Antibacterial PP material and preparation method thereof

Abstract

The invention relates to an antibacterial PP material and a preparation method thereof, and belongs to the technical field of high polymer materials. The antibacterial PP material is prepared from the following components in parts by weight: 60 to 80 parts of PP resin, 2 to 4 parts of a surfactant, 0.5 to 1.5 parts of a modified antibacterial agent, 0.5 to 1.5 parts of a flame retardant and 0.2 to 0.8 part of an antioxidant, titanium ions in the modified antibacterial agent destroy bacterial cell walls, quaternized intermediate products react with proteins of cell membranes to accelerate bacterial death, and in addition, phenolic hydroxyl groups absorb ultraviolet rays with different wavelengths to inhibit the light aging process; a compact and continuous carbon layer is formed during combustion of the flame retardant and cooperates with phosphorus-oxygen double bonds and melamine, the flame retardant efficiency is improved, aluminum hydroxide coats the surface, hydroxyl is subjected to heat absorption decomposition during combustion, the surface temperature of combustible materials is stabilized, meanwhile, an inert aluminum oxide layer is formed, and the flammability is reduced. The antibacterial PP material prepared by the invention not only has good antibacterial and anti-aging effects, but also has excellent flame retardant property.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to an antibacterial PP material and a preparation method thereof. Background Art

[0002] PP material (polypropylene) is a semi-crystalline thermoplastic. Due to its excellent mechanical properties, chemical corrosion resistance and thermal stability, it shows broad application prospects in many fields such as food packaging, medical devices and household products.

[0003] However, with the improvement of modern life quality and people's increasing attention to health and safety, people are paying more and more attention to disease prevention and health protection. During long-term use, traditional PP products are prone to breed bacteria on their surfaces due to the lack of antibacterial properties. These bacteria not only irritate human skin and cause various skin problems, but also accelerate the aging of PP materials, shorten their service life, and increase resource consumption. In addition, PP materials are derived from petrochemical materials, composed of hydrocarbon elements, are flammable, and can easily be ignited to cause fires. These problems limit the wider and deeper application of PP. Summary of the invention

[0004] In order to solve the above technical problems, the present invention provides an antibacterial PP material and a preparation method thereof.

[0005] The purpose of the present invention can be achieved through the following technical solutions: An antibacterial PP material comprises the following raw materials in parts by weight: 60-80 parts of PP resin, 2-4 parts of surfactant, 0.5-1.5 parts of modified antibacterial agent, 0.5-1.5 parts of flame retardant, and 0.2-0.8 parts of antioxidant.

[0006] The surfactant is Clariant FA14; The antioxidant is antioxidant 1098.

[0007] The modified antibacterial agent is prepared by the following method: Step A1: 5-isopropyl-2-methylbenzene-1,3-diphenol, 1,5-dichloropentane, potassium carbonate and anhydrous ethanol are mixed, stirred at 80°C, reacted for 24 hours, and then 4-dimethylaminobenzoic acid and methanol are added, reacted for 12 hours, cooled to room temperature, dried under nitrogen protection, and filtered to obtain an intermediate product; Further, the dosage ratio of 5-isopropyl-2-methylbenzene-1,3-diphenol, 1,5-dichloropentane, potassium carbonate, anhydrous ethanol, 4-dimethylaminobenzoic acid, and methanol is 0.1-0.2 mol: 3-6 mol: 0.2-0.4 mol: 8 mL: 1-2 mol: 2 mL; Step A2: Mix γ-aminopropyltriethoxysilane, ethanol-water mixed solution and nano-titanium oxide at 35°C for 10 minutes, then heat to 60°C, add the intermediate product under nitrogen protection, heat to 60°C, react for 6 hours, filter, wash, and dry at 45°C to obtain a modified antibacterial agent; further, the dosage ratio of γ-aminopropyltriethoxysilane, ethanol-water mixed solution, nano-titanium oxide, and intermediate product is 4-6g:150mL:100-150g:6-8g, and the volume ratio of ethanol to water in the ethanol-water mixed solution is 4:1.

[0008] The flame retardant is prepared by the following method: Step B1: Mix melamine, thiophene-2-carboxaldehyde and anhydrous ethanol, stir at 80° C. for 10 h, then add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, stir for 12 h, cool to room temperature, filter and wash to obtain a pre-product; Further, the usage ratio of melamine, thiophene-2-carboxaldehyde, anhydrous ethanol, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 0.05-0.08 mol: 0.1 mol: 250 mL: 0.1 mol; Step B2: mixing aluminum sulfate 18hydrate, the pre-product and deionized water, adjusting the pH to 4, heating to 50-90° C., refluxing and aging for 6 hours, cooling to room temperature, washing, filtering and drying to obtain a flame retardant; Furthermore, the usage ratio of aluminum sulfate 18hydrate, pre-product and deionized water is 88.5-95.5 g: 25-30 g: 500 mL.

[0009] A method for preparing an antibacterial PP material, specifically comprising the following steps: S1: Weigh PP resin, surfactant, modified antibacterial agent, flame retardant and antioxidant according to weight and mix them evenly to obtain a mixed material; S2: The mixed material is extruded into granules through a twin-screw extruder, the screw speed is controlled at 450-500r / min, and injection molding is performed by an injection molding machine to obtain an antibacterial PP material.

[0010] Beneficial effects of the present invention: The modified antibacterial agent prepared by the present invention firstly reacts the hydroxyl group of 5-isopropyl-2-methylbenzene-1,3-diphenol with the chlorine of 1,5-dichloropentane under the catalytic action of potassium carbonate, and then quaternizes 4-dimethylaminobenzoic acid with the chlorine atom of 1,5-dichloropentane under the catalytic action of methanol to form an intermediate product 1; secondly, the siloxy group of γ-aminopropyltriethoxysilane, a silane coupling agent, is hydrolyzed into silanol group, which reacts with the hydroxyl group on the surface of nano-titanium oxide, and then the amino group of the coupling agent is condensed with the carboxyl group of the intermediate product to form an amide bond to synthesize the modified antibacterial agent. In the modified antibacterial agent, the nano-titanium oxide is strongly oxidized under ultraviolet light to generate H 2 O 2 and active oxygen, destroying bacterial organic matter and inhibiting its growth and reproduction. At the same time, the released titanium ions destroy the bacterial cell walls, causing the cell contents to flow out and triggering protein denaturation in the bacteria, leading to bacterial death. Among them, the quaternary ammonium salt intermediates can penetrate the bacterial cell walls and react with the proteins on the bacterial cell membranes, causing membrane rupture, causing protein leakage in the bacteria, accelerating bacterial death, and thus improving the antibacterial effect. In addition, the phenolic hydroxyl groups in the intermediates have strong ultraviolet absorption capabilities and can absorb ultraviolet rays of different wavelengths, inhibiting the photoaging process and thus extending the service life of the material.

[0011] The flame retardant prepared by the present invention first utilizes the aldehyde group of thiophene-2-carboxaldehyde to undergo condensation reaction with the amino group of melamine to form an imine bond of a Schiff base, and then connects the flame retardant 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to form a pre-product; secondly, utilizing the metal salt aluminum sulfate 18hydrate to coat the flame retardant metal aluminum hydroxide nanoparticle layer on the surface to form a flame retardant. The 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in the flame retardant, as a phosphaphenanthrene compound with high thermal stability, can effectively flame retardant in the condensed phase and gas phase, promote the formation of a dense and continuous carbon layer during combustion, isolate oxygen, block heat and combustible gas exchange, and synergize with the phosphorus-oxygen double bond and melamine to improve the flame retardant efficiency; the flame retardant aluminum hydroxide is coated on the surface, and its hydroxyl group absorbs heat and decomposes during combustion, lowering the system temperature and stabilizing the surface temperature of the combustible material, thereby reducing the risk of combustion. At the same time, it reacts with the active group to form an inert aluminum oxide layer, further reducing the flammability.

[0012] The invented antibacterial PP material not only has good antibacterial and aging resistance effects, but also has excellent flame retardant properties. It can effectively inhibit bacterial growth, extend the service life of the material, reduce the possibility of fire, and effectively protect human health. DETAILED DESCRIPTION

[0013] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. Example

[0014] A method for preparing an antibacterial PP material, specifically comprising the following steps: S1: Weigh the raw materials by weight, including 60 parts of PP resin, 2 parts of Clariant FA14, 0.5 parts of modified antibacterial agent (prepared in this example), 0.5 parts of flame retardant (prepared in this example), and 0.2 parts of antioxidant 1098, and mix the PP resin, Clariant FA14, modified antibacterial agent, flame retardant and antioxidant 1098 evenly to obtain a mixed material; S2: The mixed material is extruded into granules through a twin-screw extruder, the screw speed is controlled at 450r / min, and injection molded by an injection molding machine to obtain an antibacterial PP material; The modified antibacterial agent is prepared by the following method: Step A1: 0.1 mol 5-isopropyl-2-methylbenzene-1,3-diphenol, 3 mol 1,5-dichloropentane, 0.2 mol potassium carbonate and 8 mL anhydrous ethanol were mixed, stirred at 80°C, reacted for 24 h, then 1 mol 4-dimethylaminobenzoic acid and 2 mL methanol were added, reacted for 12 h, cooled to room temperature, dried under nitrogen protection, and filtered to obtain an intermediate product; Step A2: 4 g of γ-aminopropyltriethoxysilane, 150 mL of ethanol-water mixed solution and 100 g of nano-titanium oxide were mixed at 35° C. for 10 min, then heated to 60° C., and under nitrogen protection, 6 g of the intermediate product was added, heated to 60° C., reacted for 6 h, filtered, washed, and dried at 45° C. to obtain a modified antibacterial agent; The flame retardant is prepared by the following method: Step B1: 0.05 mol of melamine, 0.1 mol of thiophene-2-carboxaldehyde and 250 mL of anhydrous ethanol were mixed, stirred at 80° C. for 10 h, and then 0.1 mol of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was added, stirred for 12 h, cooled to room temperature, filtered and washed to obtain a pre-product; Step B2: Mix 88.5 g of aluminum sulfate 18hydrate, 25 g of the pre-product and 500 mL of deionized water, adjust the pH to 4, heat to 50° C., reflux and mature for 6 hours, then cool to room temperature, wash, filter and dry to obtain a flame retardant. Example

[0015] A method for preparing an antibacterial PP material, specifically comprising the following steps: S1: Weigh the raw materials by weight, including 70 parts of PP resin, 3 parts of Clariant FA14, 1 part of modified antibacterial agent (prepared in this example), 1 part of flame retardant (prepared in this example), and 0.5 part of antioxidant 1098, and mix the PP resin, Clariant FA14, modified antibacterial agent, flame retardant and antioxidant 1098 evenly to obtain a mixed material; S2: The mixed material is extruded into granules through a twin-screw extruder, the screw speed is controlled at 475r / min, and injection molded by an injection molding machine to obtain an antibacterial PP material; The modified antibacterial agent is prepared by the following method: Step A1: 0.15 mol 5-isopropyl-2-methylbenzene-1,3-diphenol, 4.5 mol 1,5-dichloropentane, 0.3 mol potassium carbonate and 8 mL anhydrous ethanol were mixed, stirred at 80°C, reacted for 24 h, then 1.5 mol 4-dimethylaminobenzoic acid and 2 mL methanol were added, reacted for 12 h, cooled to room temperature, dried under nitrogen protection, and filtered to obtain an intermediate product; Step A2: 5 g of γ-aminopropyltriethoxysilane, 150 mL of ethanol-water mixed solution and 125 g of nano-titanium oxide were mixed at 35° C. for 10 min, then heated to 60° C., and under nitrogen protection, 7 g of the intermediate product was added, heated to 60° C., reacted for 6 h, filtered, washed, and dried at 45° C. to obtain a modified antibacterial agent; The flame retardant is prepared by the following method: Step B1: 0.06 mol of melamine, 0.1 mol of thiophene-2-carboxaldehyde and 250 mL of anhydrous ethanol were mixed, stirred at 80° C. for 10 h, and then 0.1 mol of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was added, stirred for 12 h, cooled to room temperature, filtered and washed to obtain a pre-product; Step B2: Mix 91.5 g of aluminum sulfate 18hydrate, 27 g of the pre-product and 500 mL of deionized water, adjust the pH to 4, heat to 70° C., reflux and mature for 6 hours, then cool to room temperature, wash, filter and dry to obtain a flame retardant. Example

[0016] A method for preparing an antibacterial PP material, specifically comprising the following steps: S1: Weigh the raw materials by weight, including 80 parts of PP resin, 4 parts of Clariant FA14, 1.5 parts of modified antibacterial agent (prepared in this example), 1.5 parts of flame retardant (prepared in this example), and 0.8 parts of antioxidant 1098, and mix the PP resin, Clariant FA14, modified antibacterial agent, flame retardant and antioxidant 1098 evenly to obtain a mixed material; S2: The mixed material is extruded into granules through a twin-screw extruder, the screw speed is controlled at 500r / min, and injection molded by an injection molding machine to obtain an antibacterial PP material; The modified antibacterial agent is prepared by the following method: Step A1: 0.2 mol 5-isopropyl-2-methylbenzene-1,3-diphenol, 6 mol 1,5-dichloropentane, 0.4 mol potassium carbonate and 8 mL anhydrous ethanol were mixed, stirred at 80°C, reacted for 24 h, then 2 mol 4-dimethylaminobenzoic acid and 2 mL methanol were added, reacted for 12 h, cooled to room temperature, dried under nitrogen protection, and filtered to obtain an intermediate product; Step A2: 6 g of γ-aminopropyltriethoxysilane, 150 mL of ethanol-water mixed solution and 150 g of nano-titanium oxide were mixed at 35° C. for 10 min, then heated to 60° C., and under nitrogen protection, 8 g of the intermediate product was added, heated to 60° C., reacted for 6 h, filtered, washed, and dried at 45° C. to obtain a modified antibacterial agent; The flame retardant is prepared by the following method: Step B1: 0.08 mol of melamine, 0.1 mol of thiophene-2-carboxaldehyde and 250 mL of anhydrous ethanol were mixed, stirred at 80° C. for 10 h, and then 0.1 mol of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was added, stirred for 12 h, cooled to room temperature, filtered and washed to obtain a pre-product; Step B2: Mix 95.5 g of aluminum sulfate 18hydrate, 30 g of the pre-product and 500 mL of deionized water, adjust the pH to 4, heat to 90° C., reflux and mature for 6 hours, then cool to room temperature, wash, filter and dry to obtain a flame retardant.

[0017] Comparative Example 1 This comparative example is an antibacterial PP material, which differs from Example 3 in that an equal amount of a silver salt antibacterial agent is used to replace the modified antibacterial agent prepared in Example 3, and the rest are the same.

[0018] Comparative Example 2 This comparative example is an antibacterial PP material, which differs from Example 3 in that an equal amount of magnesium hydroxide is used to replace the flame retardant prepared in Example 3, and the rest are the same.

[0019] Performance test: The antibacterial PP materials prepared in Examples 1-3 and Comparative Examples 1-2 were cut into standard test sizes, and antibacterial tests were performed according to standard QB / T 2591-2003. The vertical burning performance was tested using the GB / T2048-1996 plastic burning performance test method. The aging resistance test was performed using a BLUESTAR--X65 xenon lamp according to standard GB / T16422.2. The test results are shown in the following table:

[0020] It can be seen from the test data in the table that the antibacterial PP material prepared in Example 1 not only has a good antibacterial effect and effectively protects human health, but also has an anti-aging effect and extends the service life of the material. It can also be seen from the above table that the antibacterial PP material prepared in the present invention has an excellent flame retardant effect and reduces the possibility of fire.

[0021] The above contents are merely examples and explanations of the concept of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

Claims

1. A method for preparing an antibacterial PP material, characterized in that: The following steps are involved: S1: Weigh PP resin, surfactant, modified antibacterial agent, flame retardant and antioxidant according to weight and mix them evenly to obtain a mixed material; S2: The mixed material is extruded into granules through a twin-screw extruder, the screw speed is controlled at 450-500r / min, and injection molded by an injection molding machine to obtain an antibacterial PP material.

2. The method for preparing an antibacterial PP material according to claim 1, characterized in that: The modified antibacterial agent is prepared by the following method: Step A1: 5-isopropyl-2-methylbenzene-1,3-diphenol, 1,5-dichloropentane, potassium carbonate and anhydrous ethanol are mixed, stirred at 80°C, reacted for 24 hours, and then 4-dimethylaminobenzoic acid and methanol are added, reacted for 12 hours, cooled to room temperature, dried under nitrogen protection, and filtered to obtain an intermediate product; Step A2: Mix γ-aminopropyltriethoxysilane, ethanol-water mixed solution and nano-titanium oxide at 35°C for 10 minutes, then heat to 60°C, add the intermediate product under nitrogen protection, heat to 60°C, react for 6 hours, filter, wash, and dry at 45°C to obtain the modified antibacterial agent.

3. The method for preparing an antibacterial PP material according to claim 2, characterized in that: In step A1, the usage ratio of 5-isopropyl-2-methylbenzene-1,3-diphenol, 1,5-dichloropentane, potassium carbonate, anhydrous ethanol, 4-dimethylaminobenzoic acid and methanol is 0.1-0.2 mol: 3-6 mol: 0.2-0.4 mol: 8 mL: 1-2 mol: 2 mL.

4. The method for preparing an antibacterial PP material according to claim 2, characterized in that: In step A2, the usage ratio of γ-aminopropyltriethoxysilane, ethanol-water mixed solution, nano-titanium oxide, and intermediate product is 4-6g:150mL:100-150g:6-8g, and the volume ratio of ethanol to water in the ethanol-water mixed solution is 4:

1.

5. The method for preparing an antibacterial PP material according to claim 1, characterized in that: The flame retardant is prepared by the following method: Step B1: Mix melamine, thiophene-2-carboxaldehyde and anhydrous ethanol, stir at 80° C. for 10 h, then add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, stir for 12 h, cool to room temperature, filter and wash to obtain a pre-product; Step B2: Mix aluminum sulfate 18hydrate, the pre-product and deionized water, adjust the pH to 4, heat to 50-90° C., reflux and mature for 6 hours, cool to room temperature, wash, filter and dry to obtain a flame retardant.

6. The method for preparing an antibacterial PP material according to claim 5, characterized in that: In step B1, the usage ratio of melamine, thiophene-2-carboxaldehyde, anhydrous ethanol, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 0.05-0.08 mol: 0.1 mol: 250 mL: 0.1 mol.

7. The method for preparing an antibacterial PP material according to claim 5, characterized in that: In step B2, the dosage ratio of aluminum sulfate 18hydrate, pre-product and deionized water is 88.5-95.5 g: 25-30 g: 500 mL.

8. The method for preparing an antibacterial PP material according to claim 1, characterized in that: The surfactant was Clariant FA14, and the antioxidant was antioxidant 1098.

9. An antibacterial PP material, characterized in that: Prepared according to the preparation method according to any one of claims 1 to 8.

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