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CN111533992A - High-gloss environment-friendly antibacterial polypropylene composite material and preparation method thereof - Google Patents

High-gloss environment-friendly antibacterial polypropylene composite material and preparation method thereof Download PDF

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CN111533992A
CN111533992A CN202010360735.0A CN202010360735A CN111533992A CN 111533992 A CN111533992 A CN 111533992A CN 202010360735 A CN202010360735 A CN 202010360735A CN 111533992 A CN111533992 A CN 111533992A
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polypropylene
composite material
antibacterial
polypropylene composite
friendly
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CN111533992B (en
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梁伟成
陈晓东
孟成铭
阮静
孔伟
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Shanghai Sunny Technology Co ltd
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Abstract

The invention relates to a high-gloss environment-friendly antibacterial polypropylene composite material and a preparation method thereof, according to a formula ratio, homo-polypropylene (with a melt index of 40-60 g/10min), co-polypropylene (with a melt index of 60-100 g/10min, ethylene-propylene co-polypropylene), polyvinylidene fluoride (with a melt index of 3-5 g/10min), a foaming agent (diisopropyl azodicarboxylate), a nucleating agent and peroxide are mixed and then are melt-extruded with an antibacterial agent (a compound of dimethyl fumarate and peptide antibacterial peptide) to prepare the high-gloss environment-friendly antibacterial polypropylene composite material; the glossiness of the prepared polypropylene composite material is 82-88, and the antibacterial rates of the polypropylene composite material to escherichia coli and staphylococcus aureus are 98.9-99.9% and 98.8-99.9%, respectively. The method is simple and easy to implement, and is environment-friendly and safe; the prepared polypropylene composite material does not contain heavy metal ions, and has high glossiness and excellent antibacterial performance.

Description

High-gloss environment-friendly antibacterial polypropylene composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of polypropylene composite materials, and relates to a high-gloss environment-friendly antibacterial polypropylene composite material and a preparation method thereof.
Background
The polypropylene material has low price, excellent performance and low density, is widely applied to the fields of automobiles, household appliances, electricians, foods and the like, and can be infected and bred with various pathogenic bacteria on the surface of plastic because people inevitably contact with the plastic in daily life, so that people can be easily infected by the bacteria when contacting with the plastic. The floating population of China is numerous, the health consciousness of people is gradually strengthened, and the development of antibacterial plastics has very important practical significance for reducing disease transmission in order to avoid cross infection caused by using plastic products.
At present, the materials adopting heavy metal ion antibacterial agents are the most extensive, such as silver-carrying antibacterial agents, and the antibacterial effect is excellent, but the antibacterial agents in the materials contain heavy metal ions, so that the toxicity is high, the chemical activity is active and unstable, and the luster of the materials is lost due to the precipitation of the antibacterial agents, so that the materials have limitations in use, and the market urgently needs an environment-friendly antibacterial polypropylene material with high luster.
Patent CN201710758578.7 discloses a transparent, antibacterial polypropylene material, which is made of the following components: 92.8-96.45% of polypropylene, 3-5% of self-made antibacterial master batch, 0.5-2% of antioxidant and 0.05-0.2% of white oil, and the modified polypropylene is prepared by mixing and granulating, wherein the self-made antibacterial master batch is prepared by crosslinking 99.5-99.9% of maleic anhydride grafted polypropylene and 0.1-0.5% of 3, 3-diphenylacrolein under an acidic condition. However, the gloss is not involved, the antibacterial effect is limited and the toxicity is high.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a high-gloss environment-friendly antibacterial polypropylene composite material and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the high-gloss environment-friendly antibacterial polypropylene composite material comprises homo-polypropylene, co-polypropylene, polyvinylidene fluoride, a foaming agent and an antibacterial agent, wherein the melt index of the homo-polypropylene is 40-60 g/10min (the test condition is 230 ℃ C. is 2.16kg), the co-polypropylene is ethylene-propylene co-polypropylene with the melt index of 60-100 g/10min (the test condition is 230 ℃ C. is 2.16kg), the melt index of the polyvinylidene fluoride is 3-5 g/10min (the test condition is 230 ℃ C. is 2.16kg), the polyvinylidene fluoride is a vinylidene fluoride homopolymer, the structure of the vinylidene fluoride homopolymer is more regular, the affinity of the vinylidene fluoride homopolymer to protein is higher, such as French Suwei 6010, the antibacterial agent is a compound of dimethyl fumarate and peptide antibacterial peptide, the dimethyl fumarate and the peptide antibacterial peptide have a synergistic antibacterial effect, and the inhibition effect of the dimethyl fumarate to the enzyme activity is obvious, the antibacterial peptide has the characteristics of being non-toxic and pollution-free, excellent in antibacterial effect, non-toxic and pollution-free, renewable and environment-friendly, besides, the lysozyme and the methylene salicylic acid antibacterial peptide also have similar effects, the foaming agent is diisopropyl azodicarboxylate, and the foaming agent can also be barium azodicarboxylate, 2,2' -azobisisobutyronitrile and other substances;
the glossiness (60 degrees and ASTM523 standard) of the high-gloss environment-friendly antibacterial polypropylene composite material is 82-88, and the antibacterial rates (ISO 22196 plus 2011 standard) on escherichia coli and staphylococcus aureus are 98.9-99.9% and 98.8-99.9% respectively.
As a preferred technical scheme:
according to the high-gloss environment-friendly antibacterial polypropylene composite material, the weight part ratio of the dimethyl fumarate to the peptide antibacterial peptide in the antibacterial agent is 1-5: 0.1-1.
The high-gloss environment-friendly antibacterial polypropylene composite material also comprises a nucleating agent and peroxide;
the high-gloss environment-friendly antibacterial polypropylene composite material comprises the following components in parts by weight:
Figure BDA0002474918760000021
according to the high-gloss environment-friendly antibacterial polypropylene composite material, the nucleating agent is dibenzylidene sorbitol, and can also be a derivative of dibenzylidene sorbitol, such as bis (p-chlorobenzylidene) sorbitol (CDBS), bis (p-ethylbenzylidene) sorbitol (EDBS), bis (3, 4-dimethylbenzylidene) sorbitol (DMDBS) and the like, so that the polypropylene material can be promoted to generate more alpha crystals, the glossiness of the material is improved, the peroxide is acetylacetone peroxide, and can also be methyl ethyl ketone peroxide, cyclohexanone peroxide and the like, a moderate degradation effect is achieved on the polypropylene material, a plurality of free single chains are generated, and the single chains are used as crystal nuclei to form a synergistic effect with the nucleating agent, so that the crystallinity of the material is promoted, and the glossiness of the material is improved.
The high-gloss environment-friendly antibacterial polypropylene composite material comprises the following components in parts by weight:
Figure BDA0002474918760000022
the high-gloss environment-friendly antibacterial polypropylene composite material comprises the following components in parts by weight:
Figure BDA0002474918760000031
the invention also provides a method for preparing the high-gloss environment-friendly antibacterial polypropylene composite material, which is characterized in that the high-gloss environment-friendly antibacterial polypropylene composite material is prepared by mixing the homo-polypropylene, the co-polypropylene, the polyvinylidene fluoride, the foaming agent, the nucleating agent and the peroxide, and then melting and extruding the mixture with the antibacterial agent.
As a preferred technical scheme:
the method comprises the following specific steps:
(1) mixing homo-polypropylene, co-polypropylene, polyvinylidene fluoride, a foaming agent, a nucleating agent and peroxide in a mixer for 2-5 min according to a formula ratio;
(2) and (2) adding the mixed substances in the step (1) into a first section of cylinder of a double-screw extruder, feeding an antibacterial agent into a sixth section of cylinder of the double-screw extruder from the side, and performing extrusion granulation to obtain the high-gloss environment-friendly antibacterial polypropylene composite material.
According to the method, the rotating speed of the mixer in the step (1) is 45-50 r/min;
in the step (2), the rotating speed of the screw is 500-600 r/min, the temperature of the double-screw extruder before the sixth section of the cylinder body is 160 ℃, the temperature of the sixth section of the cylinder body is 100 ℃ in consideration of the temperature-resistant limit temperature of the antibacterial agent, and the temperature of the extruder after the sixth section of the cylinder body is also set to be 100 ℃.
The principle of the invention is as follows:
the diisopropyl azodicarboxylate is added as a foaming agent during processing, and nitrogen is released during processing of the double-screw extruder, so that on one hand, the nitrogen is used for diluting oxygen in the double-screw extruder, the stability of the antibacterial agent during processing can be maintained, and the processed material is prevented from discoloring; on the other hand, the dispersion of the antibacterial agent and the nucleating agent in the polypropylene can be promoted by utilizing the force generated by the nitrogen escaping to generate the gas flow. The invention also controls the addition amount of diisopropyl azodicarboxylate to be 1-2 wt% of the homopolymerized polypropylene, so that the content of released nitrogen is lower, the problem that nitrogen is not easy to escape due to overlarge internal air pressure of resin during processing is avoided, and in order to enable nitrogen to better escape from the resin, the homopolymerized polypropylene with higher melt index and lower melt strength (generally, the higher the melt index is, the lower the melt strength is) is adopted, so that the melt strength is low, the melt of PP resin is easier to break, the nitrogen is easier to escape from the polypropylene melt, and the whole processing process is maintained in the atmosphere of nitrogen.
According to the invention, polyvinylidene fluoride is blended in the polypropylene material, and the modified polypropylene material can more firmly adsorb bacteria by utilizing the characteristic of high affinity of polyvinylidene fluoride to protein, so that the contact between the bacteria and the antibacterial agent in the material is increased, and the antibacterial effect of the antibacterial agent is amplified.
According to the invention, ethylene propylene copolymerization polypropylene with a high melting index (60-100 g/10min) is used as a compatilizer to build a bridge for homo-polypropylene and polyvinylidene fluoride, an ethylene chain segment in the copolymerization polypropylene has good compatibility with the polyvinylidene fluoride, and a propylene chain segment has good compatibility with the homo-polypropylene; the melt index of the homopolymerized polypropylene is 40-60 g/min, the melt index of the copolymerized polypropylene is 60-100 g/min, and the melt index of the copolymerized polypropylene is higher than that of the homopolymerized polypropylene, so that the dispersibility of the copolymerized polypropylene can be better improved in a system, and the compatibility effect is improved; by controlling the content of the copolymerized polypropylene to be 5-10 wt% of the homopolymerized polypropylene, on one hand, the effect of promoting compatibility of the copolymerized polypropylene is ensured, and on the other hand, the dispersion effect of the copolymerized polypropylene in the material is enhanced, so that the copolymerized polypropylene exists in a dispersed phase form, a continuous phase is not formed, and the glossiness of the material is not influenced.
According to the invention, dimethyl fumarate and peptide antibacterial peptide are compounded as an antibacterial agent, the peptide antibacterial peptide is used for damaging a cell membrane to enable cytoplasm to flow out, the dimethyl fumarate is directly contacted with the cell membrane to inhibit the respiration of cells, so that a synergistic antibacterial effect is achieved, and in order to ensure the stability of the antibacterial agent, reasonable design is carried out on the process, the antibacterial agent is fed from the sixth section, the temperature of the sixth section and the subsequent section is set to be 100 ℃, and because the polypropylene material before the sixth section is completely plasticized, although the temperature is lower than the melting point of the material, the material at the moment is completely plasticized, and the material can be extruded, pulled into strips and cut into granules.
The invention also adopts acetylacetone peroxide in the material formula, can slightly degrade the polypropylene material during processing to generate a plurality of free single chains, and the single chains can be used as crystal nuclei to form a synergistic effect with the nucleating agent dibenzylidene sorbitol during crystallization, and specifically comprises the following steps: the slightly degraded polypropylene can generate a plurality of free single chains, the single chains can be used as crystal nucleuses, so that the polypropylene has more and smaller crystal nucleuses during crystallization, dibenzylidene sorbitol can be dimerized through intermolecular hydrogen bonds, the dimer has a stable V-shaped configuration, the free single chains generated by peroxide can be better stabilized by the V-shaped structure, the polypropylene molecular chains combined with the free single chains are stabilized, the molecular chain arrangement is more closely and regularly, therefore, the polypropylene material has smaller crystal form size and higher crystallinity, and the material has higher glossiness.
Has the advantages that:
(1) the preparation method of the high-gloss environment-friendly antibacterial polypropylene composite material is simple and easy to implement, environment-friendly and safe, and low in cost;
(2) the high-gloss environment-friendly antibacterial polypropylene composite material disclosed by the invention does not contain heavy metal ions, is low in toxicity and environment-friendly, and has high gloss and excellent antibacterial performance.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A preparation method of a high-gloss environment-friendly antibacterial polypropylene composite material adopts the following formula (in parts by weight):
Figure BDA0002474918760000051
wherein the melt index of the homopolymerized polypropylene is 40g/10min, the melt index of the ethylene-propylene copolymerized polypropylene is 60g/10min, and the melt index of the polyvinylidene fluoride is 3g/10 min;
the preparation method comprises the following steps:
(1) mixing homo-polypropylene, ethylene propylene co-polypropylene, polyvinylidene fluoride, diisopropyl azodicarboxylate, dibenzylidene sorbitol and acetylacetone peroxide in a mixer for 2min according to a formula ratio, wherein the rotating speed of the mixer is 45 r/min;
(2) adding the mixed substances in the step (1) into a first section of cylinder of a double-screw extruder, feeding dimethyl fumarate and the peptide antibacterial peptide into a sixth section of cylinder of the double-screw extruder from the side of the cylinder, and performing extrusion granulation to obtain the high-gloss environment-friendly antibacterial polypropylene composite material, wherein the rotating speed of a screw is 500r/min, the temperature of the double-screw extruder in front of the sixth section of cylinder is 160 ℃, and the temperature of the cylinder in the rear of the sixth section (including the sixth section) is 100 ℃.
The glossiness of the finally prepared high-gloss environment-friendly antibacterial polypropylene composite material is 85%, and the antibacterial rates to escherichia coli and staphylococcus aureus are 99.2% and 99.3%, respectively.
Example 2
A preparation method of a high-gloss environment-friendly antibacterial polypropylene composite material adopts the following formula (in parts by weight):
Figure BDA0002474918760000052
Figure BDA0002474918760000061
wherein the melt index of the homopolymerized polypropylene is 42g/10min, the melt index of the ethylene-propylene copolymerized polypropylene is 68g/10min, and the melt index of the polyvinylidene fluoride is 3.2g/10 min;
the preparation method comprises the following steps:
(1) mixing homo-polypropylene, ethylene propylene co-polypropylene, polyvinylidene fluoride, diisopropyl azodicarboxylate, dibenzylidene sorbitol and acetylacetone peroxide in a mixer for 5min according to a formula ratio, wherein the rotating speed of the mixer is 50 r/min;
(2) adding the mixed substances in the step (1) into a first section of cylinder of a double-screw extruder, feeding dimethyl fumarate and the peptide antibacterial peptide into a sixth section of cylinder of the double-screw extruder from the side of the cylinder, and performing extrusion granulation to obtain the high-gloss environment-friendly antibacterial polypropylene composite material, wherein the rotating speed of a screw is 600r/min, the temperature of the double-screw extruder in front of the sixth section of cylinder is 160 ℃, and the temperature of the cylinder in the rear of the sixth section (including the sixth section) is 100 ℃.
The glossiness of the finally prepared high-gloss environment-friendly antibacterial polypropylene composite material is 82, and the antibacterial rates to escherichia coli and staphylococcus aureus are 98.9% and 98.8% respectively.
Example 3
A preparation method of a high-gloss environment-friendly antibacterial polypropylene composite material adopts the following formula (in parts by weight):
wherein the melt index of the homopolymerized polypropylene is 48g/10min, the melt index of the ethylene-propylene copolymerized polypropylene is 72g/10min, and the melt index of the polyvinylidene fluoride is 3.6g/10 min;
the preparation method comprises the following steps:
(1) mixing homo-polypropylene, ethylene propylene co-polypropylene, polyvinylidene fluoride, diisopropyl azodicarboxylate, dibenzylidene sorbitol and acetylacetone peroxide in a mixer for 3min according to a formula ratio, wherein the rotating speed of the mixer is 50 r/min;
(2) adding the mixed substances in the step (1) into a first section of cylinder of a double-screw extruder, feeding dimethyl fumarate and the peptide antibacterial peptide into a sixth section of cylinder of the double-screw extruder from the side of the cylinder, and performing extrusion granulation to obtain the high-gloss environment-friendly antibacterial polypropylene composite material, wherein the rotating speed of a screw is 550r/min, the temperature of the double-screw extruder in front of the sixth section of cylinder is 160 ℃, and the temperature of the cylinder in the rear of the sixth section (including the sixth section) is 100 ℃.
The glossiness of the finally prepared high-gloss environment-friendly antibacterial polypropylene composite material is 88, and the antibacterial rates to escherichia coli and staphylococcus aureus are 98.7% and 99.9% respectively.
Example 4
A preparation method of a high-gloss environment-friendly antibacterial polypropylene composite material adopts the following formula (in parts by weight):
Figure BDA0002474918760000071
wherein the melt index of the homopolymerized polypropylene is 50g/10min, the melt index of the ethylene-propylene copolymerized polypropylene is 80g/10min, and the melt index of the polyvinylidene fluoride is 4g/10 min;
the preparation method comprises the following steps:
(1) mixing homo-polypropylene, ethylene propylene co-polypropylene, polyvinylidene fluoride, diisopropyl azodicarboxylate, dibenzylidene sorbitol and acetylacetone peroxide in a mixer for 3min according to a formula ratio, wherein the rotating speed of the mixer is 50 r/min;
(2) adding the mixed substances in the step (1) into a first section of cylinder of a double-screw extruder, feeding dimethyl fumarate and the peptide antibacterial peptide into a sixth section of cylinder of the double-screw extruder from the side of the cylinder, and performing extrusion granulation to obtain the high-gloss environment-friendly antibacterial polypropylene composite material, wherein the rotating speed of a screw is 550r/min, the temperature of the double-screw extruder in front of the sixth section of cylinder is 160 ℃, and the temperature of the cylinder in the rear of the sixth section (including the sixth section) is 100 ℃.
The glossiness of the finally prepared high-gloss environment-friendly antibacterial polypropylene composite material is 84, and the antibacterial rates to escherichia coli and staphylococcus aureus are 99.9% and 99.9% respectively.
Example 5
A preparation method of a high-gloss environment-friendly antibacterial polypropylene composite material adopts the following formula (in parts by weight):
Figure BDA0002474918760000072
Figure BDA0002474918760000081
wherein the melt index of the homopolymerized polypropylene is 55g/10min, the melt index of the ethylene-propylene copolymerized polypropylene is 88g/10min, and the melt index of the polyvinylidene fluoride is 4.3g/10 min;
the preparation method comprises the following steps:
(1) mixing homo-polypropylene, ethylene propylene co-polypropylene, polyvinylidene fluoride, diisopropyl azodicarboxylate, dibenzylidene sorbitol and acetylacetone peroxide in a mixer for 3min according to a formula ratio, wherein the rotating speed of the mixer is 50 r/min;
(2) adding the mixed substances in the step (1) into a first section of cylinder of a double-screw extruder, feeding dimethyl fumarate and the peptide antibacterial peptide into a sixth section of cylinder of the double-screw extruder from the side of the cylinder, and performing extrusion granulation to obtain the high-gloss environment-friendly antibacterial polypropylene composite material, wherein the rotating speed of a screw is 550r/min, the temperature of the double-screw extruder in front of the sixth section of cylinder is 160 ℃, and the temperature of the cylinder in the rear of the sixth section (including the sixth section) is 100 ℃.
The glossiness of the finally prepared high-gloss environment-friendly antibacterial polypropylene composite material is 86, and the antibacterial rates to escherichia coli and staphylococcus aureus are 99.1% and 98.9% respectively.
Example 6
A preparation method of a high-gloss environment-friendly antibacterial polypropylene composite material adopts the following formula (in parts by weight):
Figure BDA0002474918760000082
wherein the melt index of the homopolymerized polypropylene is 56g/10min, the melt index of the ethylene-propylene copolymerized polypropylene is 90g/10min, and the melt index of the polyvinylidene fluoride is 4.5g/10 min;
the preparation method comprises the following steps:
(1) mixing homo-polypropylene, ethylene propylene co-polypropylene, polyvinylidene fluoride, diisopropyl azodicarboxylate, dibenzylidene sorbitol and acetylacetone peroxide in a mixer for 3min according to a formula ratio, wherein the rotating speed of the mixer is 50 r/min;
(2) adding the mixed substances in the step (1) into a first section of cylinder of a double-screw extruder, feeding dimethyl fumarate and the peptide antibacterial peptide into a sixth section of cylinder of the double-screw extruder from the side of the cylinder, and performing extrusion granulation to obtain the high-gloss environment-friendly antibacterial polypropylene composite material, wherein the rotating speed of a screw is 550r/min, the temperature of the double-screw extruder in front of the sixth section of cylinder is 160 ℃, and the temperature of the cylinder in the rear of the sixth section (including the sixth section) is 100 ℃.
The glossiness of the finally prepared high-gloss environment-friendly antibacterial polypropylene composite material is 88, and the antibacterial rates to escherichia coli and staphylococcus aureus are 99.9% and 99.9% respectively.
Example 7
A preparation method of a high-gloss environment-friendly antibacterial polypropylene composite material adopts the following formula (in parts by weight):
Figure BDA0002474918760000091
wherein the melt index of the homopolymerized polypropylene is 60g/10min, the melt index of the ethylene-propylene copolymerized polypropylene is 100g/10min, and the melt index of the polyvinylidene fluoride is 4.9g/10 min;
the preparation method comprises the following steps:
(1) mixing homo-polypropylene, ethylene propylene co-polypropylene, polyvinylidene fluoride, diisopropyl azodicarboxylate, dibenzylidene sorbitol and acetylacetone peroxide in a mixer for 3min according to a formula ratio, wherein the rotating speed of the mixer is 50 r/min;
(2) adding the mixed substances in the step (1) into a first section of cylinder of a double-screw extruder, feeding dimethyl fumarate and the peptide antibacterial peptide into a sixth section of cylinder of the double-screw extruder from the side of the cylinder, and performing extrusion granulation to obtain the high-gloss environment-friendly antibacterial polypropylene composite material, wherein the rotating speed of a screw is 550r/min, the temperature of the double-screw extruder in front of the sixth section of cylinder is 160 ℃, and the temperature of the cylinder in the rear of the sixth section (including the sixth section) is 100 ℃.
The glossiness of the finally prepared high-gloss environment-friendly antibacterial polypropylene composite material is 88, and the antibacterial rates to escherichia coli and staphylococcus aureus are 99.8% and 99.9% respectively.
Example 8
A preparation method of a high-gloss environment-friendly antibacterial polypropylene composite material adopts the following formula (in parts by weight):
Figure BDA0002474918760000101
wherein the melt index of the homopolymerized polypropylene is 60g/10min, the melt index of the ethylene-propylene copolymerized polypropylene is 100g/10min, and the melt index of the polyvinylidene fluoride is 5g/10 min;
the preparation method comprises the following steps:
(1) mixing homo-polypropylene, ethylene propylene co-polypropylene, polyvinylidene fluoride, diisopropyl azodicarboxylate, dibenzylidene sorbitol and acetylacetone peroxide in a mixer for 3min according to a formula ratio, wherein the rotating speed of the mixer is 50 r/min;
(2) adding the mixed substances in the step (1) into a first section of cylinder of a double-screw extruder, feeding dimethyl fumarate and the peptide antibacterial peptide into a sixth section of cylinder of the double-screw extruder from the side of the cylinder, and performing extrusion granulation to obtain the high-gloss environment-friendly antibacterial polypropylene composite material, wherein the rotating speed of a screw is 550r/min, the temperature of the double-screw extruder in front of the sixth section of cylinder is 160 ℃, and the temperature of the cylinder in the rear of the sixth section (including the sixth section) is 100 ℃.
The glossiness of the finally prepared high-gloss environment-friendly antibacterial polypropylene composite material is 85%, and the antibacterial rates to escherichia coli and staphylococcus aureus are 99.5% and 99.2% respectively.
Comparative example 1
The preparation method of the high-gloss environment-friendly antibacterial polypropylene composite material is basically the same as that in example 1, and is different only in that the adopted formula (in parts by weight) is as follows:
Figure BDA0002474918760000102
the glossiness of the finally prepared high-gloss environment-friendly antibacterial polypropylene composite material is 83, and the antibacterial rates to escherichia coli and staphylococcus aureus are 94.2% and 93.3%, respectively.
Comparative example 2
A preparation method of a high-gloss environment-friendly antibacterial polypropylene composite material, which is basically the same as that in example 2, and is different only in that the adopted formula (in parts by weight) is as follows:
Figure BDA0002474918760000111
the glossiness of the finally prepared high-gloss environment-friendly antibacterial polypropylene composite material is 79, and the antibacterial rates to escherichia coli and staphylococcus aureus are 88.7% and 89.2% respectively.
Comparative example 3
A preparation method of a high-gloss environment-friendly antibacterial polypropylene composite material, which is basically the same as that in example 3, and is different only in that the adopted formula (in parts by weight) is as follows:
Figure BDA0002474918760000112
the glossiness of the finally prepared high-gloss environment-friendly antibacterial polypropylene composite material is 62, and the antibacterial rates to escherichia coli and staphylococcus aureus are 98.7% and 99.9% respectively.
Comparative example 4
A preparation method of a high-gloss environment-friendly antibacterial polypropylene composite material, which is basically the same as that in example 4, and is different from the following components in part by weight:
Figure BDA0002474918760000113
Figure BDA0002474918760000121
the glossiness of the finally prepared high-gloss environment-friendly antibacterial polypropylene composite material is 65, and the antibacterial rates to escherichia coli and staphylococcus aureus are 94.9% and 96.8% respectively.
Comparative example 5
A preparation method of a high-gloss environment-friendly antibacterial polypropylene composite material is basically the same as that in example 4, except that the melt index of ethylene-propylene copolymer polypropylene adopted in the formula is 50g/10min (the test condition is 230 ℃ C. by 2.16 kg).
The glossiness of the finally prepared high-gloss environment-friendly antibacterial polypropylene composite material is 83, and the antibacterial rates to escherichia coli and staphylococcus aureus are 95.2% and 95.3% respectively.
Comparative example 6
A preparation method of a high-gloss environment-friendly antibacterial polypropylene composite material, which is basically the same as that in example 4, and is different from the following components in part by weight:
Figure BDA0002474918760000122
the glossiness of the finally prepared high-gloss environment-friendly antibacterial polypropylene composite material is 83, and the antibacterial rates to escherichia coli and staphylococcus aureus are 94.2% and 94.5%, respectively.
Comparative example 7
A preparation method of a high-gloss environment-friendly antibacterial polypropylene composite material, which is basically the same as that in example 4, and is different from the following components in part by weight:
Figure BDA0002474918760000123
Figure BDA0002474918760000131
the glossiness of the finally prepared high-gloss environment-friendly antibacterial polypropylene composite material is 83, and the antibacterial rates to escherichia coli and staphylococcus aureus are 95.6% and 93.4% respectively.
Comparative example 8
A preparation method of a high-gloss environment-friendly antibacterial polypropylene composite material, which is basically the same as that in example 4, and is different from the preparation method in the step (2) only in that the temperature of the cylinder before the sixth section of the double-screw extruder is 160 ℃, and the temperature of the cylinder after the sixth section (including the sixth section) is also 160 ℃.
The glossiness of the finally prepared high-gloss environment-friendly antibacterial polypropylene composite material is 82, and the antibacterial rates to escherichia coli and staphylococcus aureus are 90.3% and 90.2% respectively.
Compared with the embodiment 1, the comparative example 1 does not add ethylene propylene copolymerized polypropylene to improve the compatibility of the homopolymerized polypropylene and the polyvinylidene fluoride, so that the overall affinity of the material to protein is reduced, and the antibacterial effect is reduced; compared with the example 2, the polyvinylidene fluoride is absent, so that the material is only pure polypropylene resin, has weak affinity to protein and can not better catch bacteria, and the antibacterial effect is reduced; comparative example 3 compared to example 3, without acetylacetone peroxide, the lack of sufficient single chains in the material as nuclei to promote crystallization, and thus the gloss is reduced; compared with the example 4, the diisopropyl azodicarboxylate is not added, the nitrogen generated by the decomposition is absent, the antibacterial agent is easily decomposed, and the dispersion effect is poor, so that the antibacterial performance of the material is reduced; compared with the example 4, the ethylene propylene copolymerization polypropylene with lower melt index is adopted, and the antibacterial effect is reduced because the melt index is lower, the dispersity is poor, and the compatibility promotion effect of the homopolymerization polypropylene and the polyvinylidene fluoride is limited. Comparative example 6 compared with example 4, dimethyl fumarate was used alone, and there was no synergistic effect of the peptide antibacterial peptide, so that the antibacterial effect was decreased. Comparative example 7 compared with example 4, the antibacterial effect was also deteriorated due to lack of the synergistic antibacterial effect of dimethyl fumarate by using only the peptide antibacterial peptide. Comparative example 8 compared with example 4, the antibacterial agent was partially failed due to the absence of a lower processing temperature after the sixth stage, so that the antibacterial effect was reduced.

Claims (9)

1. A high-gloss environment-friendly antibacterial polypropylene composite material is characterized in that: the polypropylene composite material comprises homo-polypropylene, co-polypropylene, polyvinylidene fluoride, a foaming agent and an antibacterial agent, wherein the melt index of the homo-polypropylene is 40-60 g/10min, the co-polypropylene is ethylene-propylene co-polypropylene with the melt index of 60-100 g/10min, the melt index of the polyvinylidene fluoride is 3-5 g/10min, the antibacterial agent is a compound of dimethyl fumarate and peptide antibacterial peptide, and the foaming agent is diisopropyl azodicarboxylate;
the glossiness of the high-gloss environment-friendly antibacterial polypropylene composite material is 82-88, and the antibacterial rates of the high-gloss environment-friendly antibacterial polypropylene composite material to escherichia coli and staphylococcus aureus are 98.9-99.9% and 98.8-99.9%, respectively.
2. The high-gloss environment-friendly antibacterial polypropylene composite material as claimed in claim 1, wherein the weight part ratio of the dimethyl fumarate to the peptide antibacterial peptide in the antibacterial agent is 1-5: 0.1-1.
3. The high-gloss environment-friendly antibacterial polypropylene composite material according to claim 2, further comprising a nucleating agent and a peroxide;
the high-gloss environment-friendly antibacterial polypropylene composite material comprises the following components in parts by weight:
Figure FDA0002474918750000011
4. the high-gloss environment-friendly antibacterial polypropylene composite material according to claim 3, wherein the nucleating agent is dibenzylidene sorbitol, and the peroxide is acetylacetone peroxide.
5. The high-gloss environment-friendly antibacterial polypropylene composite material according to claim 4, wherein the high-gloss environment-friendly antibacterial polypropylene composite material comprises the following components in parts by weight:
Figure FDA0002474918750000012
Figure FDA0002474918750000021
6. the high-gloss environment-friendly antibacterial polypropylene composite material according to claim 4, wherein the high-gloss environment-friendly antibacterial polypropylene composite material comprises the following components in parts by weight:
Figure FDA0002474918750000022
7. the method for preparing the high-gloss environment-friendly antibacterial polypropylene composite material as claimed in any one of claims 3 to 6, is characterized in that: the high-gloss environment-friendly antibacterial polypropylene composite material is prepared by mixing homo-polypropylene, co-polypropylene, polyvinylidene fluoride, a foaming agent, a nucleating agent and peroxide, and then melting and extruding the mixture with an antibacterial agent.
8. The method according to claim 7, characterized by the specific steps of:
(1) mixing homo-polypropylene, co-polypropylene, polyvinylidene fluoride, a foaming agent, a nucleating agent and peroxide in a mixer for 2-5 min according to a formula ratio;
(2) and (2) adding the mixed substances in the step (1) into a first section of cylinder of a double-screw extruder, feeding an antibacterial agent into a sixth section of cylinder of the double-screw extruder from the side, and performing extrusion granulation to obtain the high-gloss environment-friendly antibacterial polypropylene composite material.
9. The method according to claim 8, wherein the rotation speed of the mixer in the step (1) is 45-50 r/min;
in the step (2), the rotating speed of the screw is 500-600 r/min, the temperature of the double-screw extruder before the sixth section of the cylinder is 160 ℃, and the temperature of the sixth section of the cylinder and the cylinder after the sixth section of the cylinder is 100 ℃.
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