CN117586578B - Antibacterial environment-friendly polypropylene composite plastic and preparation method thereof - Google Patents
Antibacterial environment-friendly polypropylene composite plastic and preparation method thereof Download PDFInfo
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- CN117586578B CN117586578B CN202311595797.XA CN202311595797A CN117586578B CN 117586578 B CN117586578 B CN 117586578B CN 202311595797 A CN202311595797 A CN 202311595797A CN 117586578 B CN117586578 B CN 117586578B
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- -1 polypropylene Polymers 0.000 title claims abstract description 127
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 106
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 106
- 229920003023 plastic Polymers 0.000 title claims abstract description 92
- 239000004033 plastic Substances 0.000 title claims abstract description 92
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 83
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 228
- 239000011787 zinc oxide Substances 0.000 claims abstract description 114
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- 238000011068 loading method Methods 0.000 claims abstract description 5
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- 150000001412 amines Chemical class 0.000 claims abstract description 3
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- 238000003756 stirring Methods 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 55
- 239000008367 deionised water Substances 0.000 claims description 38
- 229910021641 deionized water Inorganic materials 0.000 claims description 38
- 230000001105 regulatory effect Effects 0.000 claims description 22
- 239000004698 Polyethylene Substances 0.000 claims description 21
- 229920000573 polyethylene Polymers 0.000 claims description 21
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 239000001993 wax Substances 0.000 claims description 15
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 14
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 13
- 229920000962 poly(amidoamine) Polymers 0.000 claims description 13
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 10
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 10
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 10
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 10
- 239000000839 emulsion Substances 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- 238000001694 spray drying Methods 0.000 claims description 9
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 8
- 229940057995 liquid paraffin Drugs 0.000 claims description 8
- LKAVYBZHOYOUSX-UHFFFAOYSA-N buta-1,3-diene;2-methylprop-2-enoic acid;styrene Chemical compound C=CC=C.CC(=C)C(O)=O.C=CC1=CC=CC=C1 LKAVYBZHOYOUSX-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 6
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 5
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 20
- 238000012360 testing method Methods 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 239000003242 anti bacterial agent Substances 0.000 description 8
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
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- 238000005299 abrasion Methods 0.000 description 1
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Abstract
The invention discloses an antibacterial environment-friendly polypropylene composite plastic, which comprises the following raw materials: polypropylene, graphene oxide loaded zinc oxide, SBS latex, nano zinc oxide, a dispersing agent, a compatilizer, an antioxidant and color master batch; the graphene oxide loaded zinc oxide is obtained by grafting pretreated graphene oxide with zinc oxide deposited on the surface and dendritic polyamide amine; and the pretreated graphene oxide is obtained by adsorbing and loading nano zinc oxide whiskers on a graphene oxide active lamellar. The invention also discloses a preparation method of the antibacterial environment-friendly polypropylene composite plastic. The invention combines nano zinc oxide into polypropylene plastic by adopting a specific process, has long antibacterial time, can effectively solve the problem of difficult degradation, has high mechanical strength, and is suitable for large-scale popularization and application.
Description
Technical Field
The invention relates to the technical field of antibacterial plastics, in particular to an antibacterial environment-friendly polypropylene composite plastic and a preparation method thereof.
Background
Polypropylene is a thermoplastic synthetic resin with excellent performance, and is colorless semitransparent thermoplastic light general plastic. The polypropylene has chemical resistance, heat resistance, electrical insulation, high strength mechanical property, good high wear resistance processing property and the like, and is widely developed and applied in a plurality of fields such as machinery, automobiles, electronic appliances, buildings, textiles, packaging, agriculture, forestry, fishery, food industry and the like.
The general polypropylene plastic does not have an antibacterial function, and an antibacterial agent is generally required to be added, so that the safety and sanitation of plastic products have become a concern with the increasing importance of people on the healthy environment, and the antibacterial plastic is generated. From the microbiological point of view, the antibiosis is focused on inhibiting the growth and propagation of bacteria in the long-term use process, and keeping the environment clean and sanitary. Generally, the requirements for the antibacterial agent are mainly that: a. antimicrobial ability and broad-spectrum antimicrobial properties; b. the lasting effect, namely washing resistance, abrasion resistance and long service life; c. compatibility with the substrate, i.e., ease of addition to the substrate, does not degrade product performance.
The antibacterial agents can be classified into 3 types of inorganic, organic and natural biological antibacterial agents. The antibacterial action mechanisms and the effectiveness of different antibacterial agents on the same pathogenic bacteria are different, and the antibacterial action mechanisms and the inhibition ranges of the same antibacterial agents on different pathogenic bacteria are also different. At present, after the polypropylene product is used, the polypropylene product needs to be degraded, the main force of the degradation is mainly microorganisms, the organic antibacterial agent is mainly a chemical synthetic substance, and the safety of the polypropylene product also has great hidden danger, and the plastic added with the inorganic antibacterial agent can cause that bacteria are difficult to survive, and the plastic product is difficult to degrade, so that the problem needs to be solved.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides an antibacterial environment-friendly polypropylene composite plastic and a preparation method thereof.
An antibacterial environment-friendly polypropylene composite plastic, which comprises the following raw materials: polypropylene, graphene oxide loaded zinc oxide, SBS latex, nano zinc oxide, a dispersing agent, a compatilizer, an antioxidant and color master batch; the mass ratio of the polypropylene to the graphene oxide loaded zinc oxide to the SBS latex to the nano zinc oxide to the dispersing agent to the compatilizer to the antioxidant to the masterbatch is 50-120:5-10:5-15:1-3:2-4:1-2:1-2:1-2; the graphene oxide loaded zinc oxide is obtained by grafting pretreated graphene oxide with zinc oxide deposited on the surface and dendritic polyamide amine; and the pretreated graphene oxide is obtained by adsorbing and loading nano zinc oxide whiskers on a graphene oxide active lamellar.
Preferably, the dispersing agent is at least one of zinc stearate, polyethylene wax and liquid paraffin.
Preferably, the compatibilizer is at least one of polypropylene grafted maleic anhydride, polyethylene grafted maleic anhydride, and methacrylic acid-styrene-butadiene polymer.
Preferably, the antioxidant is at least one of antioxidant 1010, antioxidant 168 and antioxidant 1076.
Preferably, the pretreated graphene oxide is prepared by the following specific steps: dispersing nano zinc oxide whisker into water, regulating the pH value of the system to 6-6.5, adding graphene oxide, performing ultrasonic dispersion for 1-2h, regulating the system to be neutral, standing for 10-20h, filtering, washing with water, and drying to obtain pretreated graphene oxide.
More preferably, the mass ratio of the nano zinc oxide whisker to the graphene oxide is 1-2:1-5.
More preferably, the frequency of the ultrasonic dispersion is in the range of 5 to 10kHz,
Preferably, the graphene oxide loaded zinc oxide is prepared by the following specific steps: dissolving zinc nitrate hexahydrate in water, adding hexamethylenetetramine and polyvinyl alcohol, stirring uniformly, adding pretreated graphene oxide, stirring at 60-90 ℃ for 5-10h, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide and dendritic polyamidoamine, stirring for 1-4h, filtering, washing with water, and drying to obtain graphene oxide-loaded zinc oxide.
According to the invention, nano zinc oxide whiskers are dispersed in deionized water, the pH of a system is regulated to 6-6.5, negative charges on the surfaces of the zinc oxide whiskers can be effectively adsorbed and loaded at active sites at the edges of a graphene oxide lamellar structure, but the loading capacity is low, and the bonding strength is poor through electrostatic bonding.
The nano zinc oxide grows on the surface of the pretreated graphene oxide, so that the loading capacity is extremely high, and the bonding strength is high. The surface of the obtained product is provided with a large number of active functional groups such as hydroxyl, carboxyl and the like, dendritic polyamidoamine is further grafted on the surface, so that a similar reinforcing rib structure can be formed in polypropylene, the mechanical strength of plastic is effectively enhanced, and the graphene oxide loaded zinc oxide is coated in an organic polymer structure, and the antibacterial timeliness can be effectively adjusted by being matched with externally dispersed and combined nano zinc oxide.
More preferably, the mass ratio of zinc nitrate hexahydrate, hexamethylenetetramine, polyvinyl alcohol, pretreated graphene oxide, 1-ethyl- (3-dimethylaminopropyl) carbodiimide and dendritic polyamidoamine is 1-3:2-5:1-3:2-6:0.01-0.1:1-3.
The preparation method of the antibacterial environment-friendly polypropylene composite plastic comprises the following steps:
S1, uniformly dispersing nano zinc oxide, deionized water and a dispersing agent, adding SBS emulsion, continuously stirring for 10-20min, and spray drying to obtain zinc oxide doped SBS;
S2, uniformly mixing polypropylene and zinc oxide doped SBS and graphene oxide loaded zinc oxide, adding a dispersing agent, a compatilizer, an antioxidant and color master batches, and continuously stirring for 1-5min to obtain a premix;
And S3, extruding the premix, cooling in a water tank, cooling in air, and granulating to obtain the antibacterial environment-friendly polypropylene composite plastic.
Preferably, the step S3 is extruded by a double-screw extruder, wherein the temperature of the first area is 150-160 ℃, the temperature of the second area is 180-190 ℃, the temperature of the third area is 195-205 ℃, the temperature of the fourth area is 200-210 ℃, the temperature of the fifth area is 190-205 ℃, the temperature of the machine head is 200-210 ℃, and the rotating speed of the screw of the main machine is 100-300r/min.
The beneficial effects are that:
according to the application, zinc oxide doped SBS is added into polypropylene master batch, so that zinc oxide is better dispersed in a mixed system, and after melt blending, not only is the master batch good in antibacterial effect, but also graphene oxide loaded zinc oxide is dispersed therein, so that the polypropylene master batch has high activity, wide antibacterial spectrum and stable and durable antibacterial effect. In addition, the applicant finds through experiments that the application can promote the degradation of plastics on the basis of ensuring excellent antibacterial aging, and has no obvious influence on the mechanical properties.
If nano zinc oxide is directly doped into polypropylene plastic, the compatibility is poor. According to the invention, the nano zinc oxide and the SBS emulsion are dispersed, so that the dispersion uniformity of the nano zinc oxide in the polypropylene plastic is enhanced, the polypropylene plastic has better antibacterial performance, and the graphene oxide loaded zinc oxide is uniformly distributed in the polypropylene plastic and is not only covered on the surface of the polypropylene plastic, so that the polypropylene plastic product still has better antibacterial performance and excellent antibacterial performance even after being damaged.
The invention combines nano zinc oxide into polypropylene plastic by adopting a specific process, has long antibacterial time, can effectively solve the problem of difficult degradation, has high mechanical strength, and is suitable for large-scale popularization and application.
Drawings
FIG. 1 is a graph showing the comparison of mechanical properties of the antibacterial polypropylene plastics obtained in example 5 and comparative examples 1 to 3.
FIG. 2 is a graph showing the comparison of the antibacterial effect of the antibacterial polypropylene plastics obtained in example 5 and comparative examples 1 to 3 at 0, 3 and 6 months.
FIG. 3 is a graph showing the comparison of the antibacterial effect of the antibacterial polypropylene plastics obtained in example 5 and comparative examples 1 to 3 after 1 year exposure.
FIG. 4 is a graph showing the comparison of mass loss rates of the antibacterial polypropylene plastics obtained in example 5 and comparative examples 1 to 3 after being buried in soil for 1 year.
Detailed Description
The invention is further illustrated below in connection with specific embodiments.
Example 1
An antibacterial environment-friendly polypropylene composite plastic, which comprises the following raw materials: 50kg of polypropylene, 5kg of graphene oxide loaded zinc oxide, 5kg of SBS latex, 1kg of nano zinc oxide, 2kg of liquid paraffin, 1kg of methacrylic acid-styrene-butadiene polymer, 1076 kg of antioxidant and 1kg of masterbatch.
The graphene oxide loaded zinc oxide is prepared by adopting the following specific steps: adding 1kg of zinc nitrate hexahydrate into 10kg of deionized water, uniformly stirring, adding 2kg of hexamethylenetetramine and 1kg of polyvinyl alcohol, uniformly stirring, adding 2kg of pretreated graphene oxide, stirring at the temperature of 60 ℃ for 5 hours at the stirring speed of 50r/min, adding 0.01kg of 1-ethyl- (3-dimethylaminopropyl) carbodiimide and 1kg of dendritic polyamidoamine, continuously stirring for 1 hour, filtering, washing for 1 time by adopting deionized water, and drying to obtain the graphene oxide loaded zinc oxide.
The pretreatment graphene oxide is prepared by adopting the following specific steps: dispersing 1kg of nano zinc oxide whisker into 20kg of deionized water, regulating the pH value of a system to be 6-6.5 by adopting hydrochloric acid with the concentration of 0.1mol/L, adding 1kg of graphene oxide, carrying out ultrasonic dispersion for 1h, regulating the system to be neutral by adopting sodium hydroxide solution with the concentration of 0.1mol/L at the ultrasonic frequency of 5kHz, standing for 10h, filtering, washing by adopting deionized water, and drying to obtain the pretreated graphene oxide.
The preparation method of the antibacterial environment-friendly polypropylene composite plastic comprises the following steps:
S1, adding nano zinc oxide, deionized water and liquid paraffin into a high-speed dispersing machine, dispersing for 5min at the speed of 1000r/min, adding SBS emulsion, continuously stirring for 10min, and spray drying to obtain zinc oxide doped SBS;
S2, adding polypropylene, zinc oxide doped SBS and graphene oxide loaded zinc oxide into a mixer, stirring at a speed of 500r/min for 10min, adding liquid paraffin, methacrylic acid-styrene-butadiene polymer, antioxidant 1076 and color master batch, and continuously stirring for 1min to obtain premix;
And S3, extruding the premix by a double-screw extruder, wherein the temperature of the first area is 150 ℃, the temperature of the second area is 180 ℃, the temperature of the third area is 195 ℃, the temperature of the fourth area is 200 ℃, the temperature of the fifth area is 190 ℃, the temperature of the machine head is 200 ℃, the rotating speed of a main machine screw is 100r/min, and sequentially cooling by a water tank, cooling by air and granulating to obtain the antibacterial environment-friendly polypropylene composite plastic.
Example 2
An antibacterial environment-friendly polypropylene composite plastic, which comprises the following raw materials: 120kg of polypropylene, 10kg of graphene oxide loaded zinc oxide, 15kg of SBS latex, 3kg of nano zinc oxide, 4kg of liquid paraffin, 2kg of methacrylic acid-styrene-butadiene polymer, 168 kg of antioxidant and 2kg of color master batch.
The graphene oxide loaded zinc oxide is prepared by adopting the following specific steps: 3kg of zinc nitrate hexahydrate is added into 30kg of deionized water, uniformly stirred, 5kg of hexamethylenetetramine and 3kg of polyvinyl alcohol are added, 6kg of pretreated graphene oxide is added into the mixture, the mixture is stirred for 10 hours at the temperature of 90 ℃ at the stirring speed of 100r/min, 0.1kg of 1-ethyl- (3-dimethylaminopropyl) carbodiimide and 3kg of dendritic polyamidoamine are added, the mixture is continuously stirred for 4 hours, filtered, washed for 3 times by adopting deionized water, and dried to obtain the graphene oxide loaded zinc oxide.
The pretreatment graphene oxide is prepared by adopting the following specific steps: dispersing 2kg of nano zinc oxide whisker into 50kg of deionized water, adopting hydrochloric acid with the concentration of 0.2mol/L to adjust the pH value of a system to be 6-6.5, adding 5kg of graphene oxide, carrying out ultrasonic dispersion for 2 hours, adopting sodium hydroxide solution with the concentration of 0.2mol/L to adjust the system to be neutral, standing for 20 hours, filtering, adopting deionized water to wash, and drying to obtain the pretreated graphene oxide.
The preparation method of the antibacterial environment-friendly polypropylene composite plastic comprises the following steps:
S1, adding nano zinc oxide, deionized water and liquid paraffin into a high-speed dispersing machine, dispersing for 20min at a speed of 5000r/min, adding SBS emulsion, continuously stirring for 20min, and spray drying to obtain zinc oxide doped SBS;
s2, adding polypropylene, zinc oxide doped SBS and graphene oxide loaded zinc oxide into a mixer, stirring at a speed of 1500r/min for 20min, adding liquid paraffin, methacrylic acid-styrene-butadiene polymer, antioxidant 168 and masterbatch, and continuously stirring for 5min to obtain premix;
And S3, extruding the premix by a double-screw extruder, wherein the temperature of the first area is 160 ℃, the temperature of the second area is 190 ℃, the temperature of the third area is 205 ℃, the temperature of the fourth area is 210 ℃, the temperature of the fifth area is 205 ℃, the temperature of the machine head is 210 ℃, the screw speed of the main machine is 300r/min, and sequentially cooling by a water tank, cooling by air and granulating to obtain the antibacterial environment-friendly polypropylene composite plastic.
Example 3
An antibacterial environment-friendly polypropylene composite plastic, which comprises the following raw materials: 90kg of polypropylene, 9kg of graphene oxide loaded zinc oxide, 8kg of SBS latex, 2.5kg of nano zinc oxide, 1kg of zinc stearate, 1.5kg of polyethylene wax, 1.7kg of polyethylene grafted maleic anhydride, 1076.2 kg of antioxidant and 1.6kg of masterbatch.
The graphene oxide loaded zinc oxide is prepared by adopting the following specific steps: adding 1.5kg of zinc nitrate hexahydrate into 25kg of deionized water, uniformly stirring, adding 3kg of hexamethylenetetramine and 2.5kg of polyvinyl alcohol, uniformly stirring, adding 3kg of pretreated graphene oxide, stirring at 80 ℃ for 6 hours at a stirring speed of 90r/min, adding 0.03kg of 1-ethyl- (3-dimethylaminopropyl) carbodiimide and 2.5kg of dendritic polyamidoamine, continuously stirring for 2 hours, filtering, washing for 2 times by adopting deionized water, and drying to obtain graphene oxide loaded zinc oxide.
The pretreatment graphene oxide is prepared by adopting the following specific steps: dispersing 1.7kg of nano zinc oxide whisker into 30kg of deionized water, regulating the pH value of the system to be 6-6.5 by adopting hydrochloric acid with the concentration of 0.18mol/L, adding 2kg of graphene oxide, carrying out ultrasonic dispersion for 100min, regulating the ultrasonic frequency to be 7kHz, regulating the system to be neutral by adopting sodium hydroxide solution with the concentration of 0.18mol/L, standing for 13h, filtering, washing by adopting deionized water, and drying to obtain pretreated graphene oxide.
The preparation method of the antibacterial environment-friendly polypropylene composite plastic comprises the following steps:
s1, adding nano zinc oxide, deionized water and zinc stearate into a high-speed dispersing machine, dispersing for 10min at the speed of 4000r/min, adding SBS emulsion, continuously stirring for 18min, and spray drying to obtain zinc oxide doped SBS;
S2, adding polypropylene, zinc oxide doped SBS and graphene oxide loaded zinc oxide into a mixer, stirring at a speed of 800r/min for 18min, adding polyethylene wax, polyethylene grafted maleic anhydride, an antioxidant 1076 and masterbatch, and continuously stirring for 2min to obtain a premix;
And S3, extruding the premix by a double-screw extruder, wherein the temperature of the first area is 158 ℃, the temperature of the second area is 182 ℃, the temperature of the third area is 202 ℃, the temperature of the fourth area is 204 ℃, the temperature of the fifth area is 200 ℃, the temperature of the machine head is 202 ℃, the rotating speed of a main machine screw is 240r/min, and sequentially cooling by a water tank, cooling by air and granulating to obtain the antibacterial environment-friendly polypropylene composite plastic.
Example 4
An antibacterial environment-friendly polypropylene composite plastic, which comprises the following raw materials: 110kg of polypropylene, 7kg of graphene oxide loaded zinc oxide, 12kg of SBS latex, 1.5kg of nano zinc oxide, 2kg of polyethylene wax, 1.5kg of zinc stearate, 1.3kg of polyethylene grafted maleic anhydride, 10761.8kg of antioxidant and 1.4kg of color master batch.
The graphene oxide loaded zinc oxide is prepared by adopting the following specific steps: adding 2.5kg of zinc nitrate hexahydrate into 15kg of deionized water, uniformly stirring, adding 4kg of hexamethylenetetramine and 1.5kg of polyvinyl alcohol, uniformly stirring, adding 5kg of pretreated graphene oxide, stirring at the temperature of 70 ℃ for 8h at the stirring speed of 70r/min, adding 0.07kg of 1-ethyl- (3-dimethylaminopropyl) carbodiimide and 1.5kg of dendritic polyamidoamine, continuously stirring for 2-3h, filtering, washing for 2 times by adopting deionized water, and drying to obtain the graphene oxide loaded zinc oxide.
The pretreatment graphene oxide is prepared by adopting the following specific steps: dispersing 1.7kg of nano zinc oxide whisker into 30kg of deionized water, regulating the pH value of the system to be 6-6.5 by adopting hydrochloric acid with the concentration of 0.18mol/L, adding 2kg of graphene oxide, carrying out ultrasonic dispersion for 100min, regulating the ultrasonic frequency to be 7kHz, regulating the system to be neutral by adopting sodium hydroxide solution with the concentration of 0.18mol/L, standing for 13h, filtering, washing by adopting deionized water, and drying to obtain pretreated graphene oxide.
The preparation method of the antibacterial environment-friendly polypropylene composite plastic comprises the following steps:
S1, adding nano zinc oxide, deionized water and polyethylene wax into a high-speed dispersing machine, dispersing for 10min at the speed of 4000r/min, adding SBS latex, continuously stirring for 12-18min, and spray drying to obtain zinc oxide doped SBS;
S2, adding polypropylene, zinc oxide doped SBS and graphene oxide loaded zinc oxide into a mixer, stirring at a speed of 1200r/min for 12min, adding zinc stearate, polyethylene grafted maleic anhydride, an antioxidant 1076 and masterbatch, and continuously stirring for 4min to obtain a premix;
And S3, extruding the premix by a double-screw extruder, wherein the temperature of the first area is 152 ℃, the temperature of the second area is 188 ℃, the temperature of the third area is 198 ℃, the temperature of the fourth area is 206 ℃, the temperature of the fifth area is 195 ℃, the temperature of the machine head is 208 ℃, the screw speed of the main machine is 150r/min, and the antibacterial environment-friendly polypropylene composite plastic is obtained by cooling in a water tank, cooling in air and granulating.
Example 5
An antibacterial environment-friendly polypropylene composite plastic, which comprises the following raw materials: 100kg of polypropylene, 8kg of graphene oxide loaded zinc oxide, 10kg of SBS latex, 2kg of nano zinc oxide, 3kg of polyethylene wax, 1.5kg of polypropylene grafted maleic anhydride, 1.5kg of antioxidant 1010 and 1.5kg of color master batch.
The graphene oxide loaded zinc oxide is prepared by adopting the following specific steps: adding 2kg of zinc nitrate hexahydrate into 20kg of deionized water, uniformly stirring, adding 3.5kg of hexamethylenetetramine and 2kg of polyvinyl alcohol, uniformly stirring, adding 4kg of pretreated graphene oxide, stirring at 75 ℃ for 7h at the stirring speed of 80r/min, adding 0.05kg of 1-ethyl- (3-dimethylaminopropyl) carbodiimide and 2kg of dendritic polyamidoamine, continuously stirring for 2.5h, filtering, washing for 2 times by adopting deionized water, and drying to obtain graphene oxide loaded zinc oxide.
The pretreatment graphene oxide is prepared by adopting the following specific steps: dispersing 1.5kg of nano zinc oxide whisker into 35kg of deionized water, regulating the pH value of the system to be 6-6.5 by adopting hydrochloric acid with the concentration of 0.15mol/L, adding 3kg of graphene oxide, carrying out ultrasonic dispersion for 90min, regulating the ultrasonic frequency to be 7.5kHz, regulating the system to be neutral by adopting sodium hydroxide solution with the concentration of 0.15mol/L, standing for 15h, filtering, washing by adopting deionized water, and drying to obtain pretreated graphene oxide.
The preparation method of the antibacterial environment-friendly polypropylene composite plastic comprises the following steps:
S1, adding nano zinc oxide, deionized water and polyethylene wax into a high-speed dispersing machine, dispersing for 13min at a speed of 3000r/min, adding SBS emulsion, continuously stirring for 15min, and spray drying to obtain zinc oxide doped SBS;
S2, adding polypropylene, zinc oxide doped SBS and graphene oxide loaded zinc oxide into a mixer, stirring at a speed of 1000r/min for 15min, adding polyethylene wax, polypropylene grafted maleic anhydride, antioxidant 1010 and masterbatch, and continuously stirring for 3min to obtain a premix;
And S3, extruding the premix by a double-screw extruder, wherein the temperature of the first area is 155 ℃, the temperature of the second area is 185 ℃, the temperature of the third area is 200 ℃, the temperature of the fourth area is 205 ℃, the temperature of the fifth area is 198 ℃, the temperature of the machine head is 205 ℃, the rotating speed of a main machine screw is 200r/min, and sequentially cooling by a water tank, cooling by air and granulating to obtain the antibacterial environment-friendly polypropylene composite plastic.
Comparative example 1
Commercial antimicrobial polypropylene plastics (available from certain industrial product design (Shanghai) Inc.).
Comparative example 2
An antibacterial environment-friendly polypropylene composite plastic, which comprises the following raw materials: 100kg of polypropylene, 8kg of graphene oxide loaded zinc oxide, 10kg of SBS latex, 2kg of nano zinc oxide, 3kg of polyethylene wax, 1.5kg of polypropylene grafted maleic anhydride, 1.5kg of antioxidant 1010 and 1.5kg of color master batch.
The graphene oxide loaded zinc oxide is prepared by adopting the following specific steps: adding 2kg of zinc nitrate hexahydrate into 20kg of deionized water, uniformly stirring, adding 3.5kg of hexamethylenetetramine and 2kg of polyvinyl alcohol, uniformly stirring, adding 4kg of pretreated graphene oxide, stirring at 75 ℃ for 7 hours at the stirring speed of 80r/min, filtering, washing for 2 times by adopting deionized water, and drying to obtain the graphene oxide-loaded zinc oxide.
The pretreatment graphene oxide is prepared by adopting the following specific steps: dispersing 1.5kg of nano zinc oxide whisker into 35kg of deionized water, regulating the pH value of the system to be 6-6.5 by adopting hydrochloric acid with the concentration of 0.15mol/L, adding 3kg of graphene oxide, carrying out ultrasonic dispersion for 90min, regulating the ultrasonic frequency to be 7.5kHz, regulating the system to be neutral by adopting sodium hydroxide solution with the concentration of 0.15mol/L, standing for 15h, filtering, washing by adopting deionized water, and drying to obtain pretreated graphene oxide.
The preparation method of the antibacterial environment-friendly polypropylene composite plastic comprises the following steps:
S1, adding nano zinc oxide, deionized water and polyethylene wax into a high-speed dispersing machine, dispersing for 13min at a speed of 3000r/min, adding SBS emulsion, continuously stirring for 15min, and spray drying to obtain zinc oxide doped SBS;
S2, adding polypropylene, zinc oxide doped SBS and graphene oxide loaded zinc oxide into a mixer, stirring at a speed of 1000r/min for 15min, adding polyethylene wax, polypropylene grafted maleic anhydride, antioxidant 1010 and masterbatch, and continuously stirring for 3min to obtain a premix;
And S3, extruding the premix by a double-screw extruder, wherein the temperature of the first area is 155 ℃, the temperature of the second area is 185 ℃, the temperature of the third area is 200 ℃, the temperature of the fourth area is 205 ℃, the temperature of the fifth area is 198 ℃, the temperature of the machine head is 205 ℃, the rotating speed of a main machine screw is 200r/min, and sequentially cooling by a water tank, cooling by air and granulating to obtain the antibacterial environment-friendly polypropylene composite plastic.
Comparative example 3
An antibacterial environment-friendly polypropylene composite plastic, which comprises the following raw materials: 100kg of polypropylene, 8kg of graphene oxide loaded zinc oxide, 10kg of SBS latex, 2kg of nano zinc oxide, 3kg of polyethylene wax, 1.5kg of polypropylene grafted maleic anhydride, 1.5kg of antioxidant 1010 and 1.5kg of color master batch.
The graphene oxide loaded zinc oxide is prepared by adopting the following specific steps: adding 4kg of pretreated graphene oxide into 20kg of deionized water, uniformly stirring, stirring at the temperature of 75 ℃ for 7 hours at the stirring speed of 80r/min, adding 0.05kg of 1-ethyl- (3-dimethylaminopropyl) carbodiimide and 2kg of dendritic polyamidoamine, continuously stirring for 2.5 hours, filtering, washing with deionized water for 2 times, and drying to obtain the graphene oxide-loaded zinc oxide.
The pretreatment graphene oxide is prepared by adopting the following specific steps: dispersing 1.5kg of nano zinc oxide whisker into 35kg of deionized water, regulating the pH value of the system to be 6-6.5 by adopting hydrochloric acid with the concentration of 0.15mol/L, adding 3kg of graphene oxide, carrying out ultrasonic dispersion for 90min, regulating the ultrasonic frequency to be 7.5kHz, regulating the system to be neutral by adopting sodium hydroxide solution with the concentration of 0.15mol/L, standing for 15h, filtering, washing by adopting deionized water, and drying to obtain pretreated graphene oxide.
The preparation method of the antibacterial environment-friendly polypropylene composite plastic comprises the following steps:
S1, adding nano zinc oxide, deionized water and polyethylene wax into a high-speed dispersing machine, dispersing for 13min at a speed of 3000r/min, adding SBS emulsion, continuously stirring for 15min, and spray drying to obtain zinc oxide doped SBS;
S2, adding polypropylene, zinc oxide doped SBS and graphene oxide loaded zinc oxide into a mixer, stirring at a speed of 1000r/min for 15min, adding polyethylene wax, polypropylene grafted maleic anhydride, antioxidant 1010 and masterbatch, and continuously stirring for 3min to obtain a premix;
And S3, extruding the premix by a double-screw extruder, wherein the temperature of the first area is 155 ℃, the temperature of the second area is 185 ℃, the temperature of the third area is 200 ℃, the temperature of the fourth area is 205 ℃, the temperature of the fifth area is 198 ℃, the temperature of the machine head is 205 ℃, the rotating speed of a main machine screw is 200r/min, and sequentially cooling by a water tank, cooling by air and granulating to obtain the antibacterial environment-friendly polypropylene composite plastic.
Determination of tensile Properties of plastics section 1, see GB/T1040.1-2018: general rule and GB/T1040.2-2022 determination of Plastic tensile Properties part 2: test conditions for molded and extruded plastics the antibacterial polypropylene plastics obtained in example 5 and comparative examples 1 to 3 were subjected to tensile strength test, the sample size being type 1A, and the test speed being 50mm/min; the antibacterial polypropylene plastics obtained in example 5 and comparative examples 1 to 3 were subjected to bending strength test with reference to GB/T9341-2008 "determination of Plastic bending Property", and the test sample size was 80mm long, 10mm wide, 4mm thick, test speed 5mm/min; the antibacterial polypropylene plastics obtained in example 5 and comparative examples 1 to 3 were subjected to impact strength test with reference to GB/T1843-2008 "determination of impact Strength of Plastic cantilever beam", and the sample size was type A.
As a result, as shown in FIG. 1, the mechanical properties of the antibacterial polypropylene plastic obtained in example 5 were significantly better than those of the comparative example. In contrast, comparative example 2, which was not grafted with dendritic polyamidoamine, failed to form a rib-like structure in polypropylene, resulting in a mechanical strength similar to that of comparative example 1. Comparative example 3, although grafting was performed using dendritic polyamidoamine, the pretreated graphene oxide surface was not zinc oxide loaded, making its reinforcing effect inferior to example 5.
The antibacterial effect of the antibacterial polypropylene plastics obtained in example 5 and comparative examples 1 to 3 was tested with reference to GB/T31402-2015 test method for antibacterial property of Plastic surface, and E.coli (ATCC 8739) and Staphylococcus aureus (ATCC 6538P) were used as test subjects, the test time was performed immediately after the preparation of each group of antibacterial polypropylene plastics was completed (0 month), and each group of antibacterial polypropylene plastics was left at normal temperature for 3 months and 6 months, respectively.
As a result, as shown in FIG. 2, the antibacterial polypropylene plastics obtained in comparative example 1 and comparative example 3 were reduced in antibacterial efficiency as the standing time was prolonged. The antibacterial polypropylene plastics obtained in example 5 and comparative example 2 still have good antibacterial property after being placed for 6 months, which indicates that the antibacterial polypropylene plastics have durable antibacterial property.
The antibacterial polypropylene plastics obtained in example 5 and comparative examples 1 to 3 were injection molded to prepare plastic test pieces having dimensions of 50mm long, 20mm wide and 1mm thick, and after the plastic test pieces were left exposed in a cool and ventilated place for 1 year, the plastic test pieces were sterilized with 75% alcohol, and 10CFU of staphylococcus aureus, helicobacter pylori and candida albicans were respectively implanted in the center of each group of plastic test pieces under a sterile environment, and were cultured at 37 ℃ for 7d, and the colony numbers were observed and recorded.
As shown in FIG. 3, the antibacterial polypropylene plastic obtained in example 5 still has excellent antibacterial effect after 1 year of empty, and the antibacterial effect of the antibacterial polypropylene plastic obtained in the invention is proved to be durable.
The antibacterial polypropylene plastics obtained in example 5 and comparative examples 1 to 3 were injection molded to prepare plastic test pieces having dimensions of 50mm in length, 20mm in width and 1mm in thickness, air-dried at room temperature, and the weight of the plastic test pieces was weighed and recorded as the initial weight; then, the plastic test piece is buried in soil and stored for 1 year in a constant temperature environment of 37 ℃, the plastic test piece is taken out and washed, air-dried at room temperature, the weight of the plastic test piece is weighed, the weight is recorded as the weight after degradation, and the degradation degree of the plastic test piece is characterized by calculating the mass loss rate.
As shown in FIG. 4, although the antibacterial polypropylene plastic obtained in example 5 has a durable antibacterial effect, the soil environment is more complex, and the microorganism content and variety are much more than those in the normal environment; under the soil state, the invention can be rapidly decomposed by microorganisms, thereby accelerating the degradation of plastics.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (8)
1. An antibacterial environment-friendly polypropylene composite plastic is characterized by comprising the following raw materials: polypropylene, graphene oxide loaded zinc oxide, SBS latex, nano zinc oxide, a dispersing agent, a compatilizer, an antioxidant and color master batch; the mass ratio of the polypropylene to the graphene oxide loaded zinc oxide to the SBS latex to the nano zinc oxide to the dispersing agent to the compatilizer to the antioxidant to the masterbatch is 50-120:5-10:5-15:1-3:2-4:1-2:1-2:1-2;
the graphene oxide loaded zinc oxide is obtained by grafting pretreated graphene oxide with zinc oxide deposited on the surface and dendritic polyamide amine; the pretreated graphene oxide is obtained by adsorbing nano zinc oxide whiskers and loading the nano zinc oxide whiskers on a graphene oxide active lamellar;
The graphene oxide loaded zinc oxide is prepared by adopting the following specific steps: dissolving zinc nitrate hexahydrate in water, adding hexamethylenetetramine and polyvinyl alcohol, uniformly stirring, adding pretreated graphene oxide, stirring for 5-10 hours at 60-90 ℃, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide and dendritic polyamidoamine, continuously stirring for 1-4 hours, filtering, washing with water, and drying to obtain graphene oxide-loaded zinc oxide;
the pretreatment graphene oxide is prepared by adopting the following specific steps: dispersing nano zinc oxide whisker into water, regulating the pH value of the system to 6-6.5, adding graphene oxide, performing ultrasonic dispersion for 1-2h, regulating the system to be neutral, standing for 10-20h, filtering, washing with water, and drying to obtain pretreated graphene oxide.
2. The antibacterial environment-friendly polypropylene composite plastic according to claim 1, wherein the dispersing agent is at least one of zinc stearate, polyethylene wax and liquid paraffin.
3. The antibacterial environment-friendly polypropylene composite plastic according to claim 1, wherein the compatilizer is at least one of polypropylene grafted maleic anhydride, polyethylene grafted maleic anhydride and methacrylic acid-styrene-butadiene polymer.
4. The antibacterial environment-friendly polypropylene composite plastic according to claim 1, wherein the antioxidant is at least one of antioxidant 1010, antioxidant 168 and antioxidant 1076.
5. The antibacterial environment-friendly polypropylene composite plastic according to claim 1, wherein the mass ratio of the nano zinc oxide whisker to the graphene oxide is 1-2:1-5.
6. The antibacterial environment-friendly polypropylene composite plastic according to claim 1, wherein the mass ratio of zinc nitrate hexahydrate, hexamethylenetetramine, polyvinyl alcohol, pretreated graphene oxide, 1-ethyl- (3-dimethylaminopropyl) carbodiimide and dendritic polyamidoamine is 1-3:2-5:1-3:2-6:0.01-0.1:1-3.
7. A method for preparing the antibacterial environment-friendly polypropylene composite plastic as claimed in any one of claims 1 to 6, which comprises the following steps:
S1, uniformly dispersing nano zinc oxide, deionized water and a dispersing agent, adding SBS emulsion, continuously stirring for 10-20min, and spray drying to obtain zinc oxide doped SBS;
S2, uniformly mixing polypropylene and zinc oxide doped SBS and graphene oxide loaded zinc oxide, adding a dispersing agent, a compatilizer, an antioxidant and color master batches, and continuously stirring for 1-5min to obtain a premix;
And S3, extruding the premix, cooling in a water tank, cooling in air, and granulating to obtain the antibacterial environment-friendly polypropylene composite plastic.
8. The method for preparing the antibacterial environment-friendly polypropylene composite plastic according to claim 7, wherein the step S3 is extruded by a double-screw extruder, wherein the temperature of a first area is 150-160 ℃, the temperature of a second area is 180-190 ℃, the temperature of a third area is 195-205 ℃, the temperature of a fourth area is 200-210 ℃, the temperature of a fifth area is 190-205 ℃, the temperature of a machine head is 200-210 ℃, and the rotating speed of a main screw is 100-300r/min.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104059344A (en) * | 2014-07-01 | 2014-09-24 | 南京理工大学 | Polylactic acid/modified graphene oxide antibacterial plastic and preparation method |
| CN108690263A (en) * | 2017-04-12 | 2018-10-23 | 合肥杰事杰新材料股份有限公司 | A kind of antibacterial polyolefin and preparation method thereof |
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104059344A (en) * | 2014-07-01 | 2014-09-24 | 南京理工大学 | Polylactic acid/modified graphene oxide antibacterial plastic and preparation method |
| CN108690263A (en) * | 2017-04-12 | 2018-10-23 | 合肥杰事杰新材料股份有限公司 | A kind of antibacterial polyolefin and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 高强高韧超支化聚酰胺胺/氧化石墨烯仿贝壳复合膜;张亮;王晓敏;刘春华;杨文;郝文涛;;合肥工业大学学报(自然科学版);20160828(08);第1118页左列倒数第2段 * |
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