Antibacterial color masterbatch and preparation method thereof
By using aminosilane-modified jade powder and tris(acryloyloxyethyl) phosphate imidazole derivative in antibacterial masterbatch, the problem of poor compatibility between inorganic antibacterial agents and organic polymer resins was solved. This achieved uniform dispersion of antibacterial fillers in plastics and stability of efficient antibacterial performance, thus improving the heat resistance and antibacterial effect of the products.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- ANHUI CANCHENG NEW MATERIAL TECH CO LTD
- Filing Date
- 2026-04-29
- Publication Date
- 2026-05-29
AI Technical Summary
In existing antibacterial masterbatches, inorganic antibacterial agents have poor compatibility with organic polymer resins, resulting in uneven dispersion, which affects the mechanical properties of the product and the stability of the antibacterial effect. Furthermore, organic antibacterial agents have poor heat resistance and are prone to volatilization, while natural antibacterial agents have poor chemical stability and are prone to losing their activity.
An antibacterial filler is generated by the addition reaction of aminosilane-modified jade powder and tris(acryloyloxyethyl) phosphate imidazole derivative. Through the addition reaction, imidazole molecules are grafted onto the surface of jade powder to form a stable chemical structure, realizing the tight combination of inorganic antibacterial materials and organic antibacterial agents, promoting uniform dispersion in low-density polyethylene, and improving the stability and heat resistance of antibacterial properties.
It achieves uniform dispersion of antibacterial fillers during plastic processing, with stable antibacterial properties, good heat resistance and flame retardancy, and multiple antibacterial mechanisms, enhancing bactericidal effect and biocompatibility.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of polymer materials technology, specifically relating to an antibacterial masterbatch and its preparation method. Background Technology
[0002] Antibacterial masterbatch is generally added during the processing of polymer materials. It is an additive that gives materials antibacterial properties. It is obtained by blending and granulating antibacterial agents, carrier resins, dispersants and other additives. It is a core material used in the production of antibacterial plastics.
[0003] With the improvement of people's living standards and the enhancement of health awareness, antibacterial plastic products are increasingly widely used in food packaging, medical and health care, household appliances and daily necessities. Adding antibacterial masterbatch to plastics can avoid the problem of uneven dispersion that occurs when adding antibacterial agents directly during the plastic product manufacturing process, and has become the mainstream technical means for preparing antibacterial plastics.
[0004] Currently, there are many types of antibacterial agents used in antibacterial masterbatches, which can be roughly divided into three categories: inorganic antibacterial agents, organic antibacterial agents, and natural antibacterial agents. Inorganic antibacterial agents, compared to organic and natural antibacterial agents, have advantages such as strong drug resistance, long-lasting effect, no toxic side effects, and good heat resistance. However, they have poor compatibility with organic polymer resins, leading to uneven dispersion and consequently affecting the mechanical properties and stability of the antibacterial effect of the product. Organic antibacterial agents mainly include small molecule compounds such as quaternary ammonium salts, quaternary phosphonium salts, guanidine salts, and imidazoles. They are fast-acting and have excellent bactericidal effects against specific molds, but their heat resistance is poor, and they are prone to precipitation and volatilization during use, leading to a significant decrease or even loss of antibacterial performance. Natural antibacterial agents have good safety, but most natural antibacterial agents are sensitive to environmental factors, have poor chemical stability, and easily lose their antibacterial activity during granulation, thus having poor applicability.
[0005] Therefore, developing an antibacterial masterbatch that can remain stable during high-temperature processing, be uniformly dispersed in the matrix, and whose antibacterial components are not easily migrated or lost is of great practical significance. Summary of the Invention
[0006] The purpose of this invention is to provide an antibacterial masterbatch and its preparation method, which can solve the problems existing in the prior art.
[0007] The objective of this invention can be achieved through the following technical solutions: An antibacterial masterbatch, comprising the following raw materials by weight: Low-density polyethylene 60-80 parts, antibacterial filler 1-8 parts, antioxidant 1-3 parts, dispersant 0.1-1 parts, color powder 10-20 parts; The antibacterial filler was obtained by an addition reaction of aminosilane-modified jade powder and tris(acryloyloxyethyl) phosphate imidazole derivative; The tri(acryloyloxyethyl) phosphate imidazole derivative is obtained by an addition reaction between tri(acryloyloxyethyl) phosphate and imidazole.
[0008] Imidazole small-molecule organic antibacterial agents have strong bactericidal activity but poor heat resistance. This invention involves an addition reaction between imidazole and tris(acryloyloxyethyl) phosphate to generate a tris(acryloyloxyethyl) phosphate imidazole derivative. The phosphate group has good flame retardancy, and multiple double bonds provide reactive sites for the subsequent bonding of the derivative with jade powder. Jade powder mainly consists of silicon dioxide and magnesium oxide, possessing antibacterial, antifungal, and environmentally friendly properties, good chemical stability, and heat resistance. By modifying the jade powder and utilizing the addition reaction of amino and acryloyloxy groups, the imidazole ring and phosphate structure are chemically bonded to the jade powder surface. The jade powder provides a heat-resistant barrier for the imidazole organic antibacterial molecule. Furthermore, the double bonds on the acryloyloxy group involving tris(acryloyloxyethyl) phosphate promote cross-linking between the antibacterial filler and the resin. Through this molecular cross-linking mechanism, the inorganic antibacterial material (jade powder) and the organic antibacterial agent (imidazole) are tightly bound to low-density polyethylene, promoting uniform dispersion of the antibacterial filler in the low-density polyethylene and preventing the migration and loss of the antibacterial active components. The antibacterial filler contains inorganic antibacterial materials, phosphate groups and imidazole rings, which have a synergistic bactericidal effect and high heat resistance and flame retardancy, making the antibacterial masterbatch stable in antibacterial performance during plastic processing.
[0009] Furthermore, the preparation steps of the antibacterial filler are as follows: S1. Tris(acryloyloxyethyl) phosphate, triethylamine and 1-methylimidazole are mixed to obtain a mixture. Imidazole is dissolved in tetrahydrofuran to obtain an imidazole solution. Under a nitrogen atmosphere, the imidazole solution is added dropwise to the mixture while stirring. The mixture is stirred at room temperature for 12-24 hours. The solvent is removed by rotary evaporation to obtain the tris(acryloyloxyethyl) phosphate imidazole derivative. S2. Disperse aminosilane-modified jade powder in tetrahydrofuran, dissolve tris(acryloyloxyethyl) phosphate imidazole derivative in tetrahydrofuran, add the derivative solution to the dispersion, stir and react under nitrogen atmosphere for 48-72 h, filter, wash and dry to obtain antibacterial filler.
[0010] In the above preparation, tris(acryloyloxyethyl) phosphate contains a phosphate group and three acryloyloxy groups. The carbon-carbon double bond on it is a strong electrophilic acceptor, and the nitrogen atom on the imidazole ring acts as a nucleophile to attack the double bond, forming a carbon-nitrogen bond. This allows the tris(acryloyloxyethyl) phosphate molecular chain to be connected to the imidazole ring, generating a tris(acryloyloxyethyl) phosphate imidazole derivative. Aminosilane is then grafted onto the surface of jade powder to cover it with a large number of amino groups. The derivative is grafted onto the surface of jade powder by an addition reaction between the amino groups and the acryloyloxy groups on the tris(acryloyloxyethyl) phosphate imidazole derivative, thus obtaining an antibacterial filler.
[0011] Furthermore, the molar ratio of triethylamine to tris(acryloyloxyethyl) phosphate is (1.0-1.2):3; The molar ratio of 1-methylimidazole to tris(acryloyloxyethyl) phosphate is (0.10-0.12):1.
[0012] Furthermore, the concentration of the imidazole solution is 1.0-1.5M.
[0013] Further, the imidazole solution is added dropwise to the mixture at a molar ratio of imidazole to tris(acryloyloxyethyl) phosphate of 1.0-1.8:3.
[0014] Furthermore, the preparation steps of the aminosilane-modified jade powder are as follows: Jade powder was dispersed in ethanol to obtain a dispersion of 30-40 g / L. KH550 silane coupling agent was added to the ethanol-water mixture, and the pH was adjusted to 4-5. The mixture was stirred and hydrolyzed to obtain a hydrolysate. The hydrolysate was added to the dispersion at a concentration of 5-15% of the mass of the jade powder. The mixture was heated in a water bath at 70-80℃ and stirred for 4-6 hours. After filtration, washing and drying, aminosilane-modified jade powder was obtained.
[0015] Furthermore, the mass ratio of water to ethanol in the ethanol-water mixture is (1:9) to (2:8). The mass ratio of the KH550 silane coupling agent and the ethanol-water mixture is 1:(100-150).
[0016] Furthermore, the ratio of the aminosilane-modified jade powder to tetrahydrofuran is 20-40g:500mL.
[0017] Furthermore, the ratio of the tri(acryloyloxyethyl) phosphate imidazole derivative to tetrahydrofuran is 50-100g:500mL.
[0018] Furthermore, the derivative solution is added to the dispersion at a mass ratio of 1:(8-12) of tri(acryloyloxyethyl) phosphate imidazole derivative to aminosilane modified jade powder.
[0019] Furthermore, the antioxidant is at least one of antioxidant 1010 and antioxidant 168.
[0020] Furthermore, the dispersant is at least one of ethylene bis-stearamide, polyethylene wax, and zinc stearate.
[0021] Furthermore, the pigment is one of ultramarine blue pigment, cobalt blue pigment, cadmium yellow pigment, and titanium dioxide.
[0022] The present invention also provides a method for preparing antibacterial masterbatch, which is used to prepare the antibacterial masterbatch as described above, comprising the following steps: Step 1: Mix the raw materials according to the mass ratio; Step 2: Add the mixture to a twin-screw extruder and extrude and granulate to obtain antibacterial masterbatch.
[0023] The beneficial effects of this invention are: (1) In this invention, imidazole and tris(acryloyloxyethyl) phosphate are reacted by addition reaction to generate tris(acryloyloxyethyl) phosphate imidazole derivative. The phosphate group has good flame retardancy, and multiple double bonds can provide reactive sites for the subsequent binding of the derivative with jade powder. The tris(acryloyloxyethyl) phosphate imidazole derivative and aminosilane modified jade powder form a stable chemical structure through addition reaction. The tris(acryloyloxyethyl) phosphate imidazole derivative is grafted onto inorganic jade powder with extremely high thermal stability. The organic antibacterial compound and the inorganic antibacterial material are firmly bonded by chemical bonds, which improves the heat resistance of imidazole antibacterial molecules. The antibacterial filler can maintain high antibacterial activity after plastic processing and granulation. The antibacterial masterbatch has a long-lasting and stable antibacterial effect and good heat resistance and flame retardant properties.
[0024] (2) Based on the problem of easy migration of imidazole small molecules and poor compatibility of inorganic fillers, the present invention uses the polyacryloyloxy group of tris(acryloyloxyethyl) phosphate to graft imidazole molecules onto the surface of jade powder, providing organic molecular chains containing double bonds that can cross-link with low-density polyethylene, so that the grafted derivative molecular chains on the surface of jade powder interpenetrate and cross-link with the low-density polyethylene molecular chains, making it difficult for imidazole molecules to migrate from the interior of plastic products to the surface and precipitate. The antibacterial filler has good compatibility with resin, ensuring uniform composition of color masterbatch, and good antibacterial and mechanical properties.
[0025] (3) The antibacterial filler provided by the present invention contains antibacterial components jade powder, phosphate groups and imidazole rings, which work together to enhance the bactericidal effect. The phosphate substances selected in the antibacterial filler system have good biocompatibility and certain flame retardancy. The filler preparation process is mild, simple, safe and environmentally friendly. Detailed Implementation
[0026] 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.
[0027] Example 1 Preparation of aminosilane-modified jade powder: Weigh 0.7 kg of jade powder and add it to 2 L of ethanol. Disperse the mixture by ultrasonication for 30 min to obtain a dispersion.
[0028] Weigh 70g of deionized water and 630g of anhydrous ethanol and stir to mix evenly to obtain 700g of ethanol-water mixture. Add 70g of KH550 silane coupling agent to 700g of ethanol-water mixture, adjust the pH of the system to 4.5 with acetic acid and sodium hydroxide, and stir for 30min to obtain hydrolysate.
[0029] The hydrolysate was added to the dispersion, heated in a water bath to 75°C and stirred for 5 hours. After filtration, the mixture was washed three times each with deionized water and anhydrous ethanol, and dried in an oven at 70°C to obtain aminosilane-modified jade powder.
[0030] Preparation of antibacterial fillers: S1. Weigh 0.3763 kg (1 mol) of tris(acryloyloxyethyl) phosphate, 0.0354 kg (0.35 mol) of triethylamine and 0.0090 kg (0.11 mol) of 1-methylimidazole and mix them to obtain a mixture. Weigh 0.0326 kg (0.48 mol) of imidazole and dissolve it in tetrahydrofuran to obtain 400 mL of 1.2 M imidazole solution. Under a nitrogen atmosphere, while stirring, add all the prepared imidazole solution dropwise to the mixture. Stir the reaction at room temperature for 18 h. Remove the solvent by rotary evaporation to obtain the tris(acryloyloxyethyl) phosphate imidazole derivative.
[0031] S2. Weigh 60g of aminosilane-modified jade powder and add it to 1L of tetrahydrofuran. Disperse the mixture by ultrasonication for 20min to obtain a dispersion. Weigh 6g of tris(acryloyloxyethyl) phosphate imidazole derivative and dissolve it in 50mL of tetrahydrofuran. Add all of the obtained derivative solution to the dispersion. The mass ratio of tris(acryloyloxyethyl) phosphate imidazole derivative to aminosilane-modified jade powder is 1:10. Stir the mixture under a nitrogen atmosphere for 72h. After filtration, wash the mixture with deionized water and anhydrous ethanol in sequence. Dry the mixture in a vacuum drying oven at 60℃ to obtain the antibacterial filler.
[0032] An antibacterial masterbatch, by weight, comprises the following raw materials: 70 parts low-density polyethylene, 5 parts antibacterial filler prepared in this embodiment, 1 part antioxidant 1010, 1 part antioxidant 168, 0.5 parts ethylene bis-stearamide, and 15 parts titanium dioxide. The specific preparation steps are as follows: Step 1: Add the raw materials into a high-speed mixer according to the mass ratio, and stir at 500 rpm for 3 hours to obtain a mixture.
[0033] Step 2: Add the mixture to a twin-screw extruder, set the screw speed to 250 r / min, and set the temperatures of each zone as follows: Zone 1 120℃, Zone 2 160℃, Zone 3 200℃, Zone 4 180℃, and Zone 5 140℃. After extrusion, cool and granulate to obtain antibacterial masterbatch.
[0034] Example 2 The only difference from Example 1 is that, in preparing the antibacterial filler, the concentration of the imidazole solution in step S1 is adjusted to 1.5M.
[0035] The steps for preparing aminosilane-modified jade powder are the same as in Example 1.
[0036] Preparation of antibacterial fillers: S1. Weigh 0.3763 kg (1 mol) of tris(acryloyloxyethyl) phosphate, 0.0354 kg (0.35 mol) of triethylamine and 0.0090 kg (0.11 mol) of 1-methylimidazole and mix them to obtain a mixture. Weigh 0.0408 kg (0.60 mol) of imidazole and dissolve it in tetrahydrofuran to obtain 400 mL of 1.5 M imidazole solution. Under a nitrogen atmosphere, while stirring, add all the prepared imidazole solution dropwise to the mixture. Stir and react at room temperature for 18 h. Remove the solvent by rotary evaporation to obtain the tris(acryloyloxyethyl) phosphate imidazole derivative.
[0037] S2. Weigh 60g of aminosilane-modified jade powder and add it to 1L of tetrahydrofuran. Disperse the mixture by ultrasonication for 20min to obtain a dispersion. Weigh 6g of tris(acryloyloxyethyl) phosphate imidazole derivative and dissolve it in 50mL of tetrahydrofuran. Add all of the obtained derivative solution to the dispersion. The mass ratio of tris(acryloyloxyethyl) phosphate imidazole derivative to aminosilane-modified jade powder is 1:10. Stir the mixture under a nitrogen atmosphere for 72h. After filtration, wash the mixture with deionized water and anhydrous ethanol in sequence. Dry the mixture in a vacuum drying oven at 60℃ to obtain the antibacterial filler.
[0038] An antibacterial masterbatch, by weight, comprises the following raw materials: 70 parts low-density polyethylene, 5 parts antibacterial filler prepared in this embodiment, 1 part antioxidant 1010, 1 part antioxidant 168, 0.5 parts ethylene bis-stearamide, and 15 parts titanium dioxide. The specific preparation steps are as follows: Step 1: Add the raw materials into a high-speed mixer according to the mass ratio, and stir at 500 rpm for 3 hours to obtain a mixture.
[0039] Step 2: Add the mixture to a twin-screw extruder, set the screw speed to 250 r / min, and set the temperatures of each zone as follows: Zone 1 120℃, Zone 2 160℃, Zone 3 200℃, Zone 4 180℃, and Zone 5 140℃. After extrusion, cool and granulate to obtain antibacterial masterbatch.
[0040] Example 3 The only difference from Example 1 is that, in preparing the antibacterial filler, the concentration of the imidazole solution in step S1 is adjusted to 1.0M.
[0041] The steps for preparing aminosilane-modified jade powder are the same as in Example 1.
[0042] Preparation of antibacterial fillers: S1. Weigh 0.3763 kg (1 mol) of tris(acryloyloxyethyl) phosphate, 0.0354 kg (0.35 mol) of triethylamine and 0.0090 kg (0.11 mol) of 1-methylimidazole and mix them to obtain a mixture. Weigh 0.0272 kg (0.40 mol) of imidazole and dissolve it in tetrahydrofuran to obtain 400 mL of 1.0 M imidazole solution. Under a nitrogen atmosphere, while stirring, add all the prepared imidazole solution dropwise to the mixture. Stir the reaction at room temperature for 18 h. Remove the solvent by rotary evaporation to obtain the tris(acryloyloxyethyl) phosphate imidazole derivative.
[0043] S2. Weigh 60g of aminosilane-modified jade powder and add it to 1L of tetrahydrofuran. Disperse the mixture by ultrasonication for 20min to obtain a dispersion. Weigh 6g of tris(acryloyloxyethyl) phosphate imidazole derivative and dissolve it in 50mL of tetrahydrofuran. Add all of the obtained derivative solution to the dispersion. The mass ratio of tris(acryloyloxyethyl) phosphate imidazole derivative to aminosilane-modified jade powder is 1:10. Stir the mixture under a nitrogen atmosphere for 72h. After filtration, wash the mixture with deionized water and anhydrous ethanol in sequence. Dry the mixture in a vacuum drying oven at 60℃ to obtain the antibacterial filler.
[0044] An antibacterial masterbatch, by weight, comprises the following raw materials: 70 parts low-density polyethylene, 5 parts antibacterial filler prepared in this embodiment, 1 part antioxidant 1010, 1 part antioxidant 168, 0.5 parts ethylene bis-stearamide, and 15 parts titanium dioxide. The specific preparation steps are as follows: Step 1: Add the raw materials into a high-speed mixer according to the mass ratio, and stir at 500 rpm for 3 hours to obtain a mixture.
[0045] Step 2: Add the mixture to a twin-screw extruder, set the screw speed to 250 r / min, and set the temperatures of each zone as follows: Zone 1 120℃, Zone 2 160℃, Zone 3 200℃, Zone 4 180℃, and Zone 5 140℃. After extrusion, cool and granulate to obtain antibacterial masterbatch.
[0046] Example 4 The only difference from Example 1 is that, in the preparation of the antibacterial filler, the mass ratio of tris(acryloyloxyethyl) phosphate imidazole derivative to aminosilane modified jade powder in step S2 is adjusted to 1:12.
[0047] Preparation of aminosilane-modified jade powder: Weigh 0.7 kg of jade powder and add it to 2 L of ethanol. Disperse the mixture by ultrasonication for 30 min to obtain a dispersion.
[0048] Weigh 70g of deionized water and 630g of anhydrous ethanol and stir to mix evenly to obtain 700g of ethanol-water mixture. Add 70g of KH550 silane coupling agent to 700g of ethanol-water mixture, adjust the pH of the system to 4.5 with acetic acid and sodium hydroxide, and stir for 30min to obtain hydrolysate.
[0049] The hydrolysate was added to the dispersion, heated in a water bath to 75°C and stirred for 5 hours. After filtration, the mixture was washed three times each with deionized water and anhydrous ethanol, and dried in an oven at 70°C to obtain aminosilane-modified jade powder.
[0050] Preparation of antibacterial fillers: S1. Weigh 0.3763 kg (1 mol) of tris(acryloyloxyethyl) phosphate, 0.0354 kg (0.35 mol) of triethylamine and 0.0090 kg (0.11 mol) of 1-methylimidazole and mix them to obtain a mixture. Weigh 0.0326 kg (0.48 mol) of imidazole and dissolve it in tetrahydrofuran to obtain 400 mL of 1.2 M imidazole solution. Under a nitrogen atmosphere, while stirring, add all the prepared imidazole solution dropwise to the mixture. Stir the reaction at room temperature for 18 h. Remove the solvent by rotary evaporation to obtain the tris(acryloyloxyethyl) phosphate imidazole derivative.
[0051] S2. Weigh 60g of aminosilane-modified jade powder and add it to 1L of tetrahydrofuran. Disperse the mixture by ultrasonication for 20min to obtain a dispersion. Weigh 5g of tris(acryloyloxyethyl) phosphate imidazole derivative and dissolve it in 50mL of tetrahydrofuran. Add all of the obtained derivative solution to the dispersion. The mass ratio of tris(acryloyloxyethyl) phosphate imidazole derivative to aminosilane-modified jade powder is 1:12. Stir the mixture under a nitrogen atmosphere for 72h. After filtration, wash the mixture with deionized water and anhydrous ethanol in sequence. Dry the mixture in a vacuum drying oven at 60℃ to obtain the antibacterial filler.
[0052] An antibacterial masterbatch, by weight, comprises the following raw materials: 70 parts low-density polyethylene, 5 parts antibacterial filler prepared in this embodiment, 1 part antioxidant 1010, 1 part antioxidant 168, 0.5 parts ethylene bis-stearamide, and 15 parts titanium dioxide. The specific preparation steps are as follows: Step 1: Add the raw materials into a high-speed mixer according to the mass ratio, and stir at 500 rpm for 3 hours to obtain a mixture.
[0053] Step 2: Add the mixture to a twin-screw extruder, set the screw speed to 250 r / min, and set the temperatures of each zone as follows: Zone 1 120℃, Zone 2 160℃, Zone 3 200℃, Zone 4 180℃, and Zone 5 140℃. After extrusion, cool and granulate to obtain antibacterial masterbatch.
[0054] Example 5 The only difference from Example 1 is that, in the preparation of the antibacterial filler, the mass ratio of tris(acryloyloxyethyl) phosphate imidazole derivative to aminosilane modified jade powder in step S2 is adjusted to 1:8.
[0055] Preparation of aminosilane-modified jade powder: Weigh 0.7 kg of jade powder and add it to 2 L of ethanol. Disperse the mixture by ultrasonication for 30 min to obtain a dispersion.
[0056] Weigh 70g of deionized water and 630g of anhydrous ethanol and stir to mix evenly to obtain 700g of ethanol-water mixture. Add 70g of KH550 silane coupling agent to 700g of ethanol-water mixture, adjust the pH of the system to 4.5 with acetic acid and sodium hydroxide, and stir for 30min to obtain hydrolysate.
[0057] The hydrolysate was added to the dispersion, heated in a water bath to 75°C and stirred for 5 hours. After filtration, the mixture was washed three times each with deionized water and anhydrous ethanol, and dried in an oven at 70°C to obtain aminosilane-modified jade powder.
[0058] Preparation of antibacterial fillers: S1. Weigh 0.3763 kg (1 mol) of tris(acryloyloxyethyl) phosphate, 0.0354 kg (0.35 mol) of triethylamine and 0.0090 kg (0.11 mol) of 1-methylimidazole and mix them to obtain a mixture. Weigh 0.0326 kg (0.48 mol) of imidazole and dissolve it in tetrahydrofuran to obtain 400 mL of 1.2 M imidazole solution. Under a nitrogen atmosphere, while stirring, add all the prepared imidazole solution dropwise to the mixture. Stir the reaction at room temperature for 18 h. Remove the solvent by rotary evaporation to obtain the tris(acryloyloxyethyl) phosphate imidazole derivative.
[0059] S2. Weigh 60g of aminosilane-modified jade powder and add it to 1L of tetrahydrofuran. Disperse the mixture by ultrasonication for 20min to obtain a dispersion. Weigh 7.5g of tris(acryloyloxyethyl) phosphate imidazole derivative and dissolve it in 50mL of tetrahydrofuran. Add all of the obtained derivative solution to the dispersion. The mass ratio of tris(acryloyloxyethyl) phosphate imidazole derivative to aminosilane-modified jade powder is 1:8. Stir and react under a nitrogen atmosphere for 72h. After filtration, wash with deionized water and anhydrous ethanol in sequence, and dry in a vacuum drying oven at 60℃ to obtain antibacterial filler.
[0060] An antibacterial masterbatch, by weight, comprises the following raw materials: 70 parts low-density polyethylene, 5 parts antibacterial filler prepared in this embodiment, 1 part antioxidant 1010, 1 part antioxidant 168, 0.5 parts ethylene bis-stearamide, and 15 parts titanium dioxide. The specific preparation steps are as follows: Step 1: Add the raw materials into a high-speed mixer according to the mass ratio, and stir at 500 rpm for 3 hours to obtain a mixture.
[0061] Step 2: Add the mixture to a twin-screw extruder, set the screw speed to 250 r / min, and set the temperatures of each zone as follows: Zone 1 120℃, Zone 2 160℃, Zone 3 200℃, Zone 4 180℃, and Zone 5 140℃. After extrusion, cool and granulate to obtain antibacterial masterbatch.
[0062] Example 6 The only difference from Example 1 is that the mass fraction of antibacterial filler in the antibacterial masterbatch raw material is adjusted to 8 parts.
[0063] Preparation of aminosilane-modified jade powder: Weigh 0.7 kg of jade powder and add it to 2 L of ethanol. Disperse the mixture by ultrasonication for 30 min to obtain a dispersion.
[0064] Weigh 70g of deionized water and 630g of anhydrous ethanol and stir to mix evenly to obtain 700g of ethanol-water mixture. Add 70g of KH550 silane coupling agent to 700g of ethanol-water mixture, adjust the pH of the system to 4.5 with acetic acid and sodium hydroxide, and stir for 30min to obtain hydrolysate.
[0065] The hydrolysate was added to the dispersion, heated in a water bath to 75°C and stirred for 5 hours. After filtration, the mixture was washed three times each with deionized water and anhydrous ethanol, and dried in an oven at 70°C to obtain aminosilane-modified jade powder.
[0066] Preparation of antibacterial fillers: S1. Weigh 0.3763 kg (1 mol) of tris(acryloyloxyethyl) phosphate, 0.0354 kg (0.35 mol) of triethylamine and 0.0090 kg (0.11 mol) of 1-methylimidazole and mix them to obtain a mixture. Weigh 0.0326 kg (0.48 mol) of imidazole and dissolve it in tetrahydrofuran to obtain 400 mL of 1.2 M imidazole solution. Under a nitrogen atmosphere, while stirring, add all the prepared imidazole solution dropwise to the mixture. Stir the reaction at room temperature for 18 h. Remove the solvent by rotary evaporation to obtain the tris(acryloyloxyethyl) phosphate imidazole derivative.
[0067] S2. Weigh 60g of aminosilane-modified jade powder and add it to 1L of tetrahydrofuran. Disperse the mixture by ultrasonication for 20min to obtain a dispersion. Weigh 6g of tris(acryloyloxyethyl) phosphate imidazole derivative and dissolve it in 50mL of tetrahydrofuran. Add all of the obtained derivative solution to the dispersion. The mass ratio of tris(acryloyloxyethyl) phosphate imidazole derivative to aminosilane-modified jade powder is 1:10. Stir the mixture under a nitrogen atmosphere for 72h. After filtration, wash the mixture with deionized water and anhydrous ethanol in sequence. Dry the mixture in a vacuum drying oven at 60℃ to obtain the antibacterial filler.
[0068] An antibacterial masterbatch, by weight, comprises the following raw materials: 70 parts low-density polyethylene, 8 parts antibacterial filler prepared in this embodiment, 1 part antioxidant 1010, 1 part antioxidant 168, 0.5 parts ethylene bis-stearamide, and 15 parts titanium dioxide. The specific preparation steps are as follows: Step 1: Add the raw materials into a high-speed mixer according to the mass ratio, and stir at 500 rpm for 3 hours to obtain a mixture.
[0069] Step 2: Add the mixture to a twin-screw extruder, set the screw speed to 250 r / min, and set the temperatures of each zone as follows: Zone 1 120℃, Zone 2 160℃, Zone 3 200℃, Zone 4 180℃, and Zone 5 140℃. After extrusion, cool and granulate to obtain antibacterial masterbatch.
[0070] Example 7 The only difference from Example 1 is that the mass fraction of antibacterial filler in the antibacterial masterbatch raw material is adjusted to 1 part.
[0071] Preparation of aminosilane-modified jade powder: Weigh 0.7 kg of jade powder and add it to 2 L of ethanol. Disperse the mixture by ultrasonication for 30 min to obtain a dispersion.
[0072] Weigh 70g of deionized water and 630g of anhydrous ethanol and stir to mix evenly to obtain 700g of ethanol-water mixture. Add 70g of KH550 silane coupling agent to 700g of ethanol-water mixture, adjust the pH of the system to 4.5 with acetic acid and sodium hydroxide, and stir for 30min to obtain hydrolysate.
[0073] The hydrolysate was added to the dispersion, heated in a water bath to 75°C and stirred for 5 hours. After filtration, the mixture was washed three times each with deionized water and anhydrous ethanol, and dried in an oven at 70°C to obtain aminosilane-modified jade powder.
[0074] Preparation of antibacterial fillers: S1. Weigh 0.3763 kg (1 mol) of tris(acryloyloxyethyl) phosphate, 0.0354 kg (0.35 mol) of triethylamine and 0.0090 kg (0.11 mol) of 1-methylimidazole and mix them to obtain a mixture. Weigh 0.0326 kg (0.48 mol) of imidazole and dissolve it in tetrahydrofuran to obtain 400 mL of 1.2 M imidazole solution. Under a nitrogen atmosphere, while stirring, add all the prepared imidazole solution dropwise to the mixture. Stir the reaction at room temperature for 18 h. Remove the solvent by rotary evaporation to obtain the tris(acryloyloxyethyl) phosphate imidazole derivative.
[0075] S2. Weigh 60g of aminosilane-modified jade powder and add it to 1L of tetrahydrofuran. Disperse the mixture by ultrasonication for 20min to obtain a dispersion. Weigh 6g of tris(acryloyloxyethyl) phosphate imidazole derivative and dissolve it in 50mL of tetrahydrofuran. Add all of the obtained derivative solution to the dispersion. The mass ratio of tris(acryloyloxyethyl) phosphate imidazole derivative to aminosilane-modified jade powder is 1:10. Stir the mixture under a nitrogen atmosphere for 72h. After filtration, wash the mixture with deionized water and anhydrous ethanol in sequence. Dry the mixture in a vacuum drying oven at 60℃ to obtain the antibacterial filler.
[0076] An antibacterial masterbatch, by weight, comprises the following raw materials: 70 parts low-density polyethylene, 1 part antibacterial filler prepared in this embodiment, 1 part antioxidant 1010, 1 part antioxidant 168, 0.5 parts ethylene bis-stearamide, and 15 parts titanium dioxide. The specific preparation steps are as follows: Step 1: Add the raw materials into a high-speed mixer according to the mass ratio, and stir at 500 rpm for 3 hours to obtain a mixture.
[0077] Step 2: Add the mixture to a twin-screw extruder, set the screw speed to 250 r / min, and set the temperatures of each zone as follows: Zone 1 120℃, Zone 2 160℃, Zone 3 200℃, Zone 4 180℃, and Zone 5 140℃. After extrusion, cool and granulate to obtain antibacterial masterbatch.
[0078] Examples 8-9 The only difference from Example 1 is that the mass fraction of the raw materials in the antibacterial masterbatch is different, and the specific ratio is shown in Table 1.
[0079] Table 1
[0080] Comparative Example 1 The only difference from Example 1 is that this comparative example directly uses tris(acryloyloxyethyl) phosphate imidazole derivative as the raw material for antibacterial masterbatch.
[0081] Preparation of tri(acryloyloxyethyl) phosphate imidazole derivatives: Weigh 0.3763 kg (1 mol) of tris(acryloyloxyethyl) phosphate, 0.0354 kg (0.35 mol) of triethylamine and 0.0090 kg (0.11 mol) of 1-methylimidazole and mix them to obtain a mixture. Weigh 0.0326 kg (0.48 mol) of imidazole and dissolve it in tetrahydrofuran to obtain 400 mL of 1.2 M imidazole solution. Under a nitrogen atmosphere, while stirring, add all the prepared imidazole solution dropwise to the mixture. Stir the reaction at room temperature for 18 h. Remove the solvent by rotary evaporation to obtain the tris(acryloyloxyethyl) phosphate imidazole derivative.
[0082] An antibacterial masterbatch, by weight, comprises the following raw materials: 70 parts low-density polyethylene, 0.45 parts tris(acryloyloxyethyl) phosphate imidazole derivative prepared in this comparative example, 1 part antioxidant 1010, 1 part antioxidant 168, 0.5 parts ethylene bis-stearamide, and 15 parts titanium dioxide. The specific preparation steps are as follows: Step 1: Add the raw materials into a high-speed mixer according to the mass ratio, and stir at 500 rpm for 3 hours to obtain a mixture.
[0083] Step 2: Add the mixture to a twin-screw extruder, set the screw speed to 250 r / min, and set the temperatures of each zone as follows: Zone 1 120℃, Zone 2 160℃, Zone 3 200℃, Zone 4 180℃, and Zone 5 140℃. After extrusion, cool and granulate to obtain antibacterial masterbatch.
[0084] Comparative Example 2 The only difference from Example 1 is that this comparative example directly prepared antibacterial filler by reacting tris(acryloyloxyethyl) phosphate and aminosilane-modified jade powder.
[0085] Preparation of aminosilane-modified jade powder: Weigh 0.7 kg of jade powder and add it to 2 L of ethanol. Disperse the mixture by ultrasonication for 30 min to obtain a dispersion.
[0086] Weigh 70g of deionized water and 630g of anhydrous ethanol and stir to mix evenly to obtain 700g of ethanol-water mixture. Add 70g of KH550 silane coupling agent to 700g of ethanol-water mixture, adjust the pH of the system to 4.5 with acetic acid and sodium hydroxide, and stir for 30min to obtain hydrolysate.
[0087] The hydrolysate was added to the dispersion, heated in a water bath to 75°C and stirred for 5 hours. After filtration, the mixture was washed three times each with deionized water and anhydrous ethanol, and dried in an oven at 70°C to obtain aminosilane-modified jade powder.
[0088] Preparation of antibacterial fillers: 60g of aminosilane-modified jade powder was added to 1L of tetrahydrofuran and ultrasonically dispersed for 20min to obtain a dispersion. 6g of tris(acryloyloxyethyl) phosphate was dissolved in 50mL of tetrahydrofuran. All of the obtained derivative solution was added to the dispersion. The mass ratio of tris(acryloyloxyethyl) phosphate to aminosilane-modified jade powder was 1:10. The mixture was stirred and reacted under a nitrogen atmosphere for 72h. After filtration, the mixture was washed successively with deionized water and anhydrous ethanol and dried in a vacuum drying oven at 60℃ to obtain the antibacterial filler.
[0089] An antibacterial masterbatch, by weight, comprises the following raw materials: 70 parts low-density polyethylene, 5 parts antibacterial filler prepared in this comparative proportion, 1 part antioxidant 1010, 1 part antioxidant 168, 0.5 parts ethylene bis-stearamide, and 15 parts titanium dioxide. The specific preparation steps are as follows: Step 1: Add the raw materials into a high-speed mixer according to the mass ratio, and stir at 500 rpm for 3 hours to obtain a mixture.
[0090] Step 2: Add the mixture to a twin-screw extruder, set the screw speed to 250 r / min, and set the temperatures of each zone as follows: Zone 1 120℃, Zone 2 160℃, Zone 3 200℃, Zone 4 180℃, and Zone 5 140℃. After extrusion, cool and granulate to obtain antibacterial masterbatch.
[0091] Comparative Example 3 The only difference from Example 1 is that in the preparation of the comparative antibacterial masterbatch, aminosilane-modified jade powder and other materials are used to replace the antibacterial filler.
[0092] Preparation of aminosilane-modified jade powder: Weigh 0.7 kg of jade powder and add it to 2 L of ethanol. Disperse the mixture by ultrasonication for 30 min to obtain a dispersion.
[0093] Weigh 70g of deionized water and 630g of anhydrous ethanol and stir to mix evenly to obtain 700g of ethanol-water mixture. Add 70g of KH550 silane coupling agent to 700g of ethanol-water mixture, adjust the pH of the system to 4.5 with acetic acid and sodium hydroxide, and stir for 30min to obtain hydrolysate.
[0094] The hydrolysate was added to the dispersion, heated in a water bath to 75°C and stirred for 5 hours. After filtration, the mixture was washed three times each with deionized water and anhydrous ethanol, and dried in an oven at 70°C to obtain aminosilane-modified jade powder.
[0095] An antibacterial masterbatch, by weight, comprises the following raw materials: 70 parts low-density polyethylene, 5 parts aminosilane-modified jade powder prepared in this embodiment, 1 part antioxidant 1010, 1 part antioxidant 168, 0.5 parts ethylene bis-stearamide, and 15 parts titanium dioxide. The specific preparation steps are as follows: Step 1: Add the raw materials into a high-speed mixer according to the mass ratio, and stir at 500 rpm for 3 hours to obtain a mixture.
[0096] Step 2: Add the mixture to a twin-screw extruder, set the screw speed to 250 r / min, and set the temperatures of each zone as follows: Zone 1 120℃, Zone 2 160℃, Zone 3 200℃, Zone 4 180℃, and Zone 5 140℃. After extrusion, cool and granulate to obtain antibacterial masterbatch.
[0097] Comparative Example 4 The only difference from Example 1 is that no antibacterial filler is added to the raw materials used to prepare the comparative masterbatch.
[0098] A color masterbatch, by weight, comprises the following raw materials: 70 parts low-density polyethylene, 1 part antioxidant 1010, 1 part antioxidant 168, 0.5 parts ethylene bis-stearamide, and 15 parts titanium dioxide. The specific preparation steps are as follows: Step 1: Add the raw materials into a high-speed mixer according to the mass ratio, and stir at 500 rpm for 3 hours to obtain a mixture.
[0099] Step 2: Add the mixture to a twin-screw extruder, set the screw speed to 250 r / min, and set the temperatures of each zone as follows: Zone 1 120℃, Zone 2 160℃, Zone 3 200℃, Zone 4 180℃, and Zone 5 140℃. After extrusion, cool and granulate to obtain antibacterial masterbatch.
[0100] The performance of the color masterbatches prepared in Examples 1-9 and Comparative Examples 1-4 was tested, and the results are shown in Table 2.
[0101] Test samples were prepared using masterbatches prepared according to the examples and comparative examples. Tensile strength was tested according to ISO 527. Antibacterial rate was tested according to GB / T 31402-2023, "Determination of antibacterial activity of surfaces of plastics and other non-porous materials". Flame retardant performance was tested by vertical burning tests according to the UL-94 flame retardancy rating standard.
[0102] Table 2
[0103] As shown in Table 2, the antibacterial masterbatches prepared in Examples 1-9 not only possess excellent antibacterial properties but also exhibit good mechanical and flame-retardant properties. The results of Example 1 and Comparative Example 1 show that the grafting of jade powder and tris(acryloyloxyethyl) phosphate imidazole derivative can improve the thermal stability of the antibacterial active component, resulting in better antibacterial properties in the processed and granulated antibacterial masterbatches. Furthermore, the addition of jade powder contributes to the good mechanical properties of the antibacterial masterbatches. Combining Example 1 and Comparative Example 2, it is evident that the introduction of the imidazole ring can significantly improve the antibacterial rate of the antibacterial masterbatches against Staphylococcus aureus and Escherichia coli. Combining Example 1 and Comparative Example 4, it is clear that adding antibacterial filler to the masterbatch significantly improves all indicators of its mechanical, antibacterial, and flame-retardant properties.
[0104] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.
[0105] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.
Claims
1. An antibacterial masterbatch, characterized in that, By weight, it includes the following raw materials: Low-density polyethylene 60-80 parts, antibacterial filler 1-8 parts, antioxidant 1-3 parts, dispersant 0.1-1 parts, color powder 10-20 parts; The antibacterial filler was obtained by an addition reaction of aminosilane-modified jade powder and tris(acryloyloxyethyl) phosphate imidazole derivative; The tri(acryloyloxyethyl) phosphate imidazole derivative is obtained by an addition reaction between tri(acryloyloxyethyl) phosphate and imidazole.
2. The antibacterial masterbatch according to claim 1, characterized in that, The preparation steps of the antibacterial filler are as follows: S1. Tris(acryloyloxyethyl) phosphate, triethylamine and 1-methylimidazole are mixed to obtain a mixture. Imidazole is dissolved in tetrahydrofuran to obtain an imidazole solution. Under a nitrogen atmosphere, the imidazole solution is added dropwise to the mixture while stirring. The mixture is stirred at room temperature for 12-24 hours. The solvent is removed by rotary evaporation to obtain the tris(acryloyloxyethyl) phosphate imidazole derivative. S2. Disperse aminosilane-modified jade powder in tetrahydrofuran, dissolve tris(acryloyloxyethyl) phosphate imidazole derivative in tetrahydrofuran, add the derivative solution to the dispersion, stir and react under nitrogen atmosphere for 48-72 h, filter, wash and dry to obtain antibacterial filler.
3. The antibacterial masterbatch according to claim 2, characterized in that, The molar ratio of triethylamine to tris(acryloyloxyethyl) phosphate is (1.0-1.2):3; The molar ratio of 1-methylimidazole to tris(acryloyloxyethyl) phosphate is (0.10-0.12):
1.
4. The antibacterial masterbatch according to claim 2, characterized in that, The concentration of the imidazole solution is 1.0-1.5M.
5. The antibacterial masterbatch according to claim 2, characterized in that, The imidazole solution was added dropwise to the mixture at a molar ratio of imidazole to tris(acryloyloxyethyl) phosphate of (1.0-1.8):
3.
6. The antibacterial masterbatch according to claim 2, characterized in that, The preparation steps of the aminosilane-modified jade powder are as follows: Jade powder was dispersed in ethanol to obtain a dispersion of 30-40 g / L. KH550 silane coupling agent was added to the ethanol-water mixture, and the pH was adjusted to 4-5. The mixture was stirred and hydrolyzed to obtain a hydrolysate. The hydrolysate was added to the dispersion at a concentration of 5-15% of the mass of the jade powder. The mixture was heated in a water bath at 70-80℃ and stirred for 4-6 hours. After filtration, washing and drying, aminosilane-modified jade powder was obtained.
7. The antibacterial masterbatch according to claim 6, characterized in that, The mass ratio of water to ethanol in the ethanol-water mixture is (1:9)-(2:8). The mass ratio of the KH550 silane coupling agent and the ethanol-water mixture is 1:(100-150).
8. The antibacterial masterbatch according to claim 6, characterized in that, The ratio of aminosilane-modified jade powder to tetrahydrofuran is 20-40g:500mL; The ratio of the tri(acryloyloxyethyl) phosphate imidazole derivative to tetrahydrofuran is 50-100g:500mL.
9. An antibacterial masterbatch according to claim 6, characterized in that, The derivative solution was added to the dispersion at a mass ratio of 1:(8-12) of tri(acryloyloxyethyl) phosphate imidazole derivative to aminosilane-modified jade powder.
10. A method for preparing an antibacterial masterbatch, characterized in that, The preparation of the antibacterial masterbatch as described in any one of claims 1-9 includes the following steps: Step 1: Mix the raw materials according to the mass ratio; Step 2: Add the mixture to a twin-screw extruder and extrude and granulate to obtain antibacterial masterbatch.