CN112552585A - Modified polypropylene and preparation method thereof - Google Patents
Modified polypropylene and preparation method thereof Download PDFInfo
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- CN112552585A CN112552585A CN201910918932.7A CN201910918932A CN112552585A CN 112552585 A CN112552585 A CN 112552585A CN 201910918932 A CN201910918932 A CN 201910918932A CN 112552585 A CN112552585 A CN 112552585A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2248—Oxides; Hydroxides of metals of copper
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses modified polypropylene and a preparation method thereof, and the modified polypropylene is prepared by mixing modified nano CuO, copper chlorophyllin acid and polypropylene, wherein the modified nano CuO is obtained by subjecting the nano CuO to the action of argon plasma, and the modified nano CuO and the copper chlorophyllin acid which are subjected to the action of the argon plasma are added into the polypropylene, so that the problems that in the prior art, the consumption of antibacterial agents and scraping-resistant auxiliaries is large, and the scraping-resistant agents have adverse effects on the antibacterial effect are solved. The modified polypropylene material disclosed by the invention has excellent antibacterial performance and good scratch resistance.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to modified polypropylene and a preparation method thereof.
Background
Polypropylene is a thermoplastic resin prepared by polymerizing propylene, is nontoxic and tasteless, has low density, better strength, rigidity, hardness and heat resistance than low-pressure polyethylene, can be used at about 100 ℃, has good dielectric property and high-frequency insulation property, is not influenced by humidity, but becomes brittle at low temperature, is not wear-resistant and is easy to age. It is suitable for making general mechanical parts, corrosion-resistant parts and insulating parts. Common organic solvents such as acid and alkali hardly act on the organic solvent, and can be used for tableware.
Meanwhile, polypropylene is widely applied to the fields of point-adding, automobiles, food, medical use and the like as a general polymer material with excellent comprehensive performance, and the polypropylene material with excellent comprehensive performance is favored by manufacturers along with the continuous development of the society. And the common PP product is easy to be infected with bacteria, which poses certain threat to human health. In some fields, polypropylene is required to have excellent scratch resistance because of the requirements of antibacterial property and high appearance of products.
At present, the antibacterial and scratch-resistant polypropylene material generally realizes the antibacterial and scratch-resistant effects by adding an antibacterial agent and a scratch-resistant auxiliary agent into the polypropylene material, but the problem of large using amount exists, and meanwhile, a scratch-resistant agent is often a bacterial nutrient source and can reduce the antibacterial effect.
Disclosure of Invention
In view of the above, the invention provides a modified polypropylene and a preparation method thereof, wherein modified nano CuO and copper chlorophyllin acid which are subjected to the action of argon plasma are added into polypropylene, so that the problems that in the prior art, the dosage of an antibacterial agent and a scratch-resistant auxiliary agent is large, and the scratch-resistant agent has adverse effect on the antibacterial effect are solved.
In order to achieve the purpose, the invention adopts the following technical scheme:
the modified polypropylene is prepared by mixing modified nano CuO, copper chlorophyllin and polypropylene, wherein the modified nano CuO is obtained by subjecting nano CuO to the action of argon plasma.
Further, in the modified polypropylene, the mass ratio of each component is modified nano CuO: copper chlorophyllin acid: polypropylene (2-4), (1-3), (100-120).
Further, the modification method of the modified nano CuO comprises the following steps: and placing the nano CuO into a plasma reaction chamber, introducing the argon plasma into the plasma reaction chamber, and acting the nano CuO for 1-3 hours.
Furthermore, the particle size of the nano CuO is 60-80 nm.
Further, the argon plasma pulse voltage is 2-4kV, and the pulse frequency is 800-1000 Hz.
Further, the purity of the copper chlorophyllin acid is not lower than 98%.
Another object of the present invention is to provide a method for preparing the modified polypropylene, comprising the following steps:
uniformly mixing the modified nano CuO, copper chlorophyllin and polypropylene to obtain a mixed material;
and performing melt extrusion granulation on the mixed material to obtain the modified polypropylene.
Further, the melt extrusion is performed in a twin screw extruder.
Preferably, the working temperature of each zone of the double-screw extruder is 140-155 ℃ in the first zone, 160-175 ℃ in the second zone, 160-175 ℃ in the third zone, 160-175 ℃ in the fourth zone, 160-175 ℃ in the fifth zone, 160-175 ℃ in the sixth zone, 170-180 ℃ at the head temperature, and the screw rotating speed is 190-220 r/min.
Compared with the prior art, the invention has the following beneficial effects:
the nano CuO is acted by argon plasma, so that the surface energy of the nano CuO is reduced, and the modified nano CuO is better dispersed in the polypropylene material.
Meanwhile, copper chlorophyllin is a porphyrin compound, wherein porphyrin groups can form singlet excited molecules under the irradiation of light, electron transfer is realized, partial ion free radicals are formed, so that fluorescence entering the molecules is quenched, the energy is transferred to modified nano CuO after the fluorescence is converted into self energy, hole electron pairs with high activity generated after the modified nano CuO obtains the energy are increased, high-oxidation-reduction ions are increased, more microorganisms and bacteria can be eliminated, and the antibacterial rate is improved.
In addition, the synergistic effect of copper chlorophyllin and modified nano CuO bears the main load of the surface during the friction of the material, thereby improving the scratch resistance of polypropylene.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the specific embodiments illustrated. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The manufacturers or sources of the raw materials used in the following examples and comparative examples are as follows:
nano CuO, beijing german island gold technologies ltd; copper chlorophyllin, zhengzhou hong cheng chemical products limited; PP (model Z30S), mazineb petrochemical.
Example 1
Nano CuO with the particle size of 60nm is put into a plasma reaction chamber, and simultaneously argon plasma is introduced into the plasma reaction chamber to act on the nano CuO for 1h, so as to obtain modified nano CuO; wherein the pulse voltage of the argon plasma is 2kV, and the pulse frequency is 800 Hz.
Weighing 20g of modified nano CuO, 10g of copper chlorophyllin and 1.0kg of PP, mixing and uniformly stirring to obtain a mixed material.
And adding the mixed material into a double-screw extruder, and carrying out melt extrusion granulation to obtain modified polypropylene, which is marked as P1. Wherein the temperature of each zone of the double-screw extruder is 140 ℃ in the first zone, 160 ℃ in the second zone, 160 ℃ in the third zone, 160 ℃ in the fourth zone, 160 ℃ in the fifth zone, 160 ℃ in the sixth zone, the head temperature is 170 ℃ and the screw rotating speed is 190 r/min.
Example 2
Nano CuO with the particle size of 80nm is placed into a plasma reaction chamber, and meanwhile, argon plasma is introduced into the plasma reaction chamber to act on the nano CuO for 3 hours, so that modified nano CuO is obtained; wherein the pulse voltage of the argon plasma is 4kV, and the pulse frequency is 1000 Hz.
Weighing 40g of modified nano CuO, 30g of copper chlorophyllin and 1.2kg of PP, mixing and uniformly stirring to obtain a mixed material.
And adding the mixed material into a double-screw extruder, and carrying out melt extrusion granulation to obtain modified polypropylene, which is marked as P2. Wherein the temperature of each zone of the double-screw extruder is 155 ℃ in the first zone, 175 ℃ in the second zone, 175 ℃ in the third zone, 175 ℃ in the fourth zone, 175 ℃ in the fifth zone, 175 ℃ in the sixth zone, 180 ℃ at the head temperature, and the rotating speed of the screw is 220 r/min.
Example 3
Nano CuO with the particle size of 70nm is put into a plasma reaction chamber, and meanwhile, argon plasma is introduced into the plasma reaction chamber to act on the nano CuO for 2 hours, so that modified nano CuO is obtained; wherein the pulse voltage of the argon plasma is 3kV, and the pulse frequency is 900 Hz.
Weighing 30g of modified nano CuO, 20g of copper chlorophyllin and 1.1kg of PP, mixing and uniformly stirring to obtain a mixed material;
and adding the mixed material into a double-screw extruder, and carrying out melt extrusion granulation to obtain modified polypropylene, which is marked as P3. Wherein the temperature of each zone of the double-screw extruder is 145 ℃ in the first zone, 165 ℃ in the second zone, 170 ℃ in the third zone, 170 ℃ in the fourth zone, 170 ℃ in the fifth zone, 170 ℃ in the sixth zone, 175 ℃ at the head temperature and the screw rotating speed of 210 r/min.
Example 4
Nano CuO with the particle size of 75nm is put into a plasma reaction chamber, and meanwhile, argon plasma is introduced into the plasma reaction chamber to act on the nano CuO for 1h, so that modified nano CuO is obtained; wherein the pulse voltage of the argon plasma is 3kV, and the pulse frequency is 950 Hz.
Weighing 20g of modified nano CuO, 10g of copper chlorophyllin and 1.2kg of PP, mixing and uniformly stirring to obtain a mixed material;
and adding the mixed material into a double-screw extruder, and carrying out melt extrusion granulation to obtain modified polypropylene, which is marked as P4. Wherein the temperature of each zone of the double-screw extruder is 150 ℃ in the first zone, 165 ℃ in the second zone, 170 ℃ in the third zone, 175 ℃ in the fourth zone, 175 ℃ in the fifth zone, 175 ℃ in the sixth zone, 180 ℃ at the head and the screw rotating speed of 200 r/min.
Comparative example 1
The same PP raw material as in the above example was added to a twin-screw extruder to be melt-extruded and pelletized to obtain polypropylene, the agent D1, wherein the temperatures of the zones of the twin-screw extruder were 140 ℃ in the first zone, 160 ℃ in the second zone, 165 ℃ in the third zone, 165 ℃ in the fourth zone, 165 ℃ in the fifth zone, 165 ℃ in the sixth zone, the head temperature was 170 ℃ and the screw rotation speed was 200 r/min.
Comparative example 2
Nano CuO with the particle size of 75nm is put into a plasma reaction chamber, and meanwhile, argon plasma is introduced into the plasma reaction chamber to act on the nano CuO for 1h, so that modified nano CuO is obtained; wherein the pulse voltage of the argon plasma is 3kV, and the pulse frequency is 950 Hz.
Weighing 5g of modified nano CuO, 15g of copper chlorophyllin and 1.2kg of PP, mixing and uniformly stirring to obtain a mixed material;
and adding the mixed material into a double-screw extruder, and carrying out melt extrusion granulation to obtain modified polypropylene, which is recorded as D2. Wherein the temperature of each zone of the double-screw extruder is 150 ℃ in the first zone, 165 ℃ in the second zone, 170 ℃ in the third zone, 175 ℃ in the fourth zone, 175 ℃ in the fifth zone, 175 ℃ in the sixth zone, 180 ℃ at the head and the screw rotating speed of 200 r/min.
Comparative example 3
Nano CuO with the particle size of 75nm is put into a plasma reaction chamber, and meanwhile, argon plasma is introduced into the plasma reaction chamber to act on the nano CuO for 1h, so that modified nano CuO is obtained; wherein the pulse voltage of the argon plasma is 3kV, and the pulse frequency is 950 Hz.
Weighing 20g of modified nano CuO, 4g of copper chlorophyllin and 1.2kg of PP, mixing and uniformly stirring to obtain a mixed material;
and adding the mixed material into a double-screw extruder, and carrying out melt extrusion granulation to obtain modified polypropylene, which is recorded as D3. Wherein the temperature of each zone of the double-screw extruder is 150 ℃ in the first zone, 165 ℃ in the second zone, 170 ℃ in the third zone, 175 ℃ in the fourth zone, 175 ℃ in the fifth zone, 175 ℃ in the sixth zone, 180 ℃ at the head and the screw rotating speed of 200 r/min.
Comparative example 4
Nano CuO with the particle size of 75nm is put into a plasma reaction chamber, and meanwhile, argon plasma is introduced into the plasma reaction chamber to act on the nano CuO for 1h, so that modified nano CuO is obtained; wherein the pulse voltage of the argon plasma is 3kV, and the pulse frequency is 950 Hz.
Weighing 30g of modified nano CuO and 1.2kg of PP raw materials, mixing and uniformly stirring to obtain a mixed material.
And adding the mixed material into a double-screw extruder, and carrying out melt extrusion granulation to obtain modified polypropylene, which is recorded as D4. Wherein the temperature of each zone of the double-screw extruder is 150 ℃ in the first zone, 165 ℃ in the second zone, 170 ℃ in the third zone, 175 ℃ in the fourth zone, 175 ℃ in the fifth zone, 175 ℃ in the sixth zone, 180 ℃ at the head and the screw rotating speed of 200 r/min.
Comparative example 5
Nano CuO with the particle size of 75nm is put into a plasma reaction chamber, and meanwhile, argon plasma is introduced into the plasma reaction chamber to act on the nano CuO for 1h, so that modified nano CuO is obtained; wherein the pulse voltage of the argon plasma is 3kV, and the pulse frequency is 950 Hz.
Weighing 30g of copper chlorophyllin and 1.2kg of PP (polypropylene) raw material, mixing and uniformly stirring to obtain a mixed material;
and adding the mixed material into a double-screw extruder, and carrying out melt extrusion granulation to obtain modified polypropylene, which is recorded as D5. Wherein the temperature of each zone of the double-screw extruder is 150 ℃ in the first zone, 165 ℃ in the second zone, 170 ℃ in the third zone, 175 ℃ in the fourth zone, 175 ℃ in the fifth zone, 175 ℃ in the sixth zone, 180 ℃ at the head and the screw rotating speed of 200 r/min.
Comparative example 6
Weighing 20g of nano CuO with the particle size of 75nm, 30g of copper chlorophyllin and 1.2kg of PP raw material, mixing and uniformly stirring to obtain a mixed material;
and adding the mixed material into a double-screw extruder, and carrying out melt extrusion granulation to obtain modified polypropylene, which is recorded as D6. Wherein the temperature of each zone of the double-screw extruder is 150 ℃ in the first zone, 165 ℃ in the second zone, 170 ℃ in the third zone, 175 ℃ in the fourth zone, 175 ℃ in the fifth zone, 175 ℃ in the sixth zone, 180 ℃ at the head and the screw rotating speed of 200 r/min.
The antibacterial performance of the examples 1-4 and the comparative examples 1-6 is shown in Table 1.
TABLE 1 results of antibacterial property test in examples 1 to 4 and comparative examples 1 to 6
As can be seen from the test results in Table 1, the antibacterial property of the modified polypropylene of the present invention is better than that of the conventional polypropylene, and the antibacterial ratio is higher than that of the polypropylene material of the comparative example.
The polypropylene samples of examples 1 to 4 and comparative examples 1 to 6 were each subjected to a scratch resistance test by adding carbon black in an amount of 1% by weight, and the test results are shown in Table 2.
TABLE 2 scratch resistance test results in examples 1 to 4 and comparative examples 1 to 6
| Inspection item | Scratch-resistant coating |
| Test standard | PV 3952 |
| Test item | dL |
| P1 | 0.8 |
| P2 | 0.71 |
| P3 | 0.76 |
| P4 | 0.92 |
| D1 | 1.6 |
| D2 | 1.3 |
| D3 | 1 |
| D4 | 1.2. |
| D5 | 1.3 |
| D6 | 1.1 |
As can be seen from the test results in Table 2, the examples show that the dL value change is smaller after the scratch test, which indicates that the modified polypropylene of the present invention has better scratch resistance than the ordinary polypropylene; and the complex effect of the copper chlorophyllin and the modified nano CuO is better.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. The modified polypropylene is characterized by being prepared by mixing modified nano CuO, copper chlorophyllin and polypropylene, wherein the modified nano CuO is obtained by subjecting the nano CuO to the action of argon plasma.
2. The modified polypropylene according to claim 1, wherein the modified polypropylene comprises the following components in a mass ratio of modified nano CuO: copper chlorophyllin acid: polypropylene = (2-4): (1-3): 100-.
3. The modified polypropylene of claim 1, wherein the modified nano CuO is prepared by a modification method comprising the following steps: and placing the nano CuO into a plasma reaction chamber, introducing the argon plasma into the plasma reaction chamber, and acting the nano CuO for 1-3 hours.
4. The modified polypropylene of claim 1, wherein the nano CuO has a particle size of 60 to 80 nm.
5. The modified polypropylene of claim 1, wherein the argon plasma is pulsed at a voltage of 2-4kV and a frequency of 800-1000 Hz.
6. The modified polypropylene according to claim 1, wherein the purity of the copper chlorophyllin is not less than 98%.
7. A method for preparing the modified polypropylene according to any one of claims 1 to 6, comprising the steps of:
uniformly mixing the modified nano CuO, copper chlorophyllin and polypropylene to obtain a mixed material;
and performing melt extrusion granulation on the mixed material to obtain the modified polypropylene.
8. The method of claim 7, wherein the melt extruding is performed in a twin screw extruder.
9. The method as claimed in claim 8, wherein the operating temperature of each zone of the twin-screw extruder is 140 ℃ to 155 ℃ in the first zone, 160 ℃ to 175 ℃ in the second zone, 160 ℃ to 175 ℃ in the third zone, 160 ℃ to 175 ℃ in the fourth zone, 160 ℃ to 175 ℃ in the fifth zone, 160 ℃ to 175 ℃ in the sixth zone, 170 ℃ to 180 ℃ at the head temperature, and the screw rotation speed is 190-220 r/min.
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