CN113956566B - Polypropylene-based antibacterial master batch and preparation method and application thereof - Google Patents
Polypropylene-based antibacterial master batch and preparation method and application thereof Download PDFInfo
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- C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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Abstract
The invention discloses a polypropylene-based antibacterial master batch and a preparation method and application thereof, wherein the polypropylene-based antibacterial master batch comprises the following components in parts by weight: 90 parts of polypropylene resin; 2-10 parts of a main antibacterial agent; 2-10 parts of auxiliary antibacterial agent; 0.2-1 part of coupling agent solution; 1-10 parts of a compatilizer; the main antibacterial agent is selected from one or more of monazite powder, granite powder, phosphate rock powder or fly ash; the auxiliary antibacterial agent is selected from any one or more of tourmaline powder or fluorine antibacterial powder. The polypropylene-based antibacterial master batch disclosed by the invention has excellent antibacterial performance and lasting and stable antibacterial efficiency through the synergistic cooperation of two antibacterial agents; the automobile interior material prepared by adding the polypropylene-based antibacterial masterbatch has high-efficiency and lasting antibacterial effect, can remove dust and sterilize air in a vehicle, improves the quality of the air in the vehicle, and can still keep high dust and sterilization efficiency after being used for a long time.
Description
Technical Field
The invention relates to the technical field of high polymer materials, and particularly relates to a polypropylene-based antibacterial master batch, and a preparation method and application thereof.
Background
Polypropylene (PP) materials are widely used in the automotive field (especially automotive interiors) due to their low specific gravity, excellent mechanical properties, low cost, easy processing, chemical resistance, etc. Automotive interior mainly refers to the automobile product that the inside repacking of car was used, for example car steering wheel, car cushion, car callus on the sole, inside goods of furniture for display rather than for use, containing box, panel board lamp etc. all belong to automotive interior product. In ordinary use, the automotive upholstery usually directly contacts with a human body, objects and the like, substances such as human sweat, sebum, oil dirt, smoke dirt, dust and the like are easy to adhere to the automotive upholstery, and because the interior of an automobile is generally in a relatively closed environment, microorganisms such as bacteria, mold and the like are easy to breed, and after the microorganisms react with pollutants, low-grade fatty acids (such as pelargonic acid, capric acid and volatile compounds) can be generated, and unpleasant odors are emitted, so that the use comfort of the automobile and the body health of users are greatly influenced. Therefore, materials for automobile interior are required to have a good antibacterial function.
At present, a metal ion doping method is often adopted in industry to prepare an Ag/ZnO nano composite antibacterial agent which is used for antibacterial modification of plastics, however, if the plastics are contacted with a human body for a long time, heavy metals such as silver, zinc and the like can enter the human body through skin, respiratory tract, digestive system and other ways to cause heavy metal poisoning in the human body, the light people show symptoms such as vomit, headache, diarrhea, blood ejection, metabolic disorder and the like, and the serious symptoms can cause damage of neuron and brain functions and even cause fetal nerve tube malformation of pregnant women; and because Ag/ZnO and other metals have higher use cost and poorer compatibility with plastics, are easy to oxidize and decompose under high-temperature processing to influence the use performance, the antibacterial agent is not suitable for antibacterial modification of automotive interior materials.
In the prior art, chinese patent application CN108047560a discloses a polypropylene composite material for automotive interior parts, which is added with a hydroxyl-containing compound and its derivatives (3-methyl-4-isopropyl phenol, methyl p-hydroxybenzoate and N- (fluorodichloromethyl sulfur) titanium imide) as an antibacterial agent to improve the antibacterial performance of the material; CN110857349A discloses a novel plastic for automotive interior parts, which is prepared into a material with antibacterial performance by adding an antibacterial composition formed by combining agastache rugosus, folium artemisiae argyi, polygonum cuspidatum and lavender according to a certain proportion. However, the short-term antibacterial effect of the antibacterial material of the prior art is good, but the durability is poor, and the antibacterial performance of the antibacterial material is obviously reduced along with the prolonging of the service time.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a polypropylene-based antibacterial master batch which has excellent antibacterial performance and lasting and stable antibacterial efficiency; the automobile interior material prepared by adding the polypropylene-based antibacterial masterbatch has high-efficiency and lasting antibacterial effect, can remove dust and sterilize air in a vehicle, improves the quality of the air in the vehicle, and can still keep high dust and sterilization efficiency after being used for a long time.
The invention also aims to provide a preparation method of the polypropylene-based antibacterial master batch.
The invention also aims to provide application of the polypropylene-based antibacterial master batch.
The invention is realized by the following technical scheme:
the polypropylene-based antibacterial master batch comprises the following components in parts by weight:
90 parts of polypropylene resin;
2-10 parts of a main antibacterial agent;
2-10 parts of auxiliary antibacterial agent;
0.2-1 part of coupling agent solution;
1-10 parts of a compatilizer; .
The main antibacterial agent is selected from one or more of monazite powder, granite powder, phosphate rock powder or fly ash;
the auxiliary antibacterial agent is selected from any one or more of tourmaline powder or fluorine antibacterial powder.
According to the invention, the specific main antibacterial agent and the auxiliary antibacterial agent are added and have synergistic effect, so that the stability of the antibacterial efficiency can be effectively improved while the antibacterial efficiency is improved. Natural primary radionuclide in the mineral of the main antibacterial agent can generate trace radiation, can efficiently capture and kill bacteria, and simultaneously excites the permanent piezoelectric effect, the thermoelectric effect and the dipole effect of the auxiliary antibacterial agent, the effect can form ten-micron ionized layer micro-particles on the surface layer of the antibacterial agent by ionizing water molecules in air, and the particles can rapidly capture micro-dust particles in the air to form a better air filtering and refreshing effect and have a certain sterilization effect; under the condition of micro radiation of the main antibacterial agent, the compound auxiliary antibacterial agent can keep the ionization effect of the main antibacterial agent for a longer time, so that the air filtering and refreshing performance and the antibacterial performance are effectively improved, and the long-term dedusting antibacterial effect is kept.
Preferably, the weight ratio of the primary antibacterial agent to the secondary antibacterial agent is (0.2-5): 1; more preferably, the weight ratio of the primary antibacterial agent to the secondary antibacterial agent is (0.5-2): 1.
the antibacterial agent has small particle size and is easy to agglomerate to cause difficult dispersion, and the overall surface area of the antibacterial agent particles can be reduced if the particle size is too large, so that the dedusting antibacterial effect is reduced; preferably, the primary and secondary antimicrobial agents have a particle size D 90 Is 0.01-6 μm; more preferably, the primary and secondary antimicrobial agents have a particle size D 90 Is 0.3 μm to 0.9 μm.
The main antibacterial agent is monazite powder.
The auxiliary antibacterial agent is preferably selected from any one or more of fluorine antibacterial powder; the fluorine antibacterial powder is selected from one or more of polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoroethylene copolymer or difluoroethylene-hexafluoroethylene copolymer.
Preferably, the melt flow rate of the polypropylene resin is 10-60g/10min at 230 ℃ and 2.16 kg; more preferably, the melt flow rate of the polypropylene resin is 20-40g/10min at 230 ℃ and 2.16 kg; the melt flow rate of the polypropylene resin is tested according to the standard ISO 1133-91. The coating effect of the resin melt with too high flow rate on the antibacterial agent powder is poor, and the melt flow rate is too low, so that the production process is difficult and the performance of the subsequent automobile product added with the master batch is affected.
Coupling agents commonly used in the art for the treatment of mineral powders are suitable for use in the present invention. Preferably, the coupling agent solution of the invention is prepared by mixing a silane coupling agent and absolute ethyl alcohol in a ratio of (0.3-1): 1, preparing.
The compatilizer is selected from one or more of maleic anhydride grafted olefin copolymer or glycidyl methacrylate grafted olefin copolymer.
According to the material performance requirement, the polypropylene antibacterial master batch also comprises 0.1-1 part of processing aid in parts by weight; the processing aid is any one or more of a lubricant, an antioxidant or an anti-aging agent.
Suitable lubricant is selected from one or more of polyethylene wax or ethylene bis-oleamide synthetic wax.
Suitable antioxidant is selected from any one or compound of antioxidant 1010 (tetra [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester) and antioxidant 168 (tris (2,4-di-tert-butylphenyl) phosphite).
The suitable anti-aging agent is any one or more of a light stabilizer and an ultraviolet absorber.
The invention also provides a preparation method of the polypropylene-based antibacterial master batch, which comprises the following steps:
s1: adding the main antibacterial agent and the auxiliary antibacterial agent into a grinding tank according to the proportion, grinding for 10-15 minutes continuously, adding a coupling agent solution, continuously grinding for 10-20 minutes, and drying for 1-2 hours at 80-100 ℃; obtaining antibacterial powder after surface activity treatment;
s2: mixing the antibacterial powder prepared in the step S1 with the rest components through a high-speed mixer for 3-5min to obtain a mixture;
s3: feeding the mixture obtained in the step S2 into a double-screw extruder, and extruding and granulating after melting, plasticizing and mixing by the double-screw extruder, wherein the screw temperature of the double-screw extruder is 160-220 ℃, and the rotating speed is 300-500rpm; and (5) preparing the polypropylene-based antibacterial master batch.
The invention also provides application of the polypropylene-based antibacterial master batch in automobile interior materials.
As a preferred embodiment, the automotive interior material comprises the following components in parts by weight: 90-100 parts of a polypropylene material; 2 to 10 parts of polypropylene-based antibacterial master batch.
The polypropylene material can be selected from automobile interior polypropylene materials.
The invention also provides a preparation method of the automobile interior material, which comprises the following steps: and (3) carrying out melt blending extrusion on the components by using a double-screw extruder according to the proportion, and granulating to obtain the automotive interior material.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the polypropylene-based antibacterial master batch is prepared by adding the specific main antibacterial agent and the auxiliary antibacterial agent and realizing the synergistic effect of the main antibacterial agent and the auxiliary antibacterial agent, and has excellent antibacterial performance and lasting and stable antibacterial efficiency; the method can be used for antibacterial modification of high polymer materials, effectively improves the dust removal and antibacterial functions of the materials, and simultaneously keeps the performance of the materials unaffected. The automobile interior material prepared by adding the polypropylene-based antibacterial masterbatch has high-efficiency and lasting antibacterial effect, can remove dust and sterilize air in a vehicle, improves the quality of the air in the vehicle, and can still keep high dust and sterilization efficiency after being used for a long time.
The polypropylene-based environment-friendly antibacterial master batch has great application potential in the fields of automotive interior and home decoration materials.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way.
The raw materials used in the examples and comparative examples of the present invention are described below, but are not limited to these materials:
polypropylene resin 1: PP HP565S, available from Mediterranean Shell, with a melt flow rate of 38g/10min at 230 ℃ under 2.16 kg;
polypropylene resin 2: PP EP548R, available from Zhonghai Shell, having a melt flow rate of 25g/10min at 230 ℃ under 2.16 kg;
polypropylene resin 3: PP H9018, obtained from landlocked petrochemical, having a melt flow rate of 55g/10min at 230 ℃ under 2.16 kg;
primary antibacterial agent 1: monazite powder 1, particle size D 90 0.9 μm, commercially available;
primary antibacterial agent 2: phosphorus ore powder, particle size D 90 0.9 μm, commercially available;
primary antibacterial agent 3: granite powder with particle sizeD 90 0.9 μm, commercially available;
primary antibacterial agent 4: fly ash, particle diameter D 90 0.9 μm, commercially available;
primary antibacterial agent 5: monazite powder 2, particle size D 90 Is 6 μm, commercially available;
secondary antibacterial agent 1: tourmaline powder 1, particle diameter D 90 0.9 μm, purchased from Tianjin hongyan Tianshan stone industry nanotechnology Co., ltd;
and (3) secondary antibacterial agent 2: vinylidene fluoride-hexafluoroethylene copolymer, particle size D 90 0.9 μm, available from Dajin Japan;
secondary antibacterial agent 3: tourmaline powder 2, particle diameter D 90 6 μm, purchased from Tianjin swan Yan Tianshan Stone industry nanotechnology GmbH;
secondary antibacterial agent 4: polytetrafluoroethylene, particle diameter D 90 6 μm, available from Dajin Japan;
coupling agent solution: preparing a silane coupling agent KH-550 and absolute ethyl alcohol according to a ratio of 0.4;
1 part of compatilizer: maleic anhydride grafted polypropylene, BONDYRAM 1001CN, available from Aaron, usa;
a compatilizer 2: glycidyl methacrylate grafted polypropylene, PX6006, available from liandbasel;
antioxidant: the antioxidant 1010 and the antioxidant 168 are compounded in a weight ratio of 1:1.
The preparation method of the polypropylene antibacterial master batch comprises the following steps:
s1: adding the main antibacterial agent and the auxiliary antibacterial agent into a grinding tank to be ground according to the mixture ratio of table 1/table 2/table 3, continuously grinding for 15 minutes, adding a coupling agent solution, continuously grinding for 10 minutes, and drying for 1 hour at 80 ℃; obtaining antibacterial powder after surface activity treatment;
s2: mixing the antibacterial powder prepared in the step S1 with the rest components through a high-speed mixer for 5min to obtain a mixture;
s3: feeding the mixture obtained in the step S2 into a double-screw extruder, and extruding and granulating after melting, plasticizing and mixing by the double-screw extruder, wherein the screw temperature of the double-screw extruder is 160-220 ℃, and the rotating speed is 450rpm; and (5) preparing the polypropylene-based antibacterial master batch.
Table 1: the concrete proportion (by weight) of each component of the polypropylene antibacterial masterbatch A1-A7
Table 2: the concrete proportion (by weight) of each component of the polypropylene antibacterial masterbatch A8-A15
Table 3: the concrete proportion (by weight) of each component of the polypropylene antibacterial master batch B1-B6
The prepared polypropylene-based antibacterial master batch and a polypropylene material (polypropylene material 1 AIP-2015 LO, purchased from Jinfa technology corporation; polypropylene material 2 API-1025, purchased from Jinfa technology corporation) are extruded and granulated by a double-screw extruder according to the mixture ratio of table 4/table 5/table 6 to prepare the automobile interior antibacterial polypropylene material, and the automobile interior antibacterial polypropylene material is added into an injection molding machine and a mold for injection molding to be used as a sample for antibacterial test, wherein the injection molding machine process parameters are 200-220 ℃, the injection molding pressure is 50MPa, and the injection molding speed is 50mm/S.
The samples are respectively tested for Escherichia coli resistance (ATCC 25922) and Staphylococcus aureus resistance (ATCC 6528) according to a standard QB/T2591-2003 antibacterial test method; meanwhile, in order to examine the long-term antibacterial effect of the embodiment and the attenuation condition of the antibacterial property of the embodiment, the specific method comprises the following steps: putting a test sample into a beaker filled with 1000 mL distilled water, putting the beaker into a water bath at 55 ℃, continuously stirring by using a stirrer, changing water every 12 hours, measuring the antibacterial efficiency of the sample to escherichia coli and staphylococcus aureus after soaking for 240 hours and 720 hours, and calculating the antibacterial efficiency retention rate (%), namely the antibacterial efficiency retention rate (%) = the antibacterial efficiency value of a corresponding germ after different time/the initial antibacterial efficiency value of the corresponding germ of 100%; the results are shown in tables 4 to 6.
Table 4: example 1~7 Components proportioning by weight parts and antibacterial Property test results
Table 5: the component dosage ratios (in parts by weight) and the antibacterial performance test results of examples 8 to 16
Table 6: comparative example 1~7 component proportion (by weight) and antibacterial property test result
As can be seen from the above examples and comparative examples, the material prepared by adding the polypropylene-based antibacterial masterbatch of the invention has excellent antibacterial effect and antibacterial stability (the initial antibacterial efficiency value is high, and the antibacterial efficiency retention rate reaches more than 97% after the material is treated for 720 hours in a water bath condition at 55 ℃); the polypropylene-based antibacterial master batch disclosed by the invention can effectively improve the antibacterial efficiency and the antibacterial stability by adding the specific main antibacterial agent and the specific auxiliary antibacterial agent, and can be used for antibacterial modification of a high polymer material, so that the material has a high-efficiency and long-lasting antibacterial effect.
Specifically, comparison between comparative example 1/2 and example 1/4/6 shows that the addition amount of the main antibacterial agent of the antibacterial master batch in the comparative example 1 is too small, the initial antibacterial efficiency value of the material is low, and after the material is treated for 720 hours under the water bath condition at 55 ℃, the antibacterial efficiency retention rate of the material is low, and the antibacterial stability is poor; the addition amount of the auxiliary antibacterial agent of the antibacterial master batch in the comparative example 2 is too small, although the initial antibacterial efficiency of the material can reach 92%, after the material is treated for 720 hours under the water bath condition at 55 ℃, the antibacterial efficiency attenuation of the material is 86%, the antibacterial efficiency retention rate is only 93%, and the antibacterial stability is poor.
Compared with the embodiment 1/2/3, the comparison example 3/4/5 shows that the antibacterial master batch of the comparison example 3/4/5 is not added with the main antibacterial agent, the initial antibacterial efficiency value of the material is lower than 65%, and after the material is treated for 720 hours in a water bath condition at 55 ℃, the antibacterial efficiency retention rate of the material is lower than 90%, and the antibacterial effect and the antibacterial stability are poor;
compared with the example 6, the comparison example 6 shows that the antibacterial master batch of the comparison example 6 is not added with the auxiliary antibacterial agent, the initial antibacterial efficiency value of the material reaches 90 percent, and the material still has a good antibacterial effect, but after the material is treated for 720 hours under the water bath condition of 55 ℃, the antibacterial efficiency of the material is rapidly attenuated and is only 77 percent, the antibacterial stability is poor, and the use requirement cannot be met.
It will be appreciated by those of ordinary skill in the art that the examples provided herein are intended to assist the reader in understanding the principles of the invention and are to be construed as being without limitation to such specifically recited examples and embodiments. Those skilled in the art can make various other specific changes and combinations based on the teachings of the present invention without departing from the spirit of the invention, and these changes and combinations are within the scope of the invention.
Claims (13)
1. The polypropylene-based antibacterial master batch is characterized by comprising the following components in parts by weight:
90 parts of polypropylene resin;
2-10 parts of a main antibacterial agent;
2-10 parts of auxiliary antibacterial agent;
0.2-1 part of coupling agent solution;
1-10 parts of a compatilizer;
the main antibacterial agent is selected from one or more of monazite powder, granite powder, phosphate rock powder or fly ash;
the auxiliary antibacterial agent is selected from any one or more of tourmaline powder or fluorine antibacterial powder; the fluorine antibacterial powder is selected from one or more of polytetrafluoroethylene or difluoroethylene-hexafluoroethylene copolymer;
the coupling agent solution is prepared by mixing a silane coupling agent and absolute ethyl alcohol in a volume ratio of (0.3-1): 1, preparation.
2. The polypropylene-based antibacterial masterbatch according to claim 1, wherein the weight ratio of the primary antibacterial agent to the secondary antibacterial agent is (0.2-5): 1.
3. the polypropylene-based antibacterial masterbatch according to claim 1, wherein the weight ratio of the primary antibacterial agent to the secondary antibacterial agent is (0.5-2): 1.
4. the polypropylene-based antibacterial masterbatch according to claim 1, wherein the particle size D of the primary antibacterial agent and the secondary antibacterial agent is 90 Is 0.01-6 μm.
5. The polypropylene-based antibacterial masterbatch according to claim 1, wherein the particle size D of the primary antibacterial agent and the secondary antibacterial agent is 90 Is 0.3 μm to 0.9 μm.
6. The polypropylene-based antimicrobial masterbatch according to claim 1, wherein the primary antimicrobial agent is selected from monazite powder; the auxiliary antibacterial agent is selected from one or more of fluorine antibacterial powder.
7. The polypropylene-based antibacterial masterbatch according to claim 1, wherein the melt flow rate of the polypropylene resin is 10-60g/10min at 230 ℃ and 2.16 kg.
8. The polypropylene-based antibacterial masterbatch according to claim 1, wherein the melt flow rate of the polypropylene resin is 20-40g/10min at 230 ℃ and 2.16 kg.
9. The polypropylene-based antibacterial masterbatch according to claim 1, wherein the compatibilizer is one or more selected from maleic anhydride grafted olefin copolymer and glycidyl methacrylate grafted olefin copolymer.
10. The polypropylene-based antibacterial masterbatch according to claim 1, further comprising 0.1-1 part by weight of a processing aid; the processing aid is any one or more of a lubricant, an antioxidant or an anti-aging agent.
11. The method for preparing the polypropylene-based antibacterial masterbatch according to any one of claims 1 to 10, comprising the steps of:
s1: adding the main antibacterial agent and the auxiliary antibacterial agent into a grinding tank according to the proportion, grinding for 10-15 minutes continuously, adding a coupling agent solution, continuously grinding for 10-20 minutes, and drying for 1-2 hours at 80-100 ℃; obtaining antibacterial powder after surface activity treatment;
s2: mixing the antibacterial powder prepared in the step S1 with the rest components by a high-speed mixer for 3-5min to obtain a mixture;
s3: feeding the mixture obtained in the step S2 into a double-screw extruder, and extruding and granulating after melting, plasticizing and mixing by the double-screw extruder, wherein the screw temperature of the double-screw extruder is 160-220 ℃, and the rotating speed is 300-500rpm; and (3) preparing the polypropylene-based antibacterial master batch.
12. Use of the polypropylene-based antibacterial masterbatch according to any one of claims 1 to 10 in automotive interior materials.
13. The polypropylene-based antibacterial masterbatch used in the automotive interior material according to claim 12, wherein the automotive interior material comprises the following components in parts by weight:
90-100 parts of a polypropylene material;
2-10 parts of polypropylene-based antibacterial masterbatch according to any one of claims 1-10.
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| CN113956566B (en) * | 2021-09-24 | 2023-03-21 | 金发科技股份有限公司 | Polypropylene-based antibacterial master batch and preparation method and application thereof |
| CN114920964B (en) * | 2022-04-24 | 2023-04-11 | 宜宾天亿新材料科技有限公司 | Antibacterial tablecloth and preparation method thereof |
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| CN110746672B (en) * | 2019-09-18 | 2022-06-17 | 安徽理工大学 | Method for preparing antibacterial master batch by using waste and/or waste plastics as raw materials |
| CN112694677B (en) * | 2021-01-08 | 2022-03-22 | 会通新材料股份有限公司 | Bamboo charcoal and tourmaline composite Ag-loaded antibacterial agent, antibacterial polypropylene composition and preparation method |
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| CN113956566B (en) * | 2021-09-24 | 2023-03-21 | 金发科技股份有限公司 | Polypropylene-based antibacterial master batch and preparation method and application thereof |
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| CN104844934A (en) * | 2015-04-30 | 2015-08-19 | 南京博方生物科技有限公司 | Composite mine-plastic material and using method thereof |
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