Antibacterial glass fiber reinforced and toughened polypropylene composite material and preparation method thereof

Abstract

The invention discloses an antibacterial glass fiber reinforced and toughened polypropylene composite material and a preparation method thereof. The antibacterial glass fiber reinforced and toughened polypropylene composite material comprises the following components in parts by weight: 40-80 parts of polypropylene resin, 20-40 parts of glass fiber, 1-5 parts of a modified antibacterial agent, 1-10 parts of a compatilizer, 0.5-1.5 parts of an inorganic zinc antibacterial agent and 0.1-1 part of an antioxidant. The modified antibacterial agent is used as an organic imidazole antibacterial agent and has a synergistic effect with an inorganic zinc ion antibacterial agent, so that the material has efficient and lasting antibacterial performance; in addition, due to the stable MOFs structure in the composite material, the size of the polypropylene composite material is more stable, and meanwhile, the polypropylene composite material has more excellent mechanical properties.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and specifically relates to an antibacterial glass fiber reinforced toughened polypropylene composite material and a preparation method thereof. Background Art

[0002] Short glass fiber reinforced polypropylene, with its lightweight characteristics, effectively improves fuel efficiency or driving range, greatly reduces automobile carbon emissions, and plays a pivotal role in the automotive industry. The "skeleton" effect of short glass fiber in the resin matrix gives the material excellent mechanical strength, but its toughness is compromised to a certain extent; with the continuous warming of the "big health economy" era, the automotive industry has put forward higher requirements for the antibacterial properties of vehicle interior materials, and the design concept of creating an "ecological purification cabin" has become the mainstream trend in the industry. At present, the preparation of antibacterial polypropylene composite materials mostly uses inorganic antibacterial agents such as metal ions (such as silver ions, zinc ions, copper ions, etc.), photocatalysis (such as titanium dioxide, zinc oxide, etc.); and chitosan-based or new (zinc pyrithione, etc.) organic antibacterial agents. However, due to the high cost, it is not conducive to large-scale industrial production; the fast release rate leads to a short antibacterial effective time; and the poor compatibility with polypropylene affects its stability and dispersibility in the matrix. It is particularly important to develop a composite material suitable for the automotive industry that can achieve a balance of rigidity and toughness while meeting high antibacterial requirements. This will help promote the green and sustainable development of the automobile manufacturing industry and provide passengers with a healthier and safer riding environment. Summary of the invention

[0003] The object of the present invention is to provide an antibacterial glass fiber reinforced toughened polypropylene composite material and a preparation method thereof, so as to solve the above-mentioned problems of the prior art.

[0004] The present invention is achieved through the following technical solutions:

[0005] An antibacterial glass fiber reinforced toughened polypropylene composite material is composed of the following raw materials in parts by weight: 40-80 parts of polypropylene resin, 20-40 parts of glass fiber, 1-5 parts of modified antibacterial agent, 1-10 parts of compatibilizer, 0.5-1.5 parts of inorganic zinc antibacterial agent and 0.1-1 part of antioxidant.

[0006] The modified antibacterial agent is an organic imidazole antibacterial agent. One end of its structure is grafted with polypropylene, which can greatly improve the compatibility of the modified antibacterial agent in the polypropylene composite material. The imidazole group at the other end of the structure grows in situ with zinc ions to construct the MOFs structure. The synergistic effect of the organic / inorganic composite antibacterial agent, coupled with the constructed MOFs having a three-dimensional porous hybrid structure that can be used as a metal ion storage reservoir, continuously and slowly releases metal ions, giving the material excellent antibacterial properties; in addition, the stable MOFs form a topological network structure with the polypropylene molecular chain, which makes up for the dimensional instability caused by the glass fiber orientation, and at the same time makes the polypropylene composite material have excellent stiffness and toughness.

[0007] The compatibilizer is polypropylene grafted with maleic anhydride, and the grafting rate is 1.5%.

[0008] The modified antibacterial agent is N-methylimidazole modified polypropylene ionomer.

[0009] The inorganic zinc antibacterial agent is one or more inorganic salt-supported zinc.

[0010] The antioxidant is one or a combination of hindered phenol antioxidant 1010, phosphite antioxidant 168, etc.

[0011] The preparation method of the above antibacterial glass fiber reinforced toughened polypropylene composite material comprises the following steps:

[0012] (1) In a 500 mL round-bottom bottle equipped with a mechanical stirring paddle, add 10.0 g of propylene / 11-iodo-1-undecene copolymer (PP / IUD) and 200 mL of toluene. After complete dissolution, add N-methylimidazole and condense and reflux for 24 hours. After the reaction is completed, the reaction solution is precipitated in ethanol, the filtered product is washed three times with ethanol and acetone, and finally the prepared N-methylimidazole polypropylene ionomer is placed in a vacuum oven at 60°C and dried until the sample is constant weight to obtain a modified antibacterial agent.

[0013] (2) Weigh polypropylene resin, compatibilizer, modified antimicrobial agent, inorganic zinc antimicrobial agent and antioxidant according to weight ratio and put them into a high-speed mixer, and stir at room temperature for 10 to 30 minutes.

[0014] (3) adding the mixed material in step (2) to the main feed port of a twin-screw extruder, adding the glass fiber weighed according to the weight ratio to the side feed port of the twin-screw extruder, fully plasticizing and mixing at 190-230° C., extruding, cooling and granulating.

[0015] The modified antibacterial agent of the present invention is used as an organic imidazole antibacterial agent and an inorganic zinc ion antibacterial agent to construct a metal organic framework nanocrystalline material (MOFs) through in-situ growth of imidazole coordination groups and zinc ions. The synergistic effect of this organic / inorganic composite antibacterial agent, coupled with the constructed MOFs having a three-dimensional porous hybrid structure that can be used as a metal ion storage reservoir, continuously and slowly releases metal ions, giving the material excellent antibacterial properties; in addition, the stable MOFs form a topological network structure with the polypropylene molecular chain, which makes up for the dimensional instability caused by the glass fiber orientation, and at the same time makes the polypropylene composite material have both excellent stiffness and toughness. DETAILED DESCRIPTION

[0016] The technical solution of the present invention is further illustrated below by preferred embodiments. Without violating the purpose of the present invention, the present invention should not be limited to the contents specifically shown in the following experimental examples.

[0017] Raw materials used in the embodiments of the present invention:

[0018] Polypropylene: copolymer polypropylene PP, CNOOC Shell;

[0019] Glass fiber: chopped length 4mm, diameter 14um, China Jushi International Co., Ltd.

[0020] Compatibilizer: Maleic anhydride grafted polypropylene particles, Pulilon, grafting rate 1.5%;

[0021] Modified antimicrobial agent: N-methylimidazole modified polypropylene ionomer;

[0022] Inorganic zinc ion: one or more inorganic zinc-containing salts;

[0023] Antioxidant: one or a combination of hindered phenol antioxidant 1010, phosphite antioxidant 168, etc.;

[0024] Product performance test method:

[0025] Tensile strength: According to ISO 527 method, tensile speed 5mm / min.

[0026] Bending strength: According to ISO 178 method, test speed 2mm / min.

[0027] Flexural modulus: According to ISO 178 method, test speed 2mm / min.

[0028] Notched impact strength: According to ISO 179 method, 4mm thick specimen.

[0029] The antibacterial property is tested according to GB / T 2591-2003 standard.

[0030] The formulas and performance test results of the embodiments and comparative examples are shown in the following tables

[0031] Table 1 is the material formula (weight %) and various performance tables of Examples 1 to 9

[0032] Table 1 Example material formula and performance test results

[0033]

[0034]

[0035] Table 2 is the material formula (weight %) and various performance tables of Comparative Examples 1 to 9

[0036] Table 2 Comparative Example Material Formula and Performance Test Results

[0037]

[0038]

[0039] The results of Examples 1-9 and Comparative Examples 1-3 and Comparative Examples 4-7 show that: 1. The addition of inorganic zinc ions or modified antibacterial agents significantly improves the antibacterial rates of Escherichia coli and Staphylococcus aureus of the polypropylene composite material; 2. When inorganic zinc ions and modified antibacterial agents are added at the same time, the material has excellent antibacterial properties under the synergistic effect of the imidazole antibacterial agent and the inorganic zinc ion antibacterial agent. While ensuring the original excellent tensile strength and flexural modulus, the notched impact strength is also improved to a certain extent; 3. When the added contents of inorganic zinc ions and modified antibacterial agents are 1% and 3% respectively, the polypropylene composite material exhibits the best comprehensive performance.

Claims

1. An antibacterial glass fiber reinforced toughened polypropylene composite material, characterized in that: The invention is composed of the following raw materials in parts by weight: 40-80 parts of polypropylene resin, 20-40 parts of glass fiber, 1-5 parts of modified antibacterial agent, 1-10 parts of compatibilizer, 0.5-1.5 parts of inorganic zinc antibacterial agent and 0.1-1 part of antioxidant.

2. The antibacterial glass fiber reinforced toughened polypropylene composite material according to claim 1, characterized in that: The modified antibacterial agent is an organic imidazole antibacterial agent.

3. The antibacterial glass fiber reinforced toughened polypropylene composite material according to claim 1, characterized in that: The compatibilizer is polypropylene grafted with maleic anhydride, and the grafting rate is 1.5%.

4. The antibacterial glass fiber reinforced and toughened polypropylene composite material according to claim 1, characterized in that: The modified antibacterial agent is N-methylimidazole modified polypropylene ionomer.

5. The antibacterial glass fiber reinforced toughened polypropylene composite material according to claim 1, characterized in that: The inorganic zinc antibacterial agent is one or more inorganic salt-supported zinc.

6. The antibacterial glass fiber reinforced toughened polypropylene composite material according to claim 1, characterized in that: The antioxidant is one of the hindered phenol antioxidant 1010 and the phosphite antioxidant 168 or a combination of several of them.

7. The method for preparing the antibacterial glass fiber reinforced toughened polypropylene composite material according to any one of claims 1 to 6, characterized in that: The steps are as follows: (1) In a 500 mL round-bottom bottle equipped with a mechanical stirring paddle, 10.0 g of propylene / 11-iodo-1-undecene copolymer (PP / IUD) and 200 mL of toluene were added, and after complete dissolution, N-methylimidazole was added, and the reaction was condensed and refluxed for 24 hours; after the reaction was completed, the reaction solution was precipitated in ethanol, and the filtered product was washed three times with ethanol and acetone respectively, and finally the prepared N-methylimidazole polypropylene ionomer was placed in a vacuum oven at 60° C. and dried until the sample had a constant weight to obtain a modified antibacterial agent; (2) Weigh polypropylene resin, compatibilizer, modified antimicrobial agent, inorganic zinc antimicrobial agent and antioxidant according to weight ratio and put them into a high-speed mixer, and stir at room temperature for 10 to 30 minutes; (3) adding the mixed material in step (2) to the main feed port of a twin-screw extruder, adding the glass fiber weighed according to the weight ratio to the side feed port of the twin-screw extruder, fully plasticizing and mixing at 190-230° C., extruding, cooling and granulating.

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