Antifouling and antibacterial modified polypropylene material and preparation method thereof

Abstract

The invention discloses an antifouling and antibacterial modified polypropylene material and a preparation method thereof. The polypropylene composite material is prepared from the following raw materials in percentage by weight: 10-25% of homo-polypropylene, 40-60% of block co-polypropylene and 2-5% of maleic anhydride grafted polypropylene. The invention discloses an anti-fouling plastic which is prepared from the following components in percentage by weight: 5-15% of elastomer, 5-15% of talcum powder, 1-3% of an anti-fouling agent, 0.5-2.0% of an antibacterial agent, 0.1-0.5% of an antioxidant and 0.2-0.5% of a light stabilizer. The antibacterial agent and the antifouling agent are compounded for use, so that the antifouling and antibacterial properties of the modified polypropylene material are improved, and the material performance and the use stability are guaranteed.

Description

Technical Field

[0001] The invention belongs to the field of modified polypropylene materials, and in particular relates to an antifouling and antibacterial modified polypropylene material and a preparation method thereof. Background Art

[0002] Due to the excellent performance and processability of polypropylene, it is widely used in car interiors. However, polypropylene materials themselves cannot resist the attachment of stains and bacteria, and will inevitably adsorb various organic and inorganic substances during long-term use. The problem of dirt resistance of automotive interior parts has attracted more and more attention, especially for the increasingly large online car-hailing market. The interior environment is complex, and there is a large flow of people every day. The interior leather, plastic, and metal will produce difficult-to-remove dirt on the surface in a short period of time. The attached dirt provides a breeding ground for bacteria to grow and expand. These bacteria include Escherichia coli, Staphylococcus aureus, Salmonella, Streptococcus pneumoniae, and hemolytic Streptococcus. Long-term exposure to an environment with high bacterial concentrations may cause health problems such as respiratory tract, gastrointestinal diseases, and skin diseases, and even cause serious diseases such as pneumonia and sepsis.

[0003] Consumers are more resistant to contact bacteria and pay more and more attention to health issues. As items that consumers touch on a daily basis, the antifouling and antibacterial capabilities of automotive interior materials are becoming more and more concerned by consumers. In order to respond to these health threats and the market demand for antifouling and antibacterial materials, the development of antifouling and antibacterial interior polypropylene materials is becoming more and more important. Summary of the invention

[0004] The present invention aims to provide an antifouling and antibacterial modified polypropylene material and a preparation method thereof, so as to improve the antifouling and antibacterial ability of the modified polypropylene material for automobile interior decoration during use, and at the same time, without changing the processing technology, the material can also have better physical properties to meet the performance requirements of conventional parts.

[0005] This antifouling and antibacterial modified polypropylene material directly uses melt blending to form a masterbatch to evenly disperse antifouling and antibacterial additives into polypropylene, thereby enhancing the interfacial compatibility between polypropylene and the antifouling agent. In addition, through the introduction of grafted compounds and the compound use of antibacterial agents, the role of the antifouling and antibacterial agent can be exerted to a greater extent without affecting the performance of the modified PP material.

[0006] The objectives of the present invention are achieved through the following technical solutions.

[0007] A modified polypropylene material with antifouling and antibacterial properties, comprising the following raw materials in percentage by weight:

[0008]

[0009] In the antifouling and antibacterial modified polypropylene material used in the present invention:

[0010] The block copolymer polypropylene is a combination of two or three types of polypropylene with higher toughness, which not only has higher toughness but also has better rigidity.

[0011] The ethylene-octene copolymer elastomer synthesized by the elastomer metallocene catalyst has excellent toughening effect and aging resistance.

[0012] The maleic anhydride grafted polypropylene has a grafting rate of 3-5% and a very high volume expansion efficiency. A small amount of addition can significantly improve mechanical properties and surface quality.

[0013] The talcum powder is extremely high-mesh mineral talcum powder with an average particle size of 80-120nm, which can enhance the impact resistance, strength and heat deformation resistance of polypropylene.

[0014] The antifouling agent is a fluorine-containing compound, which has excellent corrosion resistance, temperature resistance and anti-stickiness, etc. A small amount of addition can make the surface of an object antifouling and easy to clean.

[0015] The antibacterial agent is a composite antibacterial agent of nano silver ions and nano zinc oxide, wherein the nano zinc oxide particle size is between 30-60nm and has a broad spectrum of antibacterial activity against a variety of bacteria, fungi and viruses.

[0016] The antioxidant is a phosphite, and the light stabilizer is a hindered amine.

[0017] The method for preparing the antifouling and antibacterial modified polypropylene material is characterized by the following steps:

[0018] (1) Firstly, the grafted polypropylene matrix, antifouling agent, talcum powder, antibacterial agent and antioxidant are uniformly blended according to the weight ratio, and extruded into granules, wherein the grafted polypropylene matrix, antifouling agent and antioxidant are added from the main feed, and talcum powder and antibacterial agent are added from the side feed. Then, the remaining weight ratio of the polypropylene matrix, elastomer and light stabilizing agent are uniformly mixed, and directly melt blended by a twin-screw extruder;

[0019] (2) The extrusion temperatures in the screw are: 190-200°C in zone 1, 200-220°C in zone 2, 200-220°C in zone 3, 190-210°C in zone 4, 180-200°C in zone 5, and the screw speed is 350-400r / min; melt blending is carried out in a twin-screw extruder, and after extrusion, the materials are cooled by water, dried, and pelletized, and then enter a homogenization and drying system to reduce the dispersion performance of the materials, and finally a modified polypropylene material product is obtained.

[0020] The present invention belongs to the field of modified polypropylene materials, and specifically relates to an antifouling and antibacterial modified polypropylene material. More specifically, the synergistic effect of an antibacterial agent and an antifouling agent, and the uniform dispersion performance of a masterbatch form, can be used to obtain a modified polypropylene material with excellent antifouling and antibacterial properties through melt blending.

[0021] Compared with the prior art, the present invention has the following advantages:

[0022] 1. Good anti-fouling and antibacterial effect.

[0023] 2. While meeting the requirements of anti-fouling and antibacterial properties, it also retains good mechanical properties and emission properties.

[0024] 3. The modified polypropylene prepared by the present invention greatly broadens the use scope and application environment of polypropylene materials. DETAILED DESCRIPTION

[0025] The present invention is described in detail below in conjunction with specific embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made to the present invention by those skilled in the art based on the contents of the present invention still fall within the scope of protection of the present invention.

[0026] In the modified material formula of the embodiments and comparative examples, the medium-fluidity polypropylene used is a block copolymer polypropylene with a melt flow rate (230°C×2.16KG) of 15-30 / 10min, wherein the comonomer of the block copolymer polypropylene is ethylene, and its content is in the range of 6-15mol%, and the homopolypropylene used is a homopolypropylene with a melt flow rate (230°C×2.16KG) of 10-30 / 10min.

[0027] The talc powder used is ultrafine talc white powder with an average particle size of 80-120nm.

[0028] The grafted polypropylene used is maleic anhydride grafted polypropylene, and the grafting rate is about 5%.

[0029] The antifouling agent used is a fluorine-containing compound.

[0030] The antibacterial agent used is a composite antibacterial agent of nano silver ions and nano zinc oxide, wherein the nano zinc oxide particle size is between 30-60nm

[0031] The antioxidants used were Irganox 1010 (chemical name: pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)) produced by Ciba Company, and Igrafos 168 (chemical name: tris(2,4-di-tert-butylphenyl) phosphite) produced by Ciba Company, and the light stabilizer used was 3808 produced by Cytec Company.

[0032] Example 1

[0033] Weigh 55% of medium-flow block copolymer polypropylene, 12% of homopolymer polypropylene, 4% of maleic anhydride grafted polypropylene, 15% of talc, 10% of elastomer toughening agent, 0.2% of Irganox 1010, 0.1% of Igrafos 168, 0.3% of light stabilizer 3808, and 2% of antifouling agent by weight, blend maleic anhydride grafted polypropylene, antifouling agent, talc, and antioxidant uniformly, extrude and granulate, add the grafted medium polypropylene matrix, antifouling agent, and antioxidant from the main feed, and add talc and antibacterial agent from the side feed. Then mix uniformly with the remaining weight ratio of polypropylene matrix, elastomer, and light stabilizing agent, wherein the first zone is 190-200℃, the second zone is 200-220℃, the third zone is 200-220℃, the fourth zone is 190-210℃, the fifth zone is 180-200℃, and the screw speed is 350-400r / min;

[0034] Example 2

[0035] Weigh 55% of medium-flow block copolymer polypropylene, 12% of homopolymer polypropylene, 4% of maleic anhydride grafted polypropylene, 15% of nano talc, 10% of elastomer toughening agent, 0.2% of Irganox 1010, 0.1% of Igrafos 168, 0.3% of light stabilizer 3808, and 1% of antibacterial agent by weight, blend the grafted polypropylene matrix, antibacterial agent, talc, and antioxidant uniformly, extrude and granulate, add the grafted medium polypropylene matrix, antifouling agent, and antioxidant from the main feed, and add talc and antibacterial agent from the side feed. Then mix evenly with the remaining weight ratio of polypropylene matrix, elastomer, and light stabilizer, wherein the first zone is 190-200℃, the second zone is 200-220℃, the third zone is 200-220℃, the fourth zone is 190-210℃, the fifth zone is 180-200℃, and the screw speed is 350-400r / min;

[0036] Example 3

[0037] Weigh 57% of medium-flow block copolymer polypropylene, 14% of homopolymer polypropylene, 15% of nano talc, 10% of elastomer toughening agent, 0.2% of Irganox 1010, 0.1% of Igrafos 168, 0.3% of light stabilizer 3808, 2% of antifouling agent, and 1% of antibacterial agent by weight, blend the grafted polypropylene matrix, antifouling agent, antibacterial agent, talc, and antioxidant uniformly, extrude and granulate, wherein the grafted polypropylene matrix, antifouling agent, and antioxidant are added from the main feed, and talc and antibacterial agent are added from the side feed. Then mix evenly with the remaining weight ratio of polypropylene matrix, elastomer, and light stabilizer, wherein the first zone is 190-200℃, the second zone is 200-220℃, the third zone is 200-220℃, the fourth zone is 190-210℃, the fifth zone is 180-200℃, and the screw speed is 350-400r / min;

[0038] Example 4

[0039] Weigh 55% of medium-flow block copolymer polypropylene, 12% of homopolymer polypropylene, 4% of maleic anhydride grafted polypropylene, 15% of nano talc, 10% of elastomer toughening agent, 0.2% of Irganox 1010, 0.1% of Igrafos 168, 0.3% of light stabilizer 3808, 2% of antifouling agent, and 1% of antibacterial agent by weight, blend the grafted polypropylene matrix, antifouling agent, antibacterial agent, talc, and antioxidant uniformly, extrude and granulate, wherein the grafted medium polypropylene matrix, antifouling agent, and antioxidant are added from the main feed, and talc and antibacterial agent are added from the side feed. Then, mix uniformly with the remaining weight ratio of polypropylene matrix, elastomer, and light stabilizing agent, wherein the first zone is 190-200℃, the second zone is 200-220℃, the third zone is 200-220℃, the fourth zone is 190-210℃, and the fifth zone is 180-200℃;

[0040] Example 5

[0041] Weigh 55% of medium-flow block copolymer polypropylene, 12% of homopolymer polypropylene, 4% of maleic anhydride grafted polypropylene, 15% of nano talc, 10% of elastomer toughening agent, 0.2% of Irganox 1010, 0.1% of Igrafos 168, 0.3% of light stabilizer 3808, 1% of antifouling agent, and 1% of antibacterial agent by weight, blend the grafted polypropylene matrix, antifouling agent, antibacterial agent, talc, and antioxidant uniformly, extrude and granulate, wherein the grafted medium polypropylene matrix, antifouling agent, and antioxidant are added from the main feed, and talc and antibacterial agent are added from the side feed. Then, mix uniformly with the remaining weight ratio of polypropylene matrix, elastomer, and light stabilizing agent, wherein the first zone is 190-200℃, the second zone is 200-220℃, the third zone is 200-220℃, the fourth zone is 190-210℃, and the fifth zone is 180-200℃;

[0042] Example 6

[0043] Weigh 55% of medium-flow block copolymer polypropylene, 12% of homopolymer polypropylene, 4% of maleic anhydride grafted polypropylene, 15% of nano talc, 10% of elastomer toughening agent, 0.2% of Irganox 1010, 0.1% of Igrafos 168, 0.3% of light stabilizer 3808, 2% of antifouling agent, and 0.5% of antibacterial agent by weight percentage, blend the grafted polypropylene matrix, antifouling agent, antibacterial agent, talc, and antioxidant uniformly, extrude and granulate, wherein the grafted medium polypropylene matrix, antifouling agent, and antioxidant are added from the main feed, and talc and antibacterial agent are added from the side feed. Then mix evenly with the remaining weight ratio of polypropylene matrix, elastomer, and light stabilizing agent, wherein the first zone is 190-200℃, the second zone is 200-220℃, the third zone is 200-220℃, the fourth zone is 190-210℃, and the fifth zone is 180-200℃;

[0044] Example 7

[0045] Weigh 55% of medium-flow block copolymer polypropylene, 12% of homopolymer polypropylene, 4% of maleic anhydride grafted polypropylene, 15% of nano talc, 10% of elastomer toughening agent, 0.2% of Irganox 1010, 0.1% of Igrafos 168, 0.3% of light stabilizer 3808, 2% of antifouling agent, and 1.5% of antibacterial agent by weight percentage, blend the grafted polypropylene matrix, antifouling agent, antibacterial agent, talc, and antioxidant uniformly, extrude and granulate, wherein the grafted medium polypropylene matrix, antifouling agent, and antioxidant are added from the main feed, and talc and antibacterial agent are added from the side feed. Then mix evenly with the remaining weight ratio of polypropylene matrix, elastomer, and light stabilizing agent, wherein the first zone is 190-200℃, the second zone is 200-220℃, the third zone is 200-220℃, the fourth zone is 190-210℃, and the fifth zone is 180-200℃;

[0046] Comparative Example

[0047] Weigh 58% of medium-fluidity block copolymer polypropylene, 16% of homopolymer polypropylene, 15% of common talcum powder, 10% of common elastomer toughening agent, 0.2% of Irganox 1010, 0.1% of Igrafos 168, and 0.3% of light stabilizer by weight percentage, mix the polypropylene matrix, elastomer, talcum powder, antioxidant, light stabilizer and other components uniformly by weight ratio, directly melt blend through a twin-screw extruder, and extrude granulation, wherein the first zone is 190-200°C, the second zone is 200-220°C, the third zone is 200-220°C, the fourth zone is 190-210°C, the fifth zone is 180-200°C, and the screw speed is 350-400r / min;

[0048] Performance evaluation method:

[0049] The melt flow rate was tested according to ISO 1133-1, with the test conditions of 230°C × 2.16 kg; the flexural modulus was tested according to ISO 178, with the sample size of 80 × 10 × 4 mm and the notch depth of one third of the sample thickness;

[0050] The antifouling performance test is carried out according to the wiping method in FZ / T 01118 and the requirements of GB / T 250. The results are evaluated by referring to the colorimetric card and visually judging the easy-to-remove performance and stain resistance performance levels. The stains used are liquid stains: cola, coffee, motor oil; semi-solid stains; semi-solid stains: ketchup, grease; solid stains: whiteboard markers. Before the test, three different positions of each pollutant test sample are set as parallel samples for the experiment for comparison after wiping. Each experimental position is wiped back and forth 10 times with a clean muslin cloth, a muslin cloth dipped in water, and a muslin cloth dipped in detergent water. If the stain is completely removed after wiping with the former muslin cloth, the result can be directly evaluated. Evaluation level: Grade A is not resistant to stains and is not easy to remove, with visual stain resistance and stain removal performance lower than grade 4.0; Grade B is not resistant to stains, but stains are easier to remove after being stained, with stain removal performance of 4.0-4.5; Grade C is not resistant to stains, but stains are not visually obvious after being stained, with stain removal performance ≥ grade 4.5 and stain resistance performance lower than grade 4.5; Grade D is good stain resistance and stains are not easy to be stained; Excellent stain removal performance, stains are easy to remove after being stained, stain removal performance ≥ grade 4.5 and stain resistance performance ≥ grade 4.5.

[0051] The antibacterial performance test refers to GB / T 31402. Bacteria are quantitatively inoculated on the surface of the sample to be tested with a size of (50±2)mm×(50±2)mm and a thickness of ≤5mm. The bacteria are evenly contacted with the surface of the sample by the film sticking method. After a period of cultivation, the number of live bacteria in the sample is tested and the antibacterial rate of the sample is calculated.

[0052] Table 1: Material formula of Examples 1-7 (weight %)

[0053]

[0054]

[0055] Table 2: Performance test results of Examples 1-7 and Comparative Examples

[0056]

[0057]

[0058] The control example is a conventional impact-modified polypropylene material, which exhibits poor antifouling and antibacterial properties compared to other control examples. Examples 1-2 are to explore the effects of individual antifouling agents and antibacterial agents. Obviously, whether the antifouling agent or the antibacterial agent is added alone, the antifouling and antibacterial capabilities of the material are enhanced. Examples 3-4 explore the effect of grafted polypropylene on the system. After adding maleic anhydride grafted polypropylene, the antibacterial properties of the material can reach more than 99.9%, but the ability to remove dirt is slightly lower than that of Example 3 without grafted polypropylene. Examples 5-7 verify the effect of different addition amounts on the results. After the antifouling agent content is reduced, the ability to remove dirt also decreases; when the antibacterial agent addition amount is 0.5%, the anti-Staphylococcus aureus rate is slightly reduced. In addition, the mechanical properties of all the examples are not very different from those of the control examples.

Claims

1. A modified polypropylene material with antifouling and antibacterial properties, characterized in that: The invention is composed of the following raw materials in percentage by weight: 10-25% homopolymer polypropylene; 40-60% block copolymer polypropylene; 2-5% maleic anhydride grafted polypropylene; 5-15% elastomer; 5-15% talcum powder; 1-3% antifouling agent; 0.5-2.0% antibacterial agent; 0.1-0.5% antioxidant; and 0.2-0.5% light stabilizer.

2. The antifouling and antibacterial modified polypropylene material according to claim 1, characterized in that: The block copolymer polypropylene is a combination of two or three types of polypropylene with higher toughness.

3. The antifouling and antibacterial modified polypropylene material according to claim 1, characterized in that: The elastomer is an ethylene-octene copolymer elastomer synthesized by a metallocene catalyst.

4. The antifouling and antibacterial modified polypropylene material according to claim 1, characterized in that: The maleic anhydride grafted polypropylene has a grafting rate of 3-5%.

5. The antifouling and antibacterial modified polypropylene material according to claim 1, characterized in that: The talcum powder is extremely high-mesh mineral talcum powder with an average particle size of 80-120nm.

6. The antifouling and antibacterial modified polypropylene material according to claim 1, characterized in that: The antifouling agent is a fluorine-containing compound.

7. The antifouling and antibacterial modified polypropylene material according to claim 1, characterized in that: The antibacterial agent is a composite antibacterial agent of nano silver ions and nano zinc oxide, wherein the particle size of the nano zinc oxide is between 30-60nm.

8. The antifouling and antibacterial modified polypropylene material according to claim 1, characterized in that: The antioxidant is a phosphite, and the light stabilizer is a hindered amine.

9. The method for preparing the antifouling and antibacterial modified polypropylene material according to any one of claims 1 to 8, characterized in that: The steps are as follows: (1) firstly blending the grafted polypropylene matrix, antifouling agent, talcum powder, antibacterial agent and antioxidant uniformly according to the weight ratio, and extruding and granulating, wherein the grafted polypropylene matrix, antifouling agent and antioxidant are added from the main feed, and the talcum powder and antibacterial agent are added from the side feed; then, the remaining weight ratio of the polypropylene matrix, elastomer and light stabilizing agent are uniformly mixed, and directly melt blended by a twin-screw extruder; (2) The extrusion temperatures in the screw are: 190-200°C in zone 1, 200-220°C in zone 2, 200-220°C in zone 3, 190-210°C in zone 4, 180-200°C in zone 5, and the screw speed is 350-400r / min; melt blending is carried out in a twin-screw extruder, and after extrusion, the materials are cooled by water, dried, and pelletized, and then enter a homogenization and drying system to reduce the dispersion performance of the materials, and finally a modified polypropylene material product is obtained.

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