CN112143108A - Modified polypropylene PP plastic - Google Patents
Modified polypropylene PP plastic Download PDFInfo
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- CN112143108A CN112143108A CN202011064842.5A CN202011064842A CN112143108A CN 112143108 A CN112143108 A CN 112143108A CN 202011064842 A CN202011064842 A CN 202011064842A CN 112143108 A CN112143108 A CN 112143108A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
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Abstract
The invention discloses a modified polypropylene PP plastic which is prepared from the following raw materials in parts by weight: 80-100 parts of polypropylene, 8-10 parts of antibacterial filler, 2-5 parts of flame retardant, 3-5 parts of dispersant, 3-5 parts of plasticizer and 2-3 parts of glass fiber; the antibacterial filler can act on lipid or peptidoglycan in a bacterial cell wall, and further the structure of the antibacterial filler is destroyed, so that the bacterial cell wall is damaged, the antibacterial filler is mixed with a polymer, in the long-time use process of the polymer, the antibacterial substance in the antibacterial filler cannot migrate and is separated out, further the antibacterial property of the polymer is more durable, the antibacterial filler can form positive holes when the polymer is illuminated, free electrons are released simultaneously, the free electrons can be absorbed by oxygen molecules, the negative oxygen ions are changed into negative oxygen ions with extremely strong chemical activity, the negative oxygen ions can oxidize organic matters in bacteria, and further bacteria are killed.
Description
Technical Field
The invention belongs to the technical field of plastic preparation, and particularly relates to a modified polypropylene PP plastic.
Background
The polypropylene is a colorless, odorless, nontoxic and semitransparent solid substance, is thermoplastic synthetic resin with excellent performance, is colorless and semitransparent thermoplastic light general plastic, has chemical resistance, heat resistance, electrical insulation, high-strength mechanical property, good high-wear-resistance processing performance and the like, since the advent of the world, polypropylene has rapidly gained wide development and application in many fields such as machinery, automobiles, electronic and electrical appliances, construction, textile, packaging, agriculture, forestry, fishery, food industry and the like, in recent years, with the rapid development of packaging, electronics, automobiles and other industries, polypropylene materials are gradually replacing wood products, high strength, toughness and high wear resistance have gradually replaced the mechanical function of metal, in addition, the polypropylene has good grafting and compounding functions, and has huge application space in the aspects of concrete, textile, packaging and agriculture, forestry and fishery.
The existing modified polypropylene PP plastic is low in antibacterial property, bacteria are easily bred on the surface of the plastic after the plastic is used for a long time, so that virus infection is caused, and part of the polypropylene PP plastic is added with the antibacterial agent for increasing the antibacterial property, so that the existing antibacterial agent is single in antibacterial effect, poor in antibacterial effect and easy to separate out, and the antibacterial durability of the polypropylene PP plastic is low.
Disclosure of Invention
The invention aims to provide a modified polypropylene PP plastic.
The technical problems to be solved by the invention are as follows:
the existing modified polypropylene PP plastic is low in antibacterial property, bacteria are easily bred on the surface of the plastic after the plastic is used for a long time, so that virus infection is caused, and part of the polypropylene PP plastic is added with the antibacterial agent for increasing the antibacterial property, so that the existing antibacterial agent is single in antibacterial effect, poor in antibacterial effect and easy to separate out, and the antibacterial durability of the polypropylene PP plastic is low.
The purpose of the invention can be realized by the following technical scheme:
a modified polypropylene PP plastic is prepared from the following raw materials in parts by weight: 80-100 parts of polypropylene, 8-10 parts of antibacterial filler, 2-5 parts of flame retardant, 3-5 parts of dispersant, 3-5 parts of plasticizer and 2-3 parts of glass fiber;
the modified polypropylene PP plastic is prepared by the following steps:
step S1: stirring the polypropylene and the dispersant for 10-15min at the rotation speed of 300-500r/min to prepare a first mixture;
step S2: stirring the antibacterial filler and the glass fiber for 3-5min at the rotation speed of 500-800r/min, adding the flame retardant, and continuously stirring for 10-15min to prepare a second mixture;
step S3: melting and stirring the first mixture and the second mixture for 5-10min at the rotation speed of 1000-;
step S4: and adding the molten material into a three-section double-screw extruder, extruding, cooling and granulating at the three-section temperature of 180 ℃, 200 ℃ and 210 ℃ respectively to obtain the modified polypropylene PP plastic.
Further, the flame retardant is one or more of antimony trioxide, zinc borate and aluminum hydroxide which are mixed in any proportion, the dispersant is one or two of stearic acid monoglyceride and tristearin which are mixed in any proportion, and the plasticizer is one or more of dioctyl sebacate, epoxidized soybean oil and epoxidized butyl stearate which are mixed in any proportion.
Further, the antibacterial agent is prepared by the following steps:
step A1: dissolving pyromellitic dianhydride in dimethyl sulfoxide, stirring and adding a sodium hydroxide solution under the conditions that the rotation speed is 120-150r/min and the temperature is 50-60 ℃, stirring for 5-10min, heating to 90-95 ℃, reacting for 2-3h, adjusting the pH value of a reaction solution to 5-6, cooling to room temperature, and filtering to remove filtrate to obtain an intermediate 1;
the reaction process is as follows:
step A2: dissolving piperazine and the intermediate 1 prepared in the step A1 in dimethyl sulfoxide, introducing nitrogen for protection, reacting for 15-20h at the rotation speed of 60-80r/min and the temperature of 50-55 ℃, adding absolute ethyl alcohol, filtering, washing a filter cake with the absolute ethyl alcohol for 3-5 times, washing for 20-30s each time, and drying to prepare an intermediate 2;
the reaction process is as follows:
step A3: mixing monobromododecane and acetonitrile to prepare a mixed solution, introducing nitrogen into imidazole, sodium hydroxide and acetonitrile for protection, stirring for 10-15min at the rotation speed of 120-150r/min and the temperature of 25-30 ℃, adding the mixed solution, continuously stirring for 10-15h at the temperature of 60-70 ℃, adding 4-methylbenzyl chloride and 2, 6-di-tert-butyl-4-methylphenol, stirring for 10-15min at the temperature of 25-30 ℃, and stirring for 8-10h at the temperature of 50-55 ℃ to prepare an intermediate 3;
the reaction process is as follows:
step A4: adding the intermediate 3 prepared in the step A3 and carbon tetrachloride into a reaction kettle, stirring until the intermediate 3 is completely dissolved, introducing chlorine, reacting for 1-1.5h under the condition of illumination, adding ammonia water, reacting for 1-2h under the conditions that the rotation speed is 120 plus materials/min and the temperature is 30-35 ℃, adding the intermediate 2 prepared in the step A2 and dicyclohexylcarbodiimide, and continuing to react for 4-5h to prepare an intermediate 4;
the reaction process is as follows:
step A5: adding zinc acetate and ethylene glycol into a reaction kettle, refluxing for 10-15h at the rotation speed of 150-200r/min and the temperature of 200-210 ℃, filtering to remove filtrate, adding a filter cake, deionized water and isopropanol into the reaction kettle, stirring uniformly, adding gamma-aminopropyltriethoxysilane, stirring for 1.5-2h at the temperature of 60-65 ℃, filtering to remove filtrate, and drying the filter cake to obtain a nano zinc oxide carrier;
step A6: and D, dissolving the intermediate 4 prepared in the step A4 in ethanol, adding the nano zinc oxide carrier prepared in the step A5 and dicyclohexylcarbodiimide, carrying out ultrasonic treatment for 1-1.5h at the temperature of 25-30 ℃ and the frequency of 3-5MHz, filtering to remove filtrate, and drying a filter cake to obtain the antibacterial filler.
Further, the volume ratio of the pyromellitic dianhydride to the sodium hydroxide solution in the step A1 is 1:6, and the mass fraction of the sodium hydroxide solution is 10-15%.
Further, the molar ratio of the piperazine used in step A2 to intermediate 1 is 1:1.
Further, the molar ratio of the monobromododecane, the imidazole, the sodium hydroxide and the 4-methylbenzyl chloride in the step A3 is 1:1.5-1.8:1.2:1, and the amount of the 2, 6-di-tert-butyl-4-methylphenol is 8-10% of the mass of the monobromododecane.
Further, the molar ratio of the intermediate 3 to the chlorine gas in the step A4 is 2:1, the molar ratio of the carboxyl group on the intermediate 2 to the amino group on the intermediate 3 is 2:1, and the amount of dicyclohexylcarbodiimide is 30-50% of the mass sum of the intermediate 2 and the intermediate 3.
Furthermore, the dosage ratio of the zinc acetate and the glycol in the step A5 is 1g:3mL, and the dosage of the gamma-aminopropyl triethoxysilane is 5-8% of the mass of the zinc acetate.
Further, the mass ratio of the intermediate 4 and the nano zinc oxide carrier in the step A6 is 5:1.5-2, and the amount of dicyclohexylcarbodiimide is 30-50% of the mass sum of the intermediate 4 and the nano zinc oxide carrier.
The invention has the beneficial effects that: the invention prepares an antibacterial filler in the process of preparing a modified polypropylene PP plastic, the antibacterial filler takes pyromellitic dianhydride as a raw material to prepare an intermediate 1, the intermediate 1 is polymerized with piperazine to prepare an intermediate 2, the intermediate 2 is piperazine polymer, the intermediate can act on lipid or peptidoglycan in bacterial cell walls to further destroy the structure of the bacterial cell walls, monobromododecane and imidazole are reacted to ensure that long-chain alkyl is inserted into imidazole molecules and further reacts with 4-methylbenzyl chloride to prepare an intermediate 3, the intermediate 3 is one of quaternary ammonium salts, the intermediate can reduce the activity of metabolic enzyme in microbial cells, further prevent cell respiration, interfere the production of substances required by the microbial growth and inhibit the bacterial biosynthesis process, and has long-chain alkyl which has good hydrophobicity, generating strong hydrophobic effect with bacterial cell membrane to make bacteria unable to grow normally, further substituting chlorine for methyl on benzene ring in intermediate 3, reacting with ammonia water to insert amino group, dehydrating and condensing with active carboxyl on intermediate 2 to obtain intermediate 4, controlling the dosage of intermediate 3 and intermediate 2 to make partial carboxyl on intermediate 2 react, then using zinc acetate to react with glycol, modifying with gamma-aminopropyl triethoxy silane to obtain nano zinc oxide carrier, the surface of nano zinc oxide contains a large amount of active amino group, further dehydrating and condensing with residual active carboxyl on intermediate 4 to make intermediate 4 molecule fix on the surface of nano zinc oxide to obtain antibacterial filler, after the antibacterial filler is mixed with polymer, in the course of long-time use of polymer, the antibacterial substance in the antibacterial filler can not be migrated and separated out, and then make the antibiotic property of polymer more lasting, and when the polymer receives the illumination antibiotic filler can form positive electric cavity, release free electron simultaneously, free electron can be absorbed by the oxygen molecule, becomes the negative oxygen ion that has extremely strong chemical activity, and these negative oxygen ions can the oxidation organism in the bacterium, and then kill the bacterium.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A modified polypropylene PP plastic is prepared from the following raw materials in parts by weight: 80 parts of polypropylene, 8 parts of antibacterial filler, 2 parts of antimony trioxide, 3 parts of stearic acid monoglyceride, 3 parts of dioctyl sebacate and 2 parts of glass fiber;
the modified polypropylene PP plastic is prepared by the following steps:
step S1: stirring polypropylene and glyceryl monostearate for 10min at the rotation speed of 300r/min to prepare a first mixture;
step S2: stirring the antibacterial filler and the glass fiber for 3min at the rotating speed of 500r/min, adding antimony trioxide, and continuously stirring for 10min to obtain a second mixture;
step S3: melting and stirring the first mixture and the second mixture for 5min at the rotating speed of 1000r/min and the temperature of 160 ℃, adding dioctyl sebacate, and continuously stirring for 20min to prepare a molten material;
step S4: and adding the molten material into a three-section double-screw extruder, extruding, cooling and granulating at the three-section temperature of 180 ℃, 200 ℃ and 210 ℃ respectively to obtain the modified polypropylene PP plastic.
The antibacterial agent is prepared by the following steps:
step A1: dissolving pyromellitic dianhydride in dimethyl sulfoxide, stirring at the rotation speed of 120r/min and the temperature of 50 ℃, adding a sodium hydroxide solution, stirring for 5min, heating at the temperature of 90 ℃, reacting for 2h, adjusting the pH value of a reaction solution to 5, cooling to room temperature, filtering, and removing filtrate to obtain an intermediate 1;
step A2: dissolving piperazine and the intermediate 1 prepared in the step A1 in dimethyl sulfoxide, introducing nitrogen for protection, reacting for 15 hours at the rotation speed of 60r/min and the temperature of 50 ℃, adding absolute ethyl alcohol, filtering, washing a filter cake for 3 times by using the absolute ethyl alcohol, washing for 20s each time, and drying to prepare an intermediate 2;
step A3: mixing monobromododecane and acetonitrile to prepare a mixed solution, introducing nitrogen into imidazole, sodium hydroxide and acetonitrile for protection, stirring for 10min at the rotation speed of 120r/min and the temperature of 25 ℃, adding the mixed solution, continuously stirring for 10h at the temperature of 60 ℃, adding 4-methylbenzyl chloride and 2, 6-di-tert-butyl-4-methylphenol, stirring for 10min at the temperature of 25 ℃, and stirring for 8h at the temperature of 50 ℃ to prepare an intermediate 3;
step A4: adding the intermediate 3 prepared in the step A3 and carbon tetrachloride into a reaction kettle, stirring until the intermediate 3 is completely dissolved, introducing chlorine, reacting for 1h under the condition of illumination, adding ammonia water, reacting for 1h under the conditions of the rotating speed of 120r/min and the temperature of 30 ℃, adding the intermediate 2 prepared in the step A2 and dicyclohexylcarbodiimide, and continuing to react for 4h to prepare an intermediate 4;
step A5: adding zinc acetate and ethylene glycol into a reaction kettle, refluxing for 10 hours at the rotation speed of 150r/min and the temperature of 200 ℃, filtering to remove filtrate, adding a filter cake, deionized water and isopropanol into the reaction kettle, stirring uniformly, adding gamma-aminopropyltriethoxysilane, stirring for 1.5 hours at the temperature of 60 ℃, filtering to remove filtrate, and drying the filter cake to obtain a nano zinc oxide carrier;
step A6: and D, dissolving the intermediate 4 prepared in the step A4 in ethanol, adding the nano zinc oxide carrier prepared in the step A5 and dicyclohexylcarbodiimide, carrying out ultrasonic treatment for 1h at the temperature of 25 ℃ and the frequency of 3MHz, filtering to remove filtrate, and drying a filter cake to obtain the antibacterial filler.
Example 2
A modified polypropylene PP plastic is prepared from the following raw materials in parts by weight: 85 parts of polypropylene, 9 parts of antibacterial filler, 3 parts of antimony trioxide, 4 parts of stearic acid monoglyceride, 4 parts of dioctyl sebacate and 2 parts of glass fiber;
the modified polypropylene PP plastic is prepared by the following steps:
step S1: stirring polypropylene and stearic acid monoglyceride at a rotation speed of 400r/min for 13min to prepare a first mixture;
step S2: stirring the antibacterial filler and the glass fiber for 4min at the rotating speed of 600r/min, adding antimony trioxide, and continuously stirring for 13min to obtain a second mixture;
step S3: melting and stirring the first mixture and the second mixture for 8min at the rotating speed of 1100r/min and the temperature of 170 ℃, adding dioctyl sebacate, and continuously stirring for 25min to prepare a molten material;
step S4: and adding the molten material into a three-section double-screw extruder, extruding, cooling and granulating at the three-section temperature of 180 ℃, 200 ℃ and 210 ℃ respectively to obtain the modified polypropylene PP plastic.
The antibacterial agent is prepared by the following steps:
step A1: dissolving pyromellitic dianhydride in dimethyl sulfoxide, stirring at the rotation speed of 130r/min and the temperature of 55 ℃, adding a sodium hydroxide solution, stirring for 8min, heating at the temperature of 92 ℃, reacting for 2h, adjusting the pH value of a reaction solution to 5, cooling to room temperature, and filtering to remove filtrate to obtain an intermediate 1;
step A2: dissolving piperazine and the intermediate 1 prepared in the step A1 in dimethyl sulfoxide, introducing nitrogen for protection, reacting for 18 hours at the rotation speed of 70r/min and the temperature of 53 ℃, adding absolute ethyl alcohol, filtering, washing a filter cake with the absolute ethyl alcohol for 4 times, washing for 25s each time, and drying to prepare an intermediate 2;
step A3: mixing monobromododecane and acetonitrile to prepare a mixed solution, introducing nitrogen into imidazole, sodium hydroxide and acetonitrile for protection, stirring for 13min at the rotation speed of 130r/min and the temperature of 28 ℃, adding the mixed solution, continuously stirring for 13h at the temperature of 65 ℃, adding 4-methylbenzyl chloride and 2, 6-di-tert-butyl-4-methylphenol, stirring for 13min at the temperature of 25-30 ℃, and stirring for 9h at the temperature of 52 ℃ to prepare an intermediate 3;
step A4: adding the intermediate 3 prepared in the step A3 and carbon tetrachloride into a reaction kettle, stirring until the intermediate 3 is completely dissolved, introducing chlorine, reacting for 1.2h under the condition of illumination, adding ammonia water, reacting for 1h under the conditions that the rotating speed is 130r/min and the temperature is 32 ℃, adding the intermediate 2 prepared in the step A2 and dicyclohexylcarbodiimide, and continuing to react for 4h to prepare an intermediate 4;
step A5: adding zinc acetate and ethylene glycol into a reaction kettle, refluxing for 12 hours at the rotation speed of 160r/min and the temperature of 205 ℃, filtering to remove filtrate, adding a filter cake, deionized water and isopropanol into the reaction kettle, stirring uniformly, adding gamma-aminopropyltriethoxysilane, stirring for 1.8 hours at the temperature of 63 ℃, filtering to remove filtrate, and drying the filter cake to obtain a nano zinc oxide carrier;
step A6: and D, dissolving the intermediate 4 prepared in the step A4 in ethanol, adding the nano zinc oxide carrier prepared in the step A5 and dicyclohexylcarbodiimide, carrying out ultrasonic treatment for 1.2h at the temperature of 28 ℃ and the frequency of 4MHz, filtering to remove filtrate, and drying a filter cake to obtain the antibacterial filler.
Example 3
A modified polypropylene PP plastic is prepared from the following raw materials in parts by weight: 90 parts of polypropylene, 9 parts of antibacterial filler, 4 parts of antimony trioxide, 4 parts of stearic acid monoglyceride, 4 parts of dioctyl sebacate and 4 parts of glass fiber;
the modified polypropylene PP plastic is prepared by the following steps:
step S1: stirring polypropylene and stearic acid monoglyceride at a rotation speed of 400r/min for 13min to prepare a first mixture;
step S2: stirring the antibacterial filler and the glass fiber for 4min at the rotating speed of 700r/min, adding antimony trioxide, and continuously stirring for 13min to obtain a second mixture;
step S3: melting and stirring the first mixture and the second mixture for 8min at the rotating speed of 1200r/min and the temperature of 170 ℃, adding dioctyl sebacate, and continuously stirring for 25min to prepare a molten material;
step S4: and adding the molten material into a three-section double-screw extruder, extruding, cooling and granulating at the three-section temperature of 180 ℃, 200 ℃ and 210 ℃ respectively to obtain the modified polypropylene PP plastic.
The antibacterial agent is prepared by the following steps:
step A1: dissolving pyromellitic dianhydride in dimethyl sulfoxide, stirring at the rotation speed of 140r/min and the temperature of 55 ℃, adding a sodium hydroxide solution, stirring for 8min, heating at the temperature of 93 ℃, reacting for 3h, adjusting the pH value of a reaction solution to 6, cooling to room temperature, and filtering to remove filtrate to obtain an intermediate 1;
step A2: dissolving piperazine and the intermediate 1 prepared in the step A1 in dimethyl sulfoxide, introducing nitrogen for protection, reacting for 20 hours at the rotation speed of 75r/min and the temperature of 55 ℃, adding absolute ethyl alcohol, filtering, washing a filter cake with the absolute ethyl alcohol for 4 times, washing for 25s each time, and drying to prepare an intermediate 2;
step A3: mixing monobromododecane and acetonitrile to prepare a mixed solution, introducing nitrogen into imidazole, sodium hydroxide and acetonitrile for protection, stirring for 13min at the rotation speed of 140r/min and the temperature of 28 ℃, adding the mixed solution, continuously stirring for 13h at the temperature of 65 ℃, adding 4-methylbenzyl chloride and 2, 6-di-tert-butyl-4-methylphenol, stirring for 13min at the temperature of 28 ℃, and stirring for 9h at the temperature of 55 ℃ to prepare an intermediate 3;
step A4: adding the intermediate 3 prepared in the step A3 and carbon tetrachloride into a reaction kettle, stirring until the intermediate 3 is completely dissolved, introducing chlorine, reacting for 1.3h under the condition of illumination, adding ammonia water, reacting for 2h under the conditions of the rotating speed of 140r/min and the temperature of 35 ℃, adding the intermediate 2 prepared in the step A2 and dicyclohexylcarbodiimide, and continuing to react for 5h to prepare an intermediate 4;
step A5: adding zinc acetate and ethylene glycol into a reaction kettle, refluxing for 12 hours at the rotating speed of 180r/min and the temperature of 210 ℃, filtering to remove filtrate, adding a filter cake, deionized water and isopropanol into the reaction kettle, stirring uniformly, adding gamma-aminopropyltriethoxysilane, stirring for 2 hours at the temperature of 65 ℃, filtering to remove filtrate, and drying the filter cake to obtain a nano zinc oxide carrier;
step A6: and D, dissolving the intermediate 4 prepared in the step A4 in ethanol, adding the nano zinc oxide carrier prepared in the step A5 and dicyclohexylcarbodiimide, carrying out ultrasonic treatment for 1.5h at the temperature of 30 ℃ and the frequency of 5MHz, filtering to remove filtrate, and drying a filter cake to obtain the antibacterial filler.
Example 4
A modified polypropylene PP plastic is prepared from the following raw materials in parts by weight: 100 parts of polypropylene, 10 parts of antibacterial filler, 5 parts of antimony trioxide, 5 parts of stearic acid monoglyceride, 5 parts of dioctyl sebacate and 3 parts of glass fiber;
the modified polypropylene PP plastic is prepared by the following steps:
step S1: stirring polypropylene and glyceryl monostearate for 15min at the rotation speed of 500r/min to prepare a first mixture;
step S2: stirring the antibacterial filler and the glass fiber for 3-5min at the rotating speed of 800r/min, adding antimony trioxide, and continuously stirring for 15min to obtain a second mixture;
step S3: melting and stirring the first mixture and the second mixture for 10min at the rotating speed of 1200r/min and the temperature of 180 ℃, adding dioctyl sebacate, and continuously stirring for 30min to prepare a molten material;
step S4: and adding the molten material into a three-section double-screw extruder, extruding, cooling and granulating at the three-section temperature of 180 ℃, 200 ℃ and 210 ℃ respectively to obtain the modified polypropylene PP plastic.
The antibacterial agent is prepared by the following steps:
step A1: dissolving pyromellitic dianhydride in dimethyl sulfoxide, stirring at the rotation speed of 150r/min and the temperature of 60 ℃, adding a sodium hydroxide solution, stirring for 10min, heating at the temperature of 95 ℃, reacting for 3h, adjusting the pH value of a reaction solution to 6, cooling to room temperature, and filtering to remove filtrate to obtain an intermediate 1;
step A2: dissolving piperazine and the intermediate 1 prepared in the step A1 in dimethyl sulfoxide, introducing nitrogen for protection, reacting for 20 hours at the rotation speed of 80r/min and the temperature of 55 ℃, adding absolute ethyl alcohol, filtering, washing a filter cake for 5 times by using the absolute ethyl alcohol, washing for 30s each time, and drying to prepare an intermediate 2;
step A3: mixing monobromododecane and acetonitrile to prepare a mixed solution, introducing nitrogen into imidazole, sodium hydroxide and acetonitrile for protection, stirring for 15min at the rotation speed of 150r/min and the temperature of 30 ℃, adding the mixed solution, continuously stirring for 15h at the temperature of 70 ℃, adding 4-methylbenzyl chloride and 2, 6-di-tert-butyl-4-methylphenol, stirring for 15min at the temperature of 30 ℃, and stirring for 10h at the temperature of 55 ℃ to prepare an intermediate 3;
step A4: adding the intermediate 3 prepared in the step A3 and carbon tetrachloride into a reaction kettle, stirring until the intermediate 3 is completely dissolved, introducing chlorine, reacting for 1.5h under the condition of illumination, adding ammonia water, reacting for 2h under the conditions that the rotating speed is 150r/min and the temperature is 35 ℃, adding the intermediate 2 prepared in the step A2 and dicyclohexylcarbodiimide, and continuing to react for 5h to prepare an intermediate 4;
step A5: adding zinc acetate and ethylene glycol into a reaction kettle, refluxing for 15h at the rotation speed of 200r/min and the temperature of 210 ℃, filtering to remove filtrate, adding a filter cake, deionized water and isopropanol into the reaction kettle, stirring uniformly, adding gamma-aminopropyltriethoxysilane, stirring for 2h at the temperature of 65 ℃, filtering to remove filtrate, and drying the filter cake to obtain a nano zinc oxide carrier;
step A6: and D, dissolving the intermediate 4 prepared in the step A4 in ethanol, adding the nano zinc oxide carrier prepared in the step A5 and dicyclohexylcarbodiimide, carrying out ultrasonic treatment for 1.5h at the temperature of 30 ℃ and the frequency of 5MHz, filtering to remove filtrate, and drying a filter cake to obtain the antibacterial filler.
Comparative example 1
Compared with the embodiment 1, the preparation method of the antibacterial composite material uses chitosan to replace the antibacterial filler and comprises the following specific steps:
step S1: stirring polypropylene and glyceryl monostearate for 10min at the rotation speed of 300r/min to prepare a first mixture;
step S2: stirring the antibacterial filler and the glass fiber for 3min at the rotating speed of 500r/min, adding antimony trioxide, and continuously stirring for 10min to obtain a second mixture;
step S3: melting and stirring the first mixture and the second mixture for 5min at the rotating speed of 1000r/min and the temperature of 160 ℃, adding dioctyl sebacate, and continuously stirring for 20min to prepare a molten material;
step S4: and adding the molten material into a three-section double-screw extruder, extruding, cooling and granulating at the three-section temperature of 180 ℃, 200 ℃ and 210 ℃ respectively to obtain the modified polypropylene PP plastic.
Comparative example 2
The comparative example is a polypropylene PP plastic commonly available on the market.
The polypropylene PP plastics prepared in examples 1 to 4 and comparative examples 1 to 2 were subjected to a performance test, and the test results are shown in the following Table 1;
and (3) antibacterial property: and detecting the used bacteria escherichia coli and staphylococcus aureus according to a QB/T2591-2003A antibacterial plastic antibacterial performance test method and antibacterial effect.
TABLE 1
As shown in the above Table 1, the polypropylene PP plastics prepared in the examples 1 to 4 have the Escherichia coli sterilization rate of 98.96 to 99.63 percent and the Staphylococcus aureus sterilization rate of 98.79 to 99.32 percent, the polypropylene PP plastics prepared in the comparative example 1 have the Escherichia coli sterilization rate of 90.33 percent and the Staphylococcus aureus sterilization rate of 91.28 percent, and the polypropylene PP plastics prepared in the comparative example 2 have the Escherichia coli sterilization rate of 63.27 percent and the Staphylococcus aureus sterilization rate of 53.64 percent, which indicates that the invention has good antibacterial effect.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (9)
1. A modified polypropylene PP plastic is characterized in that: the feed is prepared from the following raw materials in parts by weight: 80-100 parts of polypropylene, 8-10 parts of antibacterial filler, 2-5 parts of flame retardant, 3-5 parts of dispersant, 3-5 parts of plasticizer and 2-3 parts of glass fiber;
the modified polypropylene PP plastic is prepared by the following steps:
step S1: stirring the polypropylene and the dispersant for 10-15min at the rotation speed of 300-500r/min to prepare a first mixture;
step S2: stirring the antibacterial filler and the glass fiber for 3-5min at the rotation speed of 500-800r/min, adding the flame retardant, and continuously stirring for 10-15min to prepare a second mixture;
step S3: melting and stirring the first mixture and the second mixture for 5-10min at the rotation speed of 1000-;
step S4: and adding the molten material into a three-section double-screw extruder, extruding, cooling and granulating at the three-section temperature of 180 ℃, 200 ℃ and 210 ℃ respectively to obtain the modified polypropylene PP plastic.
2. The modified polypropylene PP plastic according to claim 1, wherein: the flame retardant is one or more of antimony trioxide, zinc borate and aluminum hydroxide which are mixed in any proportion, the dispersant is one or two of glyceryl monostearate and glyceryl tristearate which are mixed in any proportion, and the plasticizer is one or more of dioctyl sebacate, epoxidized soybean oil and epoxidized butyl stearate which are mixed in any proportion.
3. The modified polypropylene PP plastic according to claim 1, wherein: the antibacterial agent is prepared by the following steps:
step A1: dissolving pyromellitic dianhydride in dimethyl sulfoxide, stirring and adding a sodium hydroxide solution under the conditions that the rotation speed is 120-150r/min and the temperature is 50-60 ℃, stirring for 5-10min, heating to 90-95 ℃, reacting for 2-3h, adjusting the pH value of a reaction solution to 5-6, cooling to room temperature, and filtering to remove filtrate to obtain an intermediate 1;
step A2: dissolving piperazine and the intermediate 1 prepared in the step A1 in dimethyl sulfoxide, introducing nitrogen for protection, reacting for 15-20h at the rotation speed of 60-80r/min and the temperature of 50-55 ℃, adding absolute ethyl alcohol, filtering, washing a filter cake with the absolute ethyl alcohol for 3-5 times, washing for 20-30s each time, and drying to prepare an intermediate 2;
step A3: mixing monobromododecane and acetonitrile to prepare a mixed solution, introducing nitrogen into imidazole, sodium hydroxide and acetonitrile for protection, stirring for 10-15min at the rotation speed of 120-150r/min and the temperature of 25-30 ℃, adding the mixed solution, continuously stirring for 10-15h at the temperature of 60-70 ℃, adding 4-methylbenzyl chloride and 2, 6-di-tert-butyl-4-methylphenol, stirring for 10-15min at the temperature of 25-30 ℃, and stirring for 8-10h at the temperature of 50-55 ℃ to prepare an intermediate 3;
step A4: adding the intermediate 3 prepared in the step A3 and carbon tetrachloride into a reaction kettle, stirring until the intermediate 3 is completely dissolved, introducing chlorine, reacting for 1-1.5h under the condition of illumination, adding ammonia water, reacting for 1-2h under the conditions that the rotation speed is 120 plus materials/min and the temperature is 30-35 ℃, adding the intermediate 2 prepared in the step A2 and dicyclohexylcarbodiimide, and continuing to react for 4-5h to prepare an intermediate 4;
step A5: adding zinc acetate and ethylene glycol into a reaction kettle, refluxing for 10-15h at the rotation speed of 150-200r/min and the temperature of 200-210 ℃, filtering to remove filtrate, adding a filter cake, deionized water and isopropanol into the reaction kettle, stirring uniformly, adding gamma-aminopropyltriethoxysilane, stirring for 1.5-2h at the temperature of 60-65 ℃, filtering to remove filtrate, and drying the filter cake to obtain a nano zinc oxide carrier;
step A6: and D, dissolving the intermediate 4 prepared in the step A4 in ethanol, adding the nano zinc oxide carrier prepared in the step A5 and dicyclohexylcarbodiimide, carrying out ultrasonic treatment for 1-1.5h at the temperature of 25-30 ℃ and the frequency of 3-5MHz, filtering to remove filtrate, and drying a filter cake to obtain the antibacterial filler.
4. The modified polypropylene PP plastic according to claim 3, wherein: the volume ratio of the pyromellitic dianhydride to the sodium hydroxide solution in the step A1 is 1:6, and the mass fraction of the sodium hydroxide solution is 10-15%.
5. The modified polypropylene PP plastic according to claim 3, wherein: the molar ratio of the piperazine used in the step A2 to the intermediate 1 is 1:1.
6. The modified polypropylene PP plastic according to claim 3, wherein: the molar ratio of the monobromododecane, the imidazole, the sodium hydroxide and the 4-methylbenzyl chloride in the step A3 is 1:1.5-1.8:1.2:1, and the amount of the 2, 6-di-tert-butyl-4-methylphenol is 8-10% of the mass of the monobromododecane.
7. The modified polypropylene PP plastic according to claim 3, wherein: the molar ratio of the intermediate 3 to the chlorine gas in the step A4 is 2:1, the molar ratio of the carboxyl on the intermediate 2 to the amino on the intermediate 3 is 2:1, and the amount of dicyclohexylcarbodiimide is 30-50% of the mass sum of the intermediate 2 and the intermediate 3.
8. The modified polypropylene PP plastic according to claim 3, wherein: the dosage ratio of the zinc acetate and the glycol in the step A5 is 1g:3mL, and the dosage of the gamma-aminopropyl triethoxysilane is 5-8% of the mass of the zinc acetate.
9. The modified polypropylene PP plastic according to claim 3, wherein: the mass ratio of the intermediate 4 to the nano zinc oxide carrier in the step A6 is 5:1.5-2, and the mass of dicyclohexylcarbodiimide is 30-50% of the sum of the mass of the intermediate 4 and the nano zinc oxide carrier.
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| CN202011064842.5A CN112143108A (en) | 2020-09-30 | 2020-09-30 | Modified polypropylene PP plastic |
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| CN202011064842.5A CN112143108A (en) | 2020-09-30 | 2020-09-30 | Modified polypropylene PP plastic |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113512331A (en) * | 2021-07-27 | 2021-10-19 | 浙江精筑环保科技有限公司 | Mildew-proof and bacteria-removing coating and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113512331A (en) * | 2021-07-27 | 2021-10-19 | 浙江精筑环保科技有限公司 | Mildew-proof and bacteria-removing coating and preparation method thereof |
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Application publication date: 20201229 |