widely used high-molecular-weight polyester resin. It possesses advantages such as good fatigue resistance, good heat resistance, and excellent dimensional stability. However, in certain specific applications, high requirements are placed on the wear resistance and antibacterial properties of thermoplastic resins. For example, when used in lunch boxes, thermoplastic resins must not only be resistant to steam but also be usable in microwaves or refrigerators. Therefore, plastic lunch boxes require antibacterial and wear-resistant properties because microorganisms, such as bacteria and molds, can easily infect humans, animals, and plants during use, causing diseases and endangering human health and life. This limits the application of thermoplastic resin composites in certain specific fields.

[0003] Currently, the main approach to improving the antibacterial properties of thermoplastic resins is to add antibacterial agents. These are chemical substances that, for a certain period of time, keep the growth or reproduction of certain microorganisms (bacteria, fungi, yeasts, algae, and viruses, etc.) below a necessary level. Antibacterial agents are substances or products with bacteriostatic and bactericidal properties, such as silver ions. The antibacterial mechanism of silver ions and their compounds is a contact reaction mechanism. The contact reaction of silver ions causes the destruction of common components of microorganisms or causes functional disorders. When trace amounts of silver ions reach the cell membrane of microorganisms, the latter, being negatively charged, is strongly adsorbed by Coulomb attraction. The silver ions penetrate the cell wall and enter the cell, reacting with SH groups, causing protein coagulation, destroying the activity of cellular synthetic enzymes, and causing the cell to lose its ability to divide and proliferate, leading to cell death. Silver ions can also damage the electron transport system, respiratory system, and mass transport system of microorganisms.

[0004] Although nano-silver is a commonly used inorganic antibacterial agent with good biocompatibility, environmental safety, and long-lasting antibacterial properties, directly adding it to a plastic matrix can easily lead to the aggregation of the nano-antibacterial agent, which will affect its original antibacterial performance to some extent.

[0005] Regarding wear resistance, current methods typically involve adding inorganic fillers such as glass fiber, graphite, and molybdenum disulfide to alter the surface hardness of the material, or adding additives such as erucamide to improve surface lubricity. However, these materials experience significant wear, have a short service life, and are prone to causing wear on grinding components.

[0006] To address these shortcomings, this invention innovatively synthesizes a wear-resistant and antibacterial thermoplastic resin composite material, which exhibits excellent wear resistance and antibacterial properties. This type of thermoplastic resin composite material has not been reported before, which is of great practical significance for expanding the application fields of thermoplastic resin composite materials. Summary of the Invention

[0007] In view of this, the present invention innovatively synthesizes a wear-resistant and antibacterial thermoplastic resin composite material, which has excellent wear resistance and antibacterial properties, and solves the technical problem of limited wear resistance and antibacterial properties of existing thermoplastic resins.

[0008] The objective of this invention is achieved through the following technical solution:

[0009] A wear-resistant and antibacterial thermoplastic resin composite material and its preparation method, comprising the following components in parts by weight:

[0010] 90-110 parts of thermoplastic resin

[0011] 10-16 parts of functional filler

[0012] Antioxidant 0.1-0.5 parts

[0013] The functional filler is citral / PDA / boron carbide / MgO.

[0014] The preparation method of citral / PDA / boron carbide / MgO includes the following steps:

[0015] (1) Add magnesium phosphate and ammonia water to deionized water, react at room temperature, filter, wash and dry to obtain solid A;

[0016] (2) Solid A was calcined in a muffle furnace, cooled and then ground through a 500-mesh sieve to obtain solid B;

[0017] (3) Place Tris-HCl buffer solution, dopamine hydrochloride, citral, boron carbide, anhydrous ethanol, deionized water, solid B, and crosslinking agent in a reactor vessel and react in a water bath; then filter, wash, and dry to obtain citral / PDA / boron carbide / MgO.

[0018] Preferably, the mass ratio of magnesium phosphate to ammonia in step (1) is (20-30):(30-36);

[0019] The reaction time at room temperature is 4-6 hours, and the drying is carried out in a vacuum drying oven at 40-60℃ for 2-4 hours.

[0020] Preferably, in step (2), the calcination is carried out at 640-720℃ for 10-12 hours.

[0021] Preferably, in step (3), the mass ratio of Tris-HCl buffer solution, dopamine hydrochloride, citral, boron carbide, anhydrous ethanol, deionized water, solid B, and crosslinking agent is (40-50): (30-40): (18-24): (30-36): (50-60): (60-70): (10-16): (0.1-0.3).

[0022] Preferably, the crosslinking agent in step (3) is vinyltriethoxysilane, dicumyl peroxide, or benzoyl peroxide;

[0023] The water bath reaction temperature is 60-80℃ and the reaction time is 8-12h.

[0024] In step (3), the Tris-HCl buffer solution is prepared by stirring Tris solution and HCl solution for 8-12 hours, and the mass ratio of Tris solution to HCl solution is (30-36):(36-40).

[0025] In a further embodiment, the antioxidant is one or a mixture of several of the following: BASF's tris(2,4-di-tert-butyl)phosphite (Irganox 168), N,N'-hexane-1,6-dimethylbis(3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide))(Irganox 1098), and 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxyphenylmethyl)benzene (Irganox 1330).

[0026] The method for preparing the thermoplastic resin composite material is characterized by comprising the following steps:

[0027] (1) Weigh 90-110 parts of thermoplastic resin, 10-16 parts of functional filler, and 0.1-0.5 parts of antioxidant, mix and stir evenly to obtain a mixture;

[0028] (2) The mixture obtained in step (1) is extruded from the extruder and granulated to obtain the thermoplastic resin composite material.

[0029] The thermoplastic resin is one of polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyamide 6 (PA6).

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] (1) The functional filler in this application was first synthesized from magnesium phosphate to form MgO and dopamine hydrochloride as raw materials to form polydopamine; finally, MgO and polydopamine, citral and boron carbide were physically cross-linked to form citral / PDA / boron carbide / MgO composite functional filler.

[0032] Mg3(PO4)2+6NH3·H2O→3Mg(OH)2+2(NH4)3PO4

[0033] 3Mg(OH)2→MgO+H2O

[0034] (2) This application innovatively prepares a citral / PDA / boron carbide / MgO functional filler. Boron carbide, after PDA modification, exhibits enhanced binding ability with citral. Furthermore, citral itself can disrupt the cell membrane structure of microorganisms and inhibit protein and enzyme activity, thus possessing a strong bactericidal effect and exhibiting powerful antibacterial and anti-infective properties. On the other hand, the MgO contains the metal ion Mg... 2+ It also has a strong inhibitory effect on bacteria, and this dual bactericidal effect enhances the antibacterial properties of thermoplastic resin composites. Therefore, the addition of citral / PDA / boron carbide / MgO functional fillers can effectively improve the antibacterial properties of thermoplastic resin composites.

[0035] (3) The boron carbide in citral / PDA / boron carbide / MgO has a high hardness, and its presence improves the wear resistance of thermoplastic resin composites.

[0036] (4) The macromolecular PDA generated by polymerization in this application contains a large number of catechol and amino groups, which on the one hand easily adsorb Mg 2+ It can coordinate with it to form a chelate; on the other hand, it can combine with the aldehyde group in the citral structure to ultimately form a citral / PDA / boron carbide / MgO functional filler. Detailed Implementation

[0037] To facilitate understanding of the present invention, a more comprehensive description of the invention will be provided below in conjunction with 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 enable a more thorough and complete understanding of the disclosure of the present invention.

[0038] 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.

[0039] The raw materials used in the following examples are as follows:

[0040] PBT (Model 2002U), Polyplastics, Japan;

[0041] PP (model Z30S), Maoming Petrochemical;

[0042] PE (Model 5070), Panjin Ethylene;

[0043] PA6 (model CM1017), Toray Industries, Japan;

[0044] PET (model 008L), Canadian Aclo;

[0045] Tris solution, Hubei Kewode Chemical Co., Ltd.;

[0046] HCl solution, Beijing Haifuda Technology Co., Ltd.

[0047] Dopamine hydrochloride, Nanjing Wanghua Chemical Technology Co., Ltd.

[0048] Deionized water, Xiamen Aoquan Environmental Protection Technology Co., Ltd.

[0049] Magnesium phosphate, Hubei Dibo Chemical Co., Ltd.;

[0050] Ammonia water, Jinan Mengqiao Chemical Co., Ltd.;

[0051] Boron carbide, Shandong Xindongneng Chemical Co., Ltd.;

[0052] Anhydrous ethanol, Shandong Taixi Chemical Co., Ltd.;

[0053] Crosslinking agent vinyltriethoxysilane, Shandong Shouhua Chemical Co., Ltd.;

[0054] Antioxidants (models Irganox 168, Irganox 1098, Irganox 1330), BASF.

[0055] Preparation Example 1

[0056] (1) Weigh 300g of Tris solution and 360g of HCl solution, place them in a reactor dish, and stir the reaction at room temperature for 8 hours to prepare Tris-HCl buffer solution.

[0057] (2) Weigh 200g magnesium phosphate, 300g ammonia water and 700g deionized water, place them in a reactor dish, react at room temperature for 4h, filter, wash, place in a vacuum drying oven at 40℃ for 2h to obtain solid A;

[0058] (3) Solid A was placed in a muffle furnace and calcined at 640°C for 10 hours. After cooling, it was ground through a 500-mesh sieve to obtain solid B.

[0059] (4) Weigh 400g Tris-HCl buffer solution, 300g dopamine hydrochloride, 180g citral, 300g boron carbide, 500g anhydrous ethanol, 600g deionized water, 100g solid B, and 1g crosslinking agent vinyltriethoxysilane, place them in a reactor dish, and react in a water bath at 60℃ for 8h to obtain solution A;

[0060] (5) Solution A was filtered, washed, and dried in a vacuum drying oven at 50°C for 4 hours to obtain functional filler M1 of type citral / PDA / boron carbide / MgO.

[0061] Example 1

[0062] (1) Weigh 90 parts of PP, 10 parts of functional filler M1 and 0.1 parts of Irganox 1098, mix and stir evenly to obtain a mixture;

[0063] (2) The mixture obtained in step (1) is extruded from the extruder and granulated to obtain PP composite material P1.

[0064] The twin-screw extruder includes six temperature zones arranged in sequence: the temperature of the first temperature zone is 170°C, the temperature of the second temperature zone is 230°C, the temperature of the third temperature zone is 230°C, the temperature of the fourth temperature zone is 230°C, the temperature of the fifth temperature zone is 230°C, the temperature of the sixth temperature zone is 230°C, the die temperature of the twin-screw extruder is 230°C, and the screw speed is 220 r / min.

[0065] Comparative Example 1

[0066] (1) Weigh 90 parts of PP, 10 parts of antibacterial agent citral, and 0.1 parts of Irganox 1098, mix and stir evenly to obtain a mixture;

[0067] (2) The mixture obtained in step (1) is extruded from the extruder and granulated to obtain PP composite material D1.

[0068] The twin-screw extruder includes six temperature zones arranged in sequence: the temperature of the first temperature zone is 170°C, the temperature of the second temperature zone is 230°C, the temperature of the third temperature zone is 230°C, the temperature of the fourth temperature zone is 230°C, the temperature of the fifth temperature zone is 230°C, the temperature of the sixth temperature zone is 230°C, the die temperature of the twin-screw extruder is 230°C, and the screw speed is 220 r / min.

[0069] Comparative Example 2

[0070] (1) Weigh 90 parts of PP, 10 parts of wear-resistant boron carbide, and 0.1 parts of Irganox 1098, mix and stir evenly to obtain a mixture;

[0071] (2) The mixture obtained in step (1) is extruded from the extruder and granulated to obtain PP composite material D2.

[0072] The twin-screw extruder includes six temperature zones arranged in sequence: the temperature of the first temperature zone is 170°C, the temperature of the second temperature zone is 230°C, the temperature of the third temperature zone is 230°C, the temperature of the fourth temperature zone is 230°C, the temperature of the fifth temperature zone is 230°C, the temperature of the sixth temperature zone is 230°C, the die temperature of the twin-screw extruder is 230°C, and the screw speed is 220 r / min.

[0073] The PP composite materials prepared in Example 1 and Comparative Examples 1-2 were injection molded into test strips. The test data are shown in the table below:

[0074]

[0075] In summary, Example 1 of this application uses a functional filler, a citral / PDA / boron carbide / MgO composite material, which possesses antibacterial and wear-resistant properties. While Comparative Examples 1-2 used the same amounts of the antibacterial agent citral and the wear-resistant agent boron carbide, the composite material prepared in Example 1 of this application exhibits superior antibacterial and wear-resistant properties overall. Therefore, the citral / PDA / boron carbide / MgO type functional filler added in this application brings unexpected technical benefits to the antibacterial and wear-resistant properties of the composite material.

[0076] Preparation Example 2

[0077] (1) Weigh 360g of Tris solution and 400g of HCl solution, place them in a reactor dish, and stir at room temperature for 12 hours to prepare Tris-HCl buffer solution.

[0078] (2) Weigh 300g magnesium phosphate, 360g ammonia water and 900g deionized water, place them in a reactor dish, react at room temperature for 6h, filter, wash, and dry in a vacuum drying oven at 60℃ for 4h to obtain solid A.

[0079] (3) Solid A was placed in a muffle furnace and calcined at 720°C for 12 hours. After cooling, it was ground through a 500-mesh sieve to obtain solid B.

[0080] (4) Weigh 500g Tris-HCl buffer solution, 400g dopamine hydrochloride, 240g citral, 360g boron carbide, 600g anhydrous ethanol, 700g deionized water, 160g solid B, and 3g crosslinking agent vinyltriethoxysilane, place them in a reactor dish, and react in an 80℃ water bath for 12h to obtain solution A.

[0081] (5) Solution A was filtered, washed, and dried in a vacuum drying oven at 70°C for 6 hours to obtain functional filler M2 of type citral / PDA / boron carbide / MgO.

[0082] Example 2

[0083] (1) Weigh 110 parts of PBT, 16 parts of functional filler M2, 0.1 parts of antioxidant Irganox 1098, 0.2 parts of antioxidant Irganox 168, and 0.2 parts of antioxidant Irganox 1330, mix and stir evenly to obtain a mixture;

[0084] (2) The mixture obtained in step (1) is extruded from the extruder and granulated to obtain PBT composite material P2.

[0085] The twin-screw extruder includes six temperature zones arranged in sequence: the first temperature zone has a temperature of 200℃, the second temperature zone has a temperature of 230℃, the third temperature zone has a temperature of 240℃, the fourth temperature zone has a temperature of 240℃, the fifth temperature zone has a temperature of 240℃, and the sixth temperature zone has a temperature of 240℃. The die temperature of the twin-screw extruder is 240℃, and the screw speed is 300 r / min.

[0086] Comparative Example 3

[0087] (1) Weigh 110 parts of PBT, 16 parts of antibacterial agent citral, 0.1 parts of antioxidant Irganox 1098, 0.2 parts of antioxidant Irganox 168, and 0.2 parts of antioxidant Irganox 1330, mix and stir evenly to obtain a mixture;

[0088] (2) The mixture obtained in step (1) is extruded from the extruder and granulated to obtain PBT composite material D3.

[0089] The twin-screw extruder includes six temperature zones arranged in sequence: the first temperature zone has a temperature of 200℃, the second temperature zone has a temperature of 230℃, the third temperature zone has a temperature of 240℃, the fourth temperature zone has a temperature of 240℃, the fifth temperature zone has a temperature of 240℃, and the sixth temperature zone has a temperature of 240℃. The die temperature of the twin-screw extruder is 240℃, and the screw speed is 300 r / min.

[0090] Comparative Example 4

[0091] (1) Weigh 110 parts of PBT, 16 parts of wear-resistant boron carbide, 0.1 parts of antioxidant Irganox 1098, 0.2 parts of antioxidant Irganox 168, and 0.2 parts of antioxidant Irganox 1330, mix and stir evenly to obtain a mixture;

[0092] (2) The mixture obtained in step (1) is extruded from the extruder and granulated to obtain PBT composite material D4.

[0093] The twin-screw extruder includes six temperature zones arranged in sequence: the first temperature zone has a temperature of 200℃, the second temperature zone has a temperature of 230℃, the third temperature zone has a temperature of 240℃, the fourth temperature zone has a temperature of 240℃, the fifth temperature zone has a temperature of 240℃, and the sixth temperature zone has a temperature of 240℃. The die temperature of the twin-screw extruder is 240℃, and the screw speed is 300 r / min.

[0094] The PBT composite materials prepared in Example 2 and Comparative Examples 3-4 were injection molded into test strips. The test data are shown in the table below:

[0095]

[0096] In summary, the wear resistance and antibacterial properties of Example 2 are generally better than those of Comparative Examples 3-4.

[0097] Preparation Example 3

[0098] (1) Weigh 330g of Tris solution and 380g of HCl solution, place them in a reactor dish, and stir at room temperature for 10h to prepare Tris-HCl buffer solution.

[0099] (2) Weigh 250g magnesium phosphate, 330g ammonia water and 800g deionized water, place them in a reactor dish, react at room temperature for 5h, filter, wash, and dry in a vacuum drying oven at 50℃ for 3h to obtain solid A.

[0100] (3) Solid A was placed in a muffle furnace and calcined at 680°C for 11 hours. After cooling, it was ground through a 500-mesh sieve to obtain solid B.

[0101] (4) Weigh 450g Tris-HCl buffer solution, 350g dopamine hydrochloride, 210g citral, 330g boron carbide, 550g anhydrous ethanol, 650g deionized water, 130g solid B, and 2g crosslinking agent vinyltriethoxysilane, place them in a reactor dish, and react in a water bath at 70℃ for 10h to obtain solution A.

[0102] (5) Solution A was filtered, washed, and dried in a vacuum drying oven at 60°C for 5 hours to obtain functional filler M3 of type citral / PDA / boron carbide / MgO.

[0103] Example 3

[0104] (1) Weigh 100 parts of PE, 13 parts of functional filler M3, 0.1 parts of antioxidant Irganox168, and 0.2 parts of antioxidant Irganox 1098, mix and stir evenly to obtain a mixture;

[0105] (2) The mixture obtained in step (1) is extruded from the extruder and granulated to obtain PE composite material P3.

[0106] The twin-screw extruder includes six temperature zones arranged in sequence: the first temperature zone has a temperature of 120℃, the second temperature zone has a temperature of 180℃, the third temperature zone has a temperature of 180℃, the fourth temperature zone has a temperature of 180℃, the fifth temperature zone has a temperature of 180℃, and the sixth temperature zone has a temperature of 180℃. The die temperature of the twin-screw extruder is 180℃, and the screw speed is 300 r / min.

[0107] Comparative Example 5

[0108] (1) Weigh 100 parts of PE, 13 parts of antibacterial agent citral, 0.1 parts of antioxidant Irganox168, and 0.2 parts of antioxidant Irganox 1098, mix and stir evenly to obtain a mixture;

[0109] (2) The mixture obtained in step (1) is extruded from the extruder and granulated to obtain PE composite material D5.

[0110] The twin-screw extruder includes six temperature zones arranged in sequence: the first temperature zone has a temperature of 120℃, the second temperature zone has a temperature of 180℃, the third temperature zone has a temperature of 180℃, the fourth temperature zone has a temperature of 180℃, the fifth temperature zone has a temperature of 180℃, and the sixth temperature zone has a temperature of 180℃. The die temperature of the twin-screw extruder is 180℃, and the screw speed is 300 r / min.

[0111] Comparative Example 6

[0112] (1) Weigh 100 parts of PE, 13 parts of wear-resistant boron carbide, 0.1 parts of antioxidant Irganox168, and 0.2 parts of antioxidant Irganox 1098, mix and stir evenly to obtain a mixture;

[0113] (2) The mixture obtained in step (1) is extruded from the extruder and granulated to obtain PE composite material D6.

[0114] The twin-screw extruder includes six temperature zones arranged in sequence: the first temperature zone has a temperature of 120℃, the second temperature zone has a temperature of 180℃, the third temperature zone has a temperature of 180℃, the fourth temperature zone has a temperature of 180℃, the fifth temperature zone has a temperature of 180℃, and the sixth temperature zone has a temperature of 180℃. The die temperature of the twin-screw extruder is 180℃, and the screw speed is 300 r / min.

[0115] The PE composite materials prepared in Example 3 and Comparative Examples 5-6 were injection molded into test strips. The test data are shown in the table below:

[0116]

[0117] In summary, the wear resistance and antibacterial properties of Example 3 are generally better than those of Comparative Examples 5-6.

[0118] Preparation Example 4

[0119] (1) Weigh 355g of Tris solution and 395g of HCl solution, place them in a reactor dish, and stir the reaction at room temperature for 11 hours to prepare Tris-HCl buffer solution.

[0120] (2) Weigh 285g magnesium phosphate, 345g ammonia water and 795g deionized water, place them in a reactor dish, react at room temperature for 5h, filter, wash, and dry in a vacuum drying oven at 55℃ for 2h to obtain solid A.

[0121] (3) Solid A was placed in a muffle furnace and calcined at 715°C for 11 hours. After cooling, it was ground through a 500-mesh sieve to obtain solid B.

[0122] (4) Weigh 485g Tris-HCl buffer solution, 315g dopamine hydrochloride, 205g citral, 335g boron carbide, 515g anhydrous ethanol, 635g deionized water, 155g solid B, and 2.5g crosslinking agent vinyltriethoxysilane, place them in a reactor dish, and react in a water bath at 75℃ for 11h to obtain solution A.

[0123] (5) Solution A was filtered, washed, and dried in a vacuum drying oven at 55°C for 6 hours to obtain functional filler M4 of type citral / PDA / boron carbide / MgO.

[0124] Example 4

[0125] (1) Weigh 85 parts of PA6, 14 parts of functional filler M4, 0.1 parts of antioxidant Irganox 1098, and 0.2 parts of antioxidant Irganox 1330, mix and stir evenly to obtain a mixture;

[0126] (2) The mixture obtained in step (1) is extruded from the extruder and granulated to obtain PA6 composite material P4.

[0127] The twin-screw extruder includes six temperature zones arranged in sequence: the first temperature zone has a temperature of 210℃, the second temperature zone has a temperature of 260℃, the third temperature zone has a temperature of 260℃, the fourth temperature zone has a temperature of 260℃, the fifth temperature zone has a temperature of 260℃, and the sixth temperature zone has a temperature of 260℃. The die temperature of the twin-screw extruder is 260℃, and the screw speed is 320 r / min.

[0128] Comparative Example 7

[0129] (1) Weigh 85 parts of PA6, 14 parts of antibacterial agent citral, 0.1 parts of antioxidant Irganox 1098, and 0.2 parts of antioxidant Irganox 1330, mix and stir evenly to obtain a mixture;

[0130] (2) The mixture obtained in step (1) is extruded from the extruder and granulated to obtain PA6 composite material D7.

[0131] The twin-screw extruder includes six temperature zones arranged in sequence: the first temperature zone has a temperature of 210℃, the second temperature zone has a temperature of 260℃, the third temperature zone has a temperature of 260℃, the fourth temperature zone has a temperature of 260℃, the fifth temperature zone has a temperature of 260℃, and the sixth temperature zone has a temperature of 260℃. The die temperature of the twin-screw extruder is 260℃, and the screw speed is 320 r / min.

[0132] Comparative Example 8

[0133] (1) Weigh 85 parts of PA6, 14 parts of wear-resistant boron carbide, 0.1 parts of antioxidant Irganox 1098, and 0.2 parts of antioxidant Irganox 1330, mix and stir evenly to obtain a mixture;

[0134] (2) The mixture obtained in step (1) is extruded from the extruder and granulated to obtain PA6 composite material D7.

[0135] The twin-screw extruder includes six temperature zones arranged in sequence: the first temperature zone has a temperature of 210℃, the second temperature zone has a temperature of 260℃, the third temperature zone has a temperature of 260℃, the fourth temperature zone has a temperature of 260℃, the fifth temperature zone has a temperature of 260℃, and the sixth temperature zone has a temperature of 260℃. The die temperature of the twin-screw extruder is 260℃, and the screw speed is 320 r / min.

[0136] The PA6 composite materials prepared in Example 4 and Comparative Examples 7-8 were injection molded into test strips. The test data are shown in the table below:

[0137]

[0138] In summary, the wear resistance and antibacterial properties of Example 4 are generally better than those of Comparative Examples 7-8.

[0139] Preparation Example 5

[0140] (1) Weigh 345g of Tris solution and 385g of HCl solution, place them in a reactor dish, and stir at room temperature for 9 hours to prepare Tris-HCl buffer solution.

[0141] (2) Weigh 215g magnesium phosphate, 335g ammonia water and 885g deionized water, place them in a reactor dish, react at room temperature for 5h, filter, wash, and dry in a vacuum drying oven at 55℃ for 4h to obtain solid A.

[0142] (3) Solid A was placed in a muffle furnace and calcined at 705°C for 11 hours. After cooling, it was ground through a 500-mesh sieve to obtain solid B.

[0143] (4) Weigh 425g Tris-HCl buffer solution, 375g dopamine hydrochloride, 225g citral, 345g boron carbide, 525g anhydrous ethanol, 655g deionized water, 145g solid B, and 2.8g crosslinking agent vinyltriethoxysilane, place them in a reactor dish, and react in a water bath at 75℃ for 9h to obtain solution A.

[0144] (5) Solution A was filtered, washed, and dried in a vacuum drying oven at 65°C for 5 hours to obtain functional filler M5 of type citral / PDA / boron carbide / MgO.

[0145] Example 5

[0146] (1) Weigh 95 parts of PET, 13.5 parts of functional filler M5, 0.1 parts of antioxidant Irganox 1098, and 0.1 parts of antioxidant Irganox 168, mix and stir evenly to obtain a mixture;

[0147] (2) The mixture obtained in step (1) is extruded from the extruder and granulated to obtain PET composite material P5.

[0148] The twin-screw extruder includes six temperature zones arranged in sequence: the first temperature zone has a temperature of 240℃, the second temperature zone has a temperature of 280℃, the third temperature zone has a temperature of 280℃, the fourth temperature zone has a temperature of 280℃, the fifth temperature zone has a temperature of 280℃, and the sixth temperature zone has a temperature of 280℃. The die temperature of the twin-screw extruder is 280℃, and the screw speed is 280 r / min.

[0149] Comparative Example 9

[0150] (1) Weigh 95 parts of PET, 13.5 parts of antibacterial agent citral, 0.1 parts of antioxidant Irganox 1098, and 0.1 parts of antioxidant Irganox 168, mix and stir evenly to obtain a mixture;

[0151] (2) The mixture obtained in step (1) is extruded from the extruder and granulated to obtain PET composite material D9.

[0152] The twin-screw extruder includes six temperature zones arranged in sequence: the first temperature zone has a temperature of 240℃, the second temperature zone has a temperature of 280℃, the third temperature zone has a temperature of 280℃, the fourth temperature zone has a temperature of 280℃, the fifth temperature zone has a temperature of 280℃, and the sixth temperature zone has a temperature of 280℃. The die temperature of the twin-screw extruder is 280℃, and the screw speed is 280 r / min.

[0153] Comparative Example 10

[0154] (1) Weigh 95 parts of PET, 13.5 parts of wear-resistant boron carbide, 0.1 parts of antioxidant Irganox 1098, and 0.1 parts of antioxidant Irganox 168, mix and stir evenly to obtain a mixture;

[0155] (2) The mixture obtained in step (1) is extruded from the extruder and granulated to obtain PET composite material D10.

[0156] The twin-screw extruder includes six temperature zones arranged in sequence: the first temperature zone has a temperature of 240℃, the second temperature zone has a temperature of 280℃, the third temperature zone has a temperature of 280℃, the fourth temperature zone has a temperature of 280℃, the fifth temperature zone has a temperature of 280℃, and the sixth temperature zone has a temperature of 280℃. The die temperature of the twin-screw extruder is 280℃, and the screw speed is 280 r / min.

[0157] The PET composite materials prepared in Example 5 and Comparative Examples 9-10 were injection molded into test strips. The test data are shown in the table below:

[0158]

[0159] In summary, the wear resistance and antibacterial properties of Example 5 are generally better than those of Comparative Examples 9-10.

[0160] As can be seen from the above embodiments and comparative examples, the thermoplastic resin composite material prepared by the method provided by the present invention has excellent wear resistance and antibacterial properties, which can expand the application field of thermoplastic resin composite materials.

[0161] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0162] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A wear-resistant and antibacterial thermoplastic resin composite material, characterized in that: Composed of the following components in parts by weight: 90-110 parts of thermoplastic resin 10-16 parts of functional filler Antioxidant 0.1-0.5 parts The functional filler is citral / PDA / boron carbide / MgO; The preparation method of citral / PDA / boron carbide / MgO includes the following steps: (1) Add magnesium phosphate and ammonia water to deionized water, react at room temperature, filter, wash and dry to obtain solid A; (2) Solid A was calcined in a muffle furnace, cooled, and then ground through a 500-mesh sieve to obtain solid B; (3) Place Tris-HCl buffer solution, dopamine hydrochloride, citral, boron carbide, anhydrous ethanol, deionized water, solid B, and crosslinking agent in a reactor vessel and react in a water bath; then filter, wash, and dry to obtain citral / PDA / boron carbide / MgO.

2. The thermoplastic resin composite material according to claim 1, characterized in that: In step (1), the mass ratio of magnesium phosphate to ammonia is (20-30):(30-36). The reaction time at room temperature is 4-6 hours, and the drying is carried out in a vacuum drying oven at 40-60℃ for 2-4 hours.

3. The thermoplastic resin composite material according to claim 1, characterized in that: In step (2), calcination is carried out at 640-720℃ for 10-12 hours.

4. The thermoplastic resin composite material according to claim 1, characterized in that: In step (3), the mass ratio of Tris-HCl buffer solution, dopamine hydrochloride, citral, boron carbide, anhydrous ethanol, deionized water, solid B, and crosslinking agent is (40-50): (30-40): (18-24): (30-36): (50-60): (60-70): (10-16): (0.1-0.3).

5. The thermoplastic resin composite material according to claim 1, characterized in that: The crosslinking agent mentioned in step (3) is vinyltriethoxysilane, dicumyl peroxide, or benzoyl peroxide; The water bath reaction temperature is 60-80℃ and the reaction time is 8-12h.

6. The thermoplastic resin composite material according to claim 1, characterized in that: In step (3), the Tris-HCl buffer solution is prepared by stirring Tris solution and HCl solution for 8-12 hours, wherein the mass ratio of Tris solution to HCl solution is (30-36):(36-40).

7. The thermoplastic resin composite material according to claim 1, characterized in that: The antioxidant is one or a mixture of several of the following: tris(2,4-di-tert-butyl)phosphite, N,N'-hexane-1,6-dimethylbis(3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)) and 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxyphenylmethyl)benzene.

8. The thermoplastic resin composite material according to claim 1, characterized in that: The thermoplastic resin is one of polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, and polyamide 6.

9. The method for preparing the thermoplastic resin composite material according to any one of claims 1-8, characterized in that: Includes the following steps: (1) Weigh 90-110 parts of thermoplastic resin, 10-16 parts of functional filler, and 0.1-0.5 parts of antioxidant, mix and stir evenly to obtain a mixture; (2) The mixture obtained in step (1) is extruded from the extruder and granulated to obtain the thermoplastic resin composite material.

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