Preparation method and application of antibacterial agent for ABS composite material

Abstract

This invention belongs to the field of polymer composite materials technology, specifically relating to a method for preparing and applying an antibacterial agent for ABS composite materials. The method involves reacting lanthanum acetate, sodium carbonate, anhydrous ethanol, and deionized water in a reactor to obtain solution A. Solution A is then filtered, washed, dried, and cooled to obtain lanthanum carbonate. The lanthanum carbonate is then calcined to obtain lanthanum oxide. Lanthanum oxide, linalool, 3-isocyanopropyltrimethoxysilane, anhydrous ethanol, and deionized water are reacted to obtain an antibacterial agent of the linalool / 3-isocyanopropyltrimethoxysilane / lanthanum oxide type. This antibacterial agent is then used in ABS to prepare antibacterial ABS composite materials. The antibacterial agent of this invention inhibits the metabolic activity of bacteria by interfering with their respiratory chain function. Furthermore, lanthanum ions, with their high positive charge density, adsorb onto the bacterial cell membrane surface, disrupting normal cellular physiological functions and thus killing the bacteria.

Description

Technical Field

[0001] This invention belongs to the field of polymer composite materials technology, specifically relating to a method for preparing and applying an antibacterial agent for ABS composite materials. Background Technology

[0002] Acrylonitrile-butadiene-styrene (ABS) is one of the most widely used plastics in modern times due to its low price, excellent performance, wide availability, and ease of processing. In some specific applications, antibacterial properties of ABS are required, which ordinary ABS composites cannot meet. Therefore, this application presents an antibacterial ABS composite material and its preparation method, which can be used in automotive interior materials. This type of material has not been reported to date, greatly expanding the application range of ABS composites and having significant practical implications. Summary of the Invention

[0003] The purpose of this invention is to provide a method for preparing and applying an antibacterial agent for ABS composite materials, which has excellent antibacterial properties, thereby solving the technical problem of limited antibacterial properties of ABS in the prior art.

[0004] To achieve the above objectives, this application employs the following technical solution:

[0005] A method for preparing an antibacterial agent for ABS composite materials includes the following steps:

[0006] S1. Weigh the specified amounts of lanthanum acetate, sodium carbonate, anhydrous ethanol, and deionized water, add them to a reactor vessel, and stir the reaction at 40-50℃ for 8-10 hours to obtain solution A.

[0007] S2. Filter and wash solution A, place it in a vacuum drying oven at 60-80℃ for 6-8 hours, and cool to obtain lanthanum carbonate;

[0008] S3. Lanthanum carbonate is placed in a crucible and calcined in a muffle furnace at 680-720℃ for 8-10 hours, and then cooled to obtain lanthanum oxide.

[0009] S4. Weigh out the specified amounts of lanthanum oxide, linalool, 3-isocyanate-propyltrimethoxysilane, anhydrous ethanol, and deionized water, add them to a reactor dish, react at 50-70℃ for 6-8 hours, filter, wash, and place in a vacuum drying oven at 50-60℃ for 8-10 hours to obtain an antibacterial agent of the linalool / 3-isocyanate-propyltrimethoxysilane / lanthanum oxide type.

[0010] Preferably, in step S1, the mass ratio of lanthanum acetate, sodium carbonate, anhydrous ethanol, and deionized water is (30-40):(30-36):(70-90):(80-100).

[0011] Preferably, in step S4, the mass ratio of lanthanum oxide, linalool, 3-isocyanate-propyltrimethoxysilane, anhydrous ethanol, and deionized water is (30-36):(20-24):(10-16):(60-70):(80-90).

[0012] Preferably, the method further includes step S5, in which the linalool / 3-isocyanate-propyltrimethoxysilane / lanthanum oxide type antibacterial agent prepared in step S4 is mixed with the lanthanum oxide prepared in step S3 at a mass ratio of (80-100):(10-20) to obtain a composite antibacterial agent.

[0013] Application of an antibacterial agent for ABS composite materials, wherein the antibacterial agent prepared by any of the above-mentioned methods for preparing an antibacterial agent for ABS composite materials is used in antibacterial ABS composite materials.

[0014] Preferably, the antibacterial ABS composite material is composed of 95-105 parts by weight of ABS, 3-5 parts by weight of antibacterial agent and 0.1-0.5 parts by weight of antioxidant.

[0015] Preferably, the antioxidant is one or a mixture of several of the following: tris(2,4-di-tert-butyl)phosphite, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] or 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxyphenyl)benzene.

[0016] The method for preparing ABS composite material is characterized by comprising the following steps:

[0017] (1) Weigh 95-105 parts of ABS, 3-5 parts of wear-resistant and antibacterial filler, and 0.1-0.5 parts of antioxidant, mix and stir evenly to obtain a mixture;

[0018] (2) The mixture obtained in step (1) is extruded and granulated to obtain ABS composite material.

[0019] The twin-screw extruder in step (2) includes six temperature zones arranged in sequence: zone 1 temperature 180-200℃, zone 2 temperature 240-260℃, zone 3 temperature 240-260℃, zone 4 temperature 240-260℃, zone 5 temperature 240-260℃, zone 6 temperature 240-260℃, and die head temperature 240-260℃; the screw speed is 200-280 r / min.

[0020] The beneficial effects of this invention are:

[0021] 1. The specific reaction equations involved in this technical solution are as follows:

[0022] 2La(CH3COO)3+3Na2CO3→La2(CO3)3+6CH3COONa,

[0023] La2(CO3)3→La2O3+3CO2.

[0024] 2. This patent synthesizes a novel linalool / 3-isocyanate-propyltrimethoxysilane / lanthanum oxide type antibacterial agent. 3-isocyanate-propyltrimethoxysilane acts as a bridge. On the one hand, it hydrolyzes to produce Si-OH, and the Si-OH undergoes a dehydration condensation reaction to form siloxane, which coats the surface of lanthanum oxide. On the other hand, the isocyanate of 3-isocyanate-propyltrimethoxysilane can react with the hydroxyl groups of linalool, ultimately forming a novel linalool / 3-isocyanate-propyltrimethoxysilane / lanthanum oxide type antibacterial agent.

[0025] 3. The antibacterial mechanism of this antibacterial agent is as follows: ① Linalool inhibits the metabolic activity of bacteria by interfering with their respiratory chain function. Studies have shown that it can significantly reduce the activity of respiratory chain dehydrogenases and inhibit the respiratory metabolism of *Pseudomonas berrieseri*, leading to inhibited energy production and thus achieving a bactericidal effect. ② Lanthanum ions have a high positive charge density and a strong electrostatic interaction with the negative charge that is usually present on the surface of bacterial cell membranes. Rare earth ions adsorb onto the cell membrane surface, disrupting the normal physiological functions of the cell, thereby killing bacteria. Detailed Implementation

[0026] The technical solutions of the present invention will be described in detail below through embodiments. The following embodiments are merely exemplary and can only be used to explain and illustrate the technical solutions of the present invention, and should not be construed as limiting the technical solutions of the present invention.

[0027] The raw materials used in the embodiments of the present invention are as follows:

[0028] ABS (model PA-757K), Zhenjiang Qimei Chemical Co., Ltd.; Lanthanum acetate, Langfang Qianyao Technology Co., Ltd.; Sodium carbonate, Shandong Luxing Chemical Co., Ltd.; Deionized water, Jinan Yuanfei Weiye Chemical Co., Ltd.; Anhydrous ethanol, Jinan Mingfa Chemical Co., Ltd.; Linalool, Jiangsu Runfeng Synthetic Technology Co., Ltd.; 3-isocyanate-propyltrimethoxysilane, Hubei Svit New Material Technology Co., Ltd.; Antioxidants (models Irganox168, Irganox1010, Irganox1330), BASF AG, Germany.

[0029] Preparation Example 1

[0030] (1) Weigh 300g lanthanum acetate, 300g sodium carbonate, 700g anhydrous ethanol and 800g deionized water, add them to a reactor vessel, stir and react at 40°C for 8h to obtain solution A.

[0031] (2) Solution A was filtered, washed, and dried in a vacuum drying oven at 60°C for 6 hours, and then cooled to obtain lanthanum carbonate.

[0032] (3) Lanthanum carbonate was placed in a crucible and calcined in a muffle furnace at 680°C for 8 hours. After cooling, lanthanum oxide was obtained.

[0033] (4) Weigh 300g lanthanum oxide, 200g linalool, 100g 3-isocyanate-propyltrimethoxysilane, 600g anhydrous ethanol and 800g deionized water, add them to a reactor dish, react at 50°C for 6h, filter, wash, and place in a vacuum drying oven at 50°C for 8h to obtain antibacterial agent M1 of the linalool / 3-isocyanate-propyltrimethoxysilane / lanthanum oxide type.

[0034] Example 1

[0035] (1) Weigh 95 parts of ABS, 3 parts of antibacterial agent M1, and 0.1 parts of antioxidant Irganox1010, mix and stir evenly to obtain a mixture;

[0036] (2) The mixture obtained in step (1) is extruded from the extruder and granulated to obtain ABS composite material P1.

[0037] The temperatures and screw speeds of the twin-screw extruder in each zone are as follows: Zone 1 temperature 180℃, Zone 2 temperature 240℃, Zone 3 temperature 240℃, Zone 4 temperature 240℃, Zone 5 temperature 240℃, Zone 6 temperature 240℃, Die head temperature 240℃, and screw speed 200r / min.

[0038] Preparation Example 2

[0039] (1) Weigh 400g lanthanum acetate, 360g sodium carbonate, 900g anhydrous ethanol and 1.0kg deionized water, add them to a reactor vessel, stir and react at 50℃ for 10h to obtain solution A.

[0040] (2) Solution A was filtered, washed, and dried in a vacuum drying oven at 80°C for 8 hours, and then cooled to obtain lanthanum carbonate.

[0041] (3) Lanthanum carbonate was placed in a crucible and calcined in a muffle furnace at 720°C for 10 h, and then cooled to obtain lanthanum oxide.

[0042] (4) Weigh 360g of lanthanum oxide, 240g of linalool, 160g of 3-isocyanate-propyltrimethoxysilane, 700g of anhydrous ethanol and 900g of deionized water, add them to a reactor dish, react at 70°C for 8h, filter, wash, and place in a vacuum drying oven at 60°C for 10h to obtain antibacterial agent M2 of the linalool / 3-isocyanate-propyltrimethoxysilane / lanthanum oxide type.

[0043] Example 2

[0044] (1) Weigh 105 parts of ABS, 5 parts of antibacterial agent M2, 0.1 parts of Irganox1010, 0.2 parts of Irganox168, and 0.2 parts of Irganox1330, mix and stir evenly to obtain a mixture;

[0045] (2) The mixture obtained in step (1) is extruded from the extruder and granulated to obtain ABS composite material P2.

[0046] The temperatures and screw speeds of the twin-screw extruder in each zone are as follows: Zone 1 temperature 200℃, Zone 2 temperature 260℃, Zone 3 temperature 260℃, Zone 4 temperature 260℃, Zone 5 temperature 260℃, Zone 6 temperature 260℃, Die head temperature 260℃, and screw speed 280r / min.

[0047] Preparation Example 3

[0048] (1) Weigh 350g lanthanum acetate, 330g sodium carbonate, 800g anhydrous ethanol and 900g deionized water, add them to a reactor vessel, stir and react at 45°C for 9h to obtain solution A.

[0049] (2) Solution A was filtered, washed, and dried in a vacuum drying oven at 70°C for 7 hours, and then cooled to obtain lanthanum carbonate.

[0050] (3) Lanthanum carbonate was placed in a crucible and calcined in a muffle furnace at 700°C for 9 hours. After cooling, lanthanum oxide was obtained.

[0051] (4) Weigh 330g of lanthanum oxide, 220g of linalool, 130g of 3-isocyanate-propyltrimethoxysilane, 650g of anhydrous ethanol and 850g of deionized water, add them to a reactor dish, react at 60°C for 7h, filter, wash, and place in a vacuum drying oven at 55°C for 9h to obtain antibacterial agent M3 of the linalool / 3-isocyanate-propyltrimethoxysilane / lanthanum oxide type.

[0052] Example 3

[0053] (1) Weigh 100 parts of ABS, 4 parts of antibacterial agent M3, 0.1 parts of Irganox168, and 0.2 parts of Irganox1010, mix and stir evenly to obtain a mixture;

[0054] (2) The mixture obtained in step (1) is extruded from the extruder and granulated to obtain ABS composite material P3.

[0055] The temperatures and screw speeds of the twin-screw extruder in each zone are as follows: Zone 1 temperature 190℃, Zone 2 temperature 250℃, Zone 3 temperature 250℃, Zone 4 temperature 250℃, Zone 5 temperature 250℃, Zone 6 temperature 250℃, and die head temperature 250℃; screw speed 240r / min.

[0056] Preparation Example 4

[0057] (1) Weigh 330g of lanthanum acetate, 325g of sodium carbonate, 777g of anhydrous ethanol and 885g of deionized water, add them to a reactor vessel, and stir at 42°C for 9.3h to obtain solution A.

[0058] (2) Solution A was filtered, washed, and dried in a vacuum drying oven at 67°C for 7.2 h. After cooling, lanthanum carbonate was obtained.

[0059] (3) Lanthanum carbonate was placed in a crucible and calcined in a muffle furnace at 715°C for 8.3 h, and then cooled to obtain lanthanum oxide.

[0060] (4) Weigh 355g of lanthanum oxide, 235g of linalool, 158g of 3-isocyanate-propyltrimethoxysilane, 665g of anhydrous ethanol and 838g of deionized water, add them to a reactor dish, react at 55°C for 7.2h, filter and wash, place in a vacuum drying oven at 54°C for 9.3h to obtain an antibacterial agent of the linalool / 3-isocyanate-propyltrimethoxysilane / lanthanum oxide type.

[0061] (5) Weigh 100g of linalool / 3-isocyanate-propyltrimethoxysilane / lanthanum oxide type antibacterial agent and 20g of lanthanum oxide, mix them evenly and then granulate them using a granulator to obtain composite antibacterial agent M4.

[0062] Example 4

[0063] (1) Weigh 98 parts of ABS, 4.6 parts of antibacterial agent M4, 0.1 parts of Irganox1010, and 0.2 parts of Irganox1330, mix and stir evenly to obtain a mixture;

[0064] (2) The mixture obtained in step (1) is extruded from the extruder and granulated to obtain ABS composite material P4.

[0065] The temperatures and screw speeds of the twin-screw extruder in each zone are as follows: Zone 1 temperature 195℃, Zone 2 temperature 255℃, Zone 3 temperature 255℃, Zone 4 temperature 255℃, Zone 5 temperature 255℃, Zone 6 temperature 255℃, and die head temperature 255℃; screw speed 260r / min.

[0066] Preparation Example 5

[0067] (1) Weigh 365g of lanthanum acetate, 346g of sodium carbonate, 785g of anhydrous ethanol and 925g of deionized water, add them to a reactor vessel, and stir the reaction at 41°C for 8.6h to obtain solution A.

[0068] (2) Solution A was filtered, washed, and dried in a vacuum drying oven at 66°C for 6 hours, and then cooled to obtain lanthanum carbonate.

[0069] (3) Lanthanum carbonate was placed in a crucible and calcined in a muffle furnace at 705°C for 8.2 h. After cooling, lanthanum oxide was obtained.

[0070] (4) Weigh 355g of lanthanum oxide, 235g of linalool, 155g of 3-isocyanate-propyltrimethoxysilane, 635g of anhydrous ethanol and 855g of deionized water, add them to a reactor dish, react at 65°C for 7.5h, filter and wash, place in a vacuum drying oven at 52°C for 9.2h to obtain an antibacterial agent of the linalool / 3-isocyanate-propyltrimethoxysilane / lanthanum oxide type.

[0071] (5) Weigh 90g of linalool / 3-isocyanate-propyltrimethoxysilane / lanthanum oxide type antibacterial agent and 15g of lanthanum oxide, mix them evenly and then granulate them using a granulator to obtain composite antibacterial agent M5.

[0072] Example 5

[0073] (1) Weigh 97 parts of ABS, 4.5 parts of antibacterial agent M5, 0.1 parts of Irganox1010, and 0.1 parts of Irganox168, mix and stir evenly to obtain a mixture;

[0074] (2) The mixture obtained in step (1) is extruded from the extruder and granulated to obtain ABS composite material P5.

[0075] The temperatures and screw speeds of the twin-screw extruder in each zone are as follows: Zone 1 temperature 195℃, Zone 2 temperature 245℃, Zone 3 temperature 245℃, Zone 4 temperature 245℃, Zone 5 temperature 245℃, Zone 6 temperature 245℃, and die head temperature 245℃; screw speed 255 r / min.

[0076] Comparative Example 1

[0077] (1) Weigh 97 parts of ABS, 4.5 parts of chitosan powder, 0.1 parts of Irganox1010, and 0.1 parts of Irganox168, mix and stir evenly to obtain a mixture;

[0078] (2) The mixture obtained in step (1) is extruded from the extruder and granulated to obtain ABS composite material D1.

[0079] The temperatures and screw speeds of the twin-screw extruder in each zone are as follows: Zone 1 temperature 195℃, Zone 2 temperature 245℃, Zone 3 temperature 245℃, Zone 4 temperature 245℃, Zone 5 temperature 245℃, Zone 6 temperature 245℃, and die head temperature 245℃; screw speed 255 r / min.

[0080] The performance data of the ABS composite materials of Examples 1-5 and Comparative Examples 1-2 are shown in the table below:

[0081]

[0082] As can be seen from the table above:

[0083] In summary, P1-5 has better antibacterial properties than D1, which indicates that the ABS composite material of the present invention has better antibacterial properties.

[0084] The above-disclosed embodiments are merely a few specific examples of this application, but this application is not limited thereto. Any variations that can be conceived by those skilled in the art should fall within the protection scope of this application.

Claims

1. A method for the preparation of an antimicrobial agent for ABS composites, characterized by, The method comprises the following steps: S1, a certain amount of lanthanum acetate, sodium carbonate, anhydrous ethanol and deionized water are weighed and added into a reaction vessel, and stirred at 40-50℃ for 8-10h to obtain solution A; S2, the solution A is filtered, washed, and dried in a vacuum drying oven at 60-80℃ for 6-8h to obtain lanthanum carbonate; S3, the lanthanum carbonate is placed in a crucible and calcined in a muffle furnace at 680-720℃ for 8-10h to obtain lanthanum oxide; S4, a certain amount of lanthanum oxide, linalool, 3-isocyanate propyl trimethoxysilane, anhydrous ethanol and deionized water are weighed and added into a reaction vessel, and reacted at 50-70℃ for 6-8h, then filtered, washed, and dried in a vacuum drying oven at 50-60℃ for 8-10h to obtain an antibacterial agent of linalool / 3-isocyanate propyl trimethoxysilane / lanthanum oxide type.

2. The method for preparing an antimicrobial agent for ABS composite according to claim 1, characterized in that, In step S1, the mass ratio of lanthanum acetate, sodium carbonate, anhydrous ethanol and deionized water is (30-40):(30-36):(70-90):(80-100).

3. The method for preparing an antimicrobial agent for ABS composite according to claim 1, characterized in that, In step S4, the mass ratio of lanthanum oxide, linalool, 3-isocyanate propyl trimethoxysilane, anhydrous ethanol and deionized water is (30-36):(20-24):(10-16):(60-70):(80-90).

4. The method for preparing an antimicrobial agent for ABS composite according to claim 1, characterized in that, Further comprising step S5, mixing the antibacterial agent of linalool / 3-isocyanate propyl trimethoxysilane / lanthanum oxide type prepared in step S4 with lanthanum oxide prepared in step S3 at a mass ratio of (80-100):(10-20) to obtain a composite antibacterial agent.

5. Use of an antimicrobial agent for ABS composites, characterized in that, The application of the antibacterial agent prepared by the method for preparing an antibacterial agent for ABS composite material according to any one of claims 1 to 4 in an antibacterial ABS composite material.

6. Use of an antimicrobial agent for ABS composites according to claim 5, characterized in that, The antibacterial ABS composite material is composed of 95-105 parts of ABS, 3-5 parts of the antibacterial agent and 0.1-0.5 parts of an antioxidant.

7. Use of an antimicrobial agent for ABS composites according to claim 6, characterized in that, The antioxidant is one or a mixture of several of tris(2,4-di-tert-butyl) phenyl phosphite, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] or 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzyl) benzene.

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