CN108034148B - Antibacterial cellulose/polypropylene composite material and preparation method thereof - Google Patents
Antibacterial cellulose/polypropylene composite material and preparation method thereof Download PDFInfo
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Abstract
An antibacterial cellulose/polypropylene composite material and a preparation method thereof relate to a cellulose/polypropylene composite material and a preparation method thereof. The problem that the bacteriostatic effect is not ideal when the existing bacteriostatic agent is added into the wood-plastic composite material is solved. The composite material comprises cellulose, polypropylene resin, a bacteriostatic agent, a compatilizer, a coupling agent, an antioxidant, a dispersing agent and a porous medium material. The method comprises the following steps: firstly, weighing raw materials; secondly, adding a coupling agent into the ethanol solution to obtain a hydrolyzed coupling agent; adding the bacteriostatic agent into the hydrolyzed coupling agent, stirring and drying to obtain a bacteriostatic agent compound; adding the bacteriostatic agent compound, the polypropylene resin A, the antioxidant and the dispersing agent into a double-screw extruder, granulating and drying to obtain bacteriostatic master batch; and thirdly, adding the antibacterial master batch, the cellulose, the polypropylene resin B, the compatilizer and the porous medium material into a double-screw extruder, granulating, drying to obtain composite granules, and performing injection molding to obtain the antibacterial composite granules. The invention is used in the field of wood-plastic composite materials.
Description
Technical Field
The invention relates to a cellulose/polypropylene composite material and a preparation method thereof.
Background
With the improvement of safety consciousness of people, higher bacteriostatic requirements exist in the use of furniture, food packages, articles for daily use and the like, so the design, production and application of bacteriostatic materials are concerned. With commonly used resins such as: composite materials in which thermosetting resins (unsaturated polyesters, epoxy resins, aminoplasts, etc.) and thermoplastic resins (polyethylene, polypropylene, polyvinyl chloride, etc.) are used as matrices are most widely used. Among them, polypropylene (PP) is low in price, excellent in performance, good in stability and easy to machine and form. However, PP itself has no antibacterial activity, and a composite material using polypropylene as a matrix is affected by the environment and is easily corroded by microorganisms after long-term use, which not only damages the service life of the material and affects health, but also increases economic burden. The antibacterial polypropylene-based composite material prepared has positive significance for inhibiting the survival of microorganisms such as bacteria and fungi and prolonging the service life of the composite material.
Common bacteriostatic agents can be divided into four types, namely inorganic bacteriostatic agents, organic bacteriostatic agents, natural bacteriostatic agents and high-molecular bacteriostatic agents. The natural bacteriostatic agent has poor stability, the high-molecular bacteriostatic agent has limitation in application, the bacteriostatic effect of the inorganic bacteriostatic agent and the bacteriostatic effect of the organic bacteriostatic agent are not ideal, the bactericidal rate of escherichia coli and staphylococcus aureus is about 80%, and the use requirement of the existing wood-plastic composite material cannot be met.
Disclosure of Invention
The invention provides a bacteriostatic cellulose/polypropylene composite material and a preparation method thereof, aiming at solving the problem that the bacteriostatic effect of the existing bacteriostatic agent added into a wood-plastic composite material is not ideal.
The antibacterial cellulose/polypropylene composite material comprises, by weight, 10.00-74.00 parts of cellulose, 11.00-87.00 parts of polypropylene resin, 0.50-5.00 parts of an antibacterial agent, 2.00-7.00 parts of a compatilizer, 0.10-2.00 parts of a coupling agent, 0.10-2.00 parts of an antioxidant, 0.10-2.00 parts of a dispersant and 0.50-3.00 parts of a porous medium material.
Further, the cellulose is one or a mixture of more of microcrystalline cellulose, cellulose whisker and nanocellulose.
Further, the polypropylene resin is a random copolymer polypropylene resin.
Further, the bacteriostatic agent comprises an inorganic bacteriostatic agent and an organic bacteriostatic agent which are combined according to any ratio; the inorganic bacteriostatic agent is one or a mixture of more of zinc oxide, nano silver, nano copper salt, silicon dioxide and anatase titanium dioxide, and the organic bacteriostatic agent is one or a mixture of more of 3-amino-1, 2, 4-triazole, 4-amino-1, 2, 4-triazole and 3, 5-diamino-1, 2, 4-triazole.
Further, the compatilizer is one or a combination of maleic anhydride grafted polypropylene and glycidyl methacrylate grafted polypropylene.
Further, the coupling agent is one or a combination of two of a silane coupling agent, an aluminate coupling agent and a titanate coupling agent.
Further, the antioxidant is one or a combination of two of phosphite antioxidant and hindered phenol antioxidant.
Further, the dispersing agent is one or a combination of two of ethylene bis stearamide, stearic acid monoglyceride and tristearin.
Further, the porous medium material is one or a mixture of several of nano silicon dioxide, montmorillonite, 4A molecular sieve, 5A molecular sieve, anatase titanium dioxide and diatomite.
The preparation method of the antibacterial cellulose/polypropylene composite material comprises the following steps:
weighing 10.00-74.00 parts of cellulose, 11.00-87.00 parts of polypropylene resin, 0.50-5.00 parts of bacteriostatic agent, 2.00-7.00 parts of compatilizer, 0.10-2.00 parts of coupling agent, 0.10-2.00 parts of antioxidant, 0.10-2.00 parts of dispersing agent and 0.50-3.00 parts of porous medium material by weight; dividing the polypropylene resin into 2 parts, namely a polypropylene resin A and a polypropylene resin B, wherein the mass ratio of the polypropylene resin A to the polypropylene resin B is 3: 7;
preparation of antibacterial master batch
Adding a coupling agent into an ethanol solution, and stirring at room temperature for 5-10 min to obtain a hydrolyzed coupling agent; the mass concentration of the ethanol solution is 80-90%;
adding the bacteriostatic agent into the hydrolyzed coupling agent, stirring for 30-40 min at the stirring speed of 800-1200 r/min to obtain a mixed solution, and drying the mixed solution at 80-90 ℃ to obtain a bacteriostatic agent compound;
adding the bacteriostatic agent compound, the polypropylene resin A, the antioxidant and the dispersing agent into a feeding barrel of a double-screw extruder, setting a feeding speed and a screw rotating speed, air-cooling, granulating, and drying to obtain bacteriostatic master batch;
and thirdly, mechanically and uniformly mixing the antibacterial master batch, the cellulose, the polypropylene resin B, the compatilizer and the porous medium material, adding the mixture into a feeding barrel of a double-screw extruder, setting the feeding speed and the screw rotating speed, carrying out air cooling granulation, drying to obtain composite granules, and carrying out injection molding to obtain the antibacterial cellulose/polypropylene composite material.
Further, in the second step, the feeding rotating speed is 200-220 r/min, and the screw rotating speed is 250-270 r/min.
Further, the temperature of each zone of the twin-screw extruder in the step two is set as follows: the melt temperatures of the first zone, the second zone, the third zone, the fourth zone, the fifth zone, the sixth zone and the machine head are respectively 150 ℃, 155 ℃, 165 ℃, 155 ℃, 150 ℃ and 165 ℃.
Furthermore, in the third step, the feeding rotating speed is 200-220 r/min, and the screw rotating speed is 250-270 r/min.
Further, the temperature of each zone of the double-screw extruder in the third step is set as follows: the melt temperatures of the first zone, the second zone, the third zone, the fourth zone, the fifth zone, the sixth zone and the machine head are respectively 150 ℃, 155 ℃, 165 ℃, 155 ℃, 150 ℃ and 165 ℃.
Further, the injection molding conditions in the third step are as follows: the temperature is 170-175 ℃, the pressure is 80-90 MPa, and the injection molding speed is 65-85 mm/s.
The other preparation method of the antibacterial cellulose/polypropylene composite material comprises the following steps:
weighing 10.00-74.00 parts of cellulose, 11.00-87.00 parts of polypropylene resin, 0.50-5.00 parts of bacteriostatic agent, 2.00-7.00 parts of compatilizer, 0.10-2.00 parts of coupling agent, 0.10-2.00 parts of antioxidant, 0.10-2.00 parts of dispersing agent and 0.50-3.00 parts of porous medium material by weight;
and secondly, adding the raw materials weighed in the step one into a feeding barrel of a double-screw extruder, setting a feeding speed and a screw rotating speed, carrying out air cooling, granulating, drying to obtain composite granules, and carrying out injection molding to obtain the antibacterial cellulose/polypropylene composite material.
Further, in the second step, the feeding rotating speed is 200-220 r/min, and the screw rotating speed is 250-270 r/min.
Further, the temperature of each zone of the twin-screw extruder in the step two is set as follows: the melt temperatures of the first zone, the second zone, the third zone, the fourth zone, the fifth zone, the sixth zone and the machine head are respectively 150 ℃, 155 ℃, 165 ℃, 155 ℃, 150 ℃ and 165 ℃.
Further, the injection molding conditions in the second step are as follows: the temperature is 170-175 ℃, the pressure is 80-90 MPa, and the injection molding speed is 65-85 mm/s.
The invention has the beneficial effects that:
the antibacterial cellulose/polypropylene composite material disclosed by the invention has a glossy surface and antibacterial performance, can replace some conventional wood-plastic composite materials, prolongs the service life of the material, inhibits the breeding of microorganisms, improves the safety performance, and more conforms to the modern healthy, safe and environment-friendly concept.
According to the cellulose/polypropylene composite material, the optimal usage amount of raw materials and the type of the bacteriostatic agent are screened out through the reasonable proportion of the matrix resin, the organic filler, the compatilizer and the bacteriostatic agent, so that the bacteriostatic performance of the composite material is improved, and the cellulose/polypropylene composite material is widely applied to automotive upholsteries, furniture, floors, articles for daily use and the like.
The azole bacteriostat is an aromatic heterocyclic compound containing biological activity, has the efficacies of broad-spectrum bacteriostasis, cancer and inflammation resistance, virus resistance and the like, and can not only block the synthesis of bacterial DNA, but also destroy the cell structure, electron and substance transmission system of bacteria and cause the damage of the living function of the bacteria and the death when triazole acts with the cells of the microorganisms (such as bacteria, viruses and the like). Therefore, the triazole has better functions of inhibiting the growth and the reproduction of bacteria and fungi, and is an excellent bacteriostatic material.
The abrasiveness, alkalinity, oxidizability of the metal oxide and the electrostatic attraction to microorganisms make the zinc oxide have strong bacteriostasis, and have the effects of inhibiting the growth of bacteria and microorganisms, destroying cell structures and inducing the leakage of substances in cells. Therefore, according to the advantages of the azole compounds and the advantages of the metal oxides, the triazole and the zinc oxide are combined to obtain the combined bacteriostatic agent, so that the combined bacteriostatic agent combines the advantages of the azole bacteriostatic agent and the inorganic metal bacteriostatic agent, and plays a role in strongly inhibiting bacteria and fungi. In addition, in subsequent performance tests, the mechanical property of the combined bacteriostatic agent is better than that of a single bacteriostatic agent. The molecular structure of the azole compound of the organic bacteriostatic agent contains nitrogen atoms and-C ═ N double bonds, which are easy to chelate with metal ions, the molecular chain is increased, a physical entangled skeleton structure is formed in the polymer, when the material is subjected to an external force, the entangled skeleton structure in the matrix can absorb and transfer impact energy, the polymer is reinforced, and the mechanical property is obviously improved.
The mechanical property of the antibacterial cellulose/polypropylene composite material is remarkably improved, wherein the tensile strength can reach 31.45MPa, the bending strength can reach 35.54MPa, the sterilization rate on escherichia coli can reach 97.88%, and the sterilization rate on staphylococcus aureus can reach 96.56%.
Detailed Description
The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.
The first embodiment is as follows: the antibacterial cellulose/polypropylene composite material comprises, by weight, 10.00-74.00 parts of cellulose, 11.00-87.00 parts of polypropylene resin, 0.50-5.00 parts of antibacterial agent, 2.00-7.00 parts of compatilizer, 0.10-2.00 parts of coupling agent, 0.10-2.00 parts of antioxidant, 0.10-2.00 parts of dispersing agent and 0.50-3.00 parts of porous medium material; the bacteriostatic agent comprises an inorganic bacteriostatic agent and an organic bacteriostatic agent; the inorganic bacteriostatic agent is one or a mixture of more of zinc oxide, nano silver, nano copper salt, silicon dioxide and anatase titanium dioxide, and the organic bacteriostatic agent is one or a mixture of more of 3-amino-1, 2, 4-triazole, 4-amino-1, 2, 4-triazole and 3, 5-diamino-1, 2, 4-triazole.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the cellulose is one or a mixture of more of microcrystalline cellulose, cellulose whisker and nano-cellulose. The rest is the same as the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the polypropylene resin is a random copolymer polypropylene resin. The other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: the compatilizer is one or a combination of maleic anhydride grafted polypropylene and glycidyl methacrylate grafted polypropylene. The others are the same as in one of the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the coupling agent is one or a composition of two of silane coupling agent, aluminate coupling agent and titanate coupling agent. The other is the same as one of the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: the antioxidant is one or a composition of two of phosphite antioxidant and hindered phenol antioxidant. The other is the same as one of the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: the dispersing agent is one or a combination of two of ethylene bis stearamide, stearic acid monoglyceride and tristearin. The other is the same as one of the first to sixth embodiments.
The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: the porous medium material is one or a mixture of several of nano silicon dioxide, montmorillonite, a 4A molecular sieve, a 5A molecular sieve, anatase titanium dioxide and diatomite. The other is the same as one of the first to seventh embodiments.
The specific implementation method nine: the preparation method of the antibacterial cellulose/polypropylene composite material comprises the following steps:
weighing 10.00-74.00 parts of cellulose, 11.00-87.00 parts of polypropylene resin, 0.50-5.00 parts of bacteriostatic agent, 2.00-7.00 parts of compatilizer, 0.10-2.00 parts of coupling agent, 0.10-2.00 parts of antioxidant, 0.10-2.00 parts of dispersing agent and 0.50-3.00 parts of porous medium material by weight; dividing the polypropylene resin into 2 parts, namely a polypropylene resin A and a polypropylene resin B, wherein the mass ratio of the polypropylene resin A to the polypropylene resin B is 3: 7;
the bacteriostatic agent comprises an inorganic bacteriostatic agent and an organic bacteriostatic agent; the inorganic bacteriostatic agent is one or a mixture of more of zinc oxide, nano silver, nano copper salt, silicon dioxide and anatase titanium dioxide, and the organic bacteriostatic agent is one or a mixture of more of 3-amino-1, 2, 4-triazole, 4-amino-1, 2, 4-triazole and 3, 5-diamino-1, 2, 4-triazole.
Preparation of antibacterial master batch
Adding a coupling agent into an ethanol solution, and stirring at room temperature for 5-10 min to obtain a hydrolyzed coupling agent; the mass concentration of the ethanol solution is 80-90%;
adding the bacteriostatic agent into the hydrolyzed coupling agent, stirring for 30-40 min at the stirring speed of 800-1200 r/min to obtain a mixed solution, and drying the mixed solution at 80-90 ℃ to obtain a bacteriostatic agent compound;
adding the bacteriostatic agent compound, the polypropylene resin A, the antioxidant and the dispersing agent into a feeding barrel of a double-screw extruder, setting a feeding speed and a screw rotating speed, air-cooling, granulating, and drying to obtain bacteriostatic master batch;
and thirdly, mechanically and uniformly mixing the antibacterial master batch, the cellulose, the polypropylene resin B, the compatilizer and the porous medium material, adding the mixture into a feeding barrel of a double-screw extruder, setting the feeding speed and the screw rotating speed, carrying out air cooling granulation, drying to obtain composite granules, and carrying out injection molding to obtain the antibacterial cellulose/polypropylene composite material.
The detailed implementation mode is ten: the present embodiment differs from the ninth embodiment in that: in the second step, the feeding rotating speed is 200-220 r/min, and the screw rotating speed is 250-270 r/min. The rest is the same as the embodiment nine.
The concrete implementation mode eleven: this embodiment is nine or ten different from the specific embodiment: in the second step, the temperature of each area of the double-screw extruder is set as follows: the melt temperatures of the first zone, the second zone, the third zone, the fourth zone, the fifth zone, the sixth zone and the machine head are respectively 150 ℃, 155 ℃, 165 ℃, 155 ℃, 150 ℃ and 165 ℃. The others are the same as the ninth or tenth embodiment.
The specific implementation mode twelve: this embodiment is different from one of the ninth to eleventh embodiments in that: in the third step, the feeding speed is 200-220 r/min, and the screw rotating speed is 250-270 r/min. The others are the same as in one of the ninth to eleventh embodiments.
The specific implementation mode is thirteen: this embodiment differs from one of the ninth to twelfth embodiments in that: the temperature of each area of the double-screw extruder in the third step is set as follows: the melt temperatures of the first zone, the second zone, the third zone, the fourth zone, the fifth zone, the sixth zone and the machine head are respectively 150 ℃, 155 ℃, 165 ℃, 155 ℃, 150 ℃ and 165 ℃. The rest is the same as the ninth to twelfth embodiments.
The specific implementation mode is fourteen: this embodiment differs from one of the ninth to thirteenth embodiments in that: the conditions of injection molding in the third step are as follows: the temperature is 170-175 ℃, the pressure is 80-90 MPa, and the injection molding speed is 65-85 mm/s. The others are the same as in one of the ninth to thirteenth embodiments.
The concrete implementation mode is fifteen: the preparation method of the antibacterial cellulose/polypropylene composite material comprises the following steps:
weighing 10.00-74.00 parts of cellulose, 11.00-87.00 parts of polypropylene resin, 0.50-5.00 parts of bacteriostatic agent, 2.00-7.00 parts of compatilizer, 0.10-2.00 parts of coupling agent, 0.10-2.00 parts of antioxidant, 0.10-2.00 parts of dispersing agent and 0.50-3.00 parts of porous medium material by weight;
and secondly, adding the raw materials weighed in the step one into a feeding barrel of a double-screw extruder, setting a feeding speed and a screw rotating speed, carrying out air cooling, granulating, drying to obtain composite granules, and carrying out injection molding to obtain the antibacterial cellulose/polypropylene composite material.
The specific implementation mode is sixteen: this embodiment is different from the specific embodiment by the fifteenth: in the second step, the feeding rotating speed is 200-220 r/min, and the screw rotating speed is 250-270 r/min. The rest is the same as the embodiment fifteen.
Seventeenth embodiment: this embodiment is different from the specific embodiment by the fifteenth: in the second step, the temperature of each area of the double-screw extruder is set as follows: the melt temperatures of the first zone, the second zone, the third zone, the fourth zone, the fifth zone, the sixth zone and the machine head are respectively 150 ℃, 155 ℃, 165 ℃, 155 ℃, 150 ℃ and 165 ℃. The rest is the same as the embodiment fifteen.
The specific implementation mode is eighteen: this embodiment is different from the specific embodiment by the fifteenth: the conditions of injection molding in the second step are as follows: the temperature is 170-175 ℃, the pressure is 80-90 MPa, and the injection molding speed is 65-85 mm/s. The rest is the same as the embodiment fifteen.
The following examples are given to illustrate the present invention, and the following examples are carried out on the premise of the technical solution of the present invention, and give detailed embodiments and specific procedures, but the scope of the present invention is not limited to the following examples.
Example 1: the bacteriostatic agent of the embodiment is an inorganic bacteriostatic agent
Weighing 26.7 parts of microcrystalline cellulose, 62.3 parts of polypropylene resin, 5.00 parts of bacteriostatic agent, 5.00 parts of compatilizer, 0.2 part of coupling agent, 0.2 part of antioxidant, 0.2 part of dispersant and 0.4 part of porous medium material according to parts by weight; dividing the polypropylene resin into 2 parts, namely a polypropylene resin A and a polypropylene resin B, wherein the mass ratio of the polypropylene resin A to the polypropylene resin B is 3: 7; wherein the polypropylene resin is random copolymerization polypropylene resin, the bacteriostatic agent is zinc oxide, the coupling agent is a silane coupling agent, the antioxidant is phosphite antioxidant, the dispersant is stearic acid monoglyceride, and the porous medium material is montmorillonite.
Preparation of antibacterial master batch
Adding the coupling agent into the ethanol solution, and stirring at room temperature for 5min to obtain a hydrolyzed coupling agent; the mass concentration of the ethanol solution is 80%;
adding the bacteriostatic agent into the hydrolyzed coupling agent, stirring for 30min at the stirring speed of 1200r/min to obtain a mixed solution, and drying the mixed solution at 90 ℃ to obtain a bacteriostatic agent compound;
adding the bacteriostatic agent compound, the polypropylene resin A, the antioxidant and the dispersing agent into a feeding barrel of a double-screw extruder, setting a feeding speed and a screw rotating speed, air-cooling, granulating, and drying to obtain bacteriostatic master batch;
and thirdly, mechanically and uniformly mixing the antibacterial master batch, the cellulose, the polypropylene resin B, the compatilizer and the porous medium material, adding the mixture into a feeding barrel of a double-screw extruder, setting the feeding speed and the screw rotating speed, carrying out air cooling granulation, drying to obtain composite granules, and carrying out injection molding to obtain the antibacterial cellulose/polypropylene composite material.
In the second step, the feeding rotating speed is 200r/min, and the screw rotating speed is 250 r/min.
In the second step, the temperature of each area of the double-screw extruder is set as follows: the melt temperatures of the first zone, the second zone, the third zone, the fourth zone, the fifth zone, the sixth zone and the machine head are respectively 150 ℃, 155 ℃, 165 ℃, 155 ℃, 150 ℃ and 165 ℃.
In the third step, the feeding speed is 200r/min, and the screw rotating speed is 250 r/min.
The temperature of each area of the double-screw extruder in the third step is set as follows: the melt temperatures of the first zone, the second zone, the third zone, the fourth zone, the fifth zone, the sixth zone and the machine head are respectively 150 ℃, 155 ℃, 165 ℃, 155 ℃, 150 ℃ and 165 ℃.
The conditions of injection molding in the third step are as follows: the temperature is 170 ℃, the pressure is 80MPa, and the injection molding speed is 65 mm/s.
Example 2: the bacteriostatic agent of the embodiment is an organic bacteriostatic agent
Weighing 26.7 parts of microcrystalline cellulose, 62.3 parts of polypropylene resin, 5.00 parts of bacteriostatic agent, 5.00 parts of compatilizer, 0.2 part of coupling agent, 0.2 part of antioxidant, 0.2 part of dispersant and 0.4 part of porous medium material according to parts by weight; dividing the polypropylene resin into 2 parts, namely a polypropylene resin A and a polypropylene resin B, wherein the mass ratio of the polypropylene resin A to the polypropylene resin B is 3: 7; wherein the polypropylene resin is random copolymerization polypropylene resin, the bacteriostatic agent is 3-amino-1, 2, 4-triazole, the coupling agent is a silane coupling agent, the antioxidant is a phosphite ester antioxidant, the dispersant is stearic acid monoglyceride, and the porous medium material is montmorillonite.
Preparation of antibacterial master batch
Adding the coupling agent into the ethanol solution, and stirring at room temperature for 5min to obtain a hydrolyzed coupling agent; the mass concentration of the ethanol solution is 80%;
adding the bacteriostatic agent into the hydrolyzed coupling agent, stirring for 30min at the stirring speed of 1200r/min to obtain a mixed solution, and drying the mixed solution at 90 ℃ to obtain a bacteriostatic agent compound;
adding the bacteriostatic agent compound, the polypropylene resin A, the antioxidant and the dispersing agent into a feeding barrel of a double-screw extruder, setting a feeding speed and a screw rotating speed, air-cooling, granulating, and drying to obtain bacteriostatic master batch;
and thirdly, mechanically and uniformly mixing the antibacterial master batch, the cellulose, the polypropylene resin B, the compatilizer and the porous medium material, adding the mixture into a feeding barrel of a double-screw extruder, setting the feeding speed and the screw rotating speed, carrying out air cooling granulation, drying to obtain composite granules, and carrying out injection molding to obtain the antibacterial cellulose/polypropylene composite material.
In the second step, the feeding rotating speed is 200r/min, and the screw rotating speed is 250 r/min.
In the second step, the temperature of each area of the double-screw extruder is set as follows: the melt temperatures of the first zone, the second zone, the third zone, the fourth zone, the fifth zone, the sixth zone and the machine head are respectively 150 ℃, 155 ℃, 165 ℃, 155 ℃, 150 ℃ and 165 ℃.
In the third step, the feeding speed is 200r/min, and the screw rotating speed is 250 r/min.
The temperature of each area of the double-screw extruder in the third step is set as follows: the melt temperatures of the first zone, the second zone, the third zone, the fourth zone, the fifth zone, the sixth zone and the machine head are respectively 150 ℃, 155 ℃, 165 ℃, 155 ℃, 150 ℃ and 165 ℃.
The conditions of injection molding in the third step are as follows: the temperature is 170 ℃, the pressure is 80MPa, and the injection molding speed is 65 mm/s.
Example 3: the bacteriostatic agent of the embodiment is an inorganic and organic composite bacteriostatic agent
Weighing 26.7 parts of microcrystalline cellulose, 62.3 parts of polypropylene resin, 5.00 parts of bacteriostatic agent, 5.00 parts of compatilizer, 0.2 part of coupling agent, 0.2 part of antioxidant, 0.2 part of dispersant and 0.4 part of porous medium material according to parts by weight; dividing the polypropylene resin into 2 parts, namely a polypropylene resin A and a polypropylene resin B, wherein the mass ratio of the polypropylene resin A to the polypropylene resin B is 3: 7; the polypropylene resin is a random copolymerization polypropylene resin, the bacteriostatic agent is 3-amino-1, 2, 4-triazole and zinc oxide, the mass ratio of the 3-amino-1, 2, 4-triazole to the zinc oxide is 3:1, the coupling agent is a silane coupling agent, the antioxidant is a phosphite ester antioxidant, the dispersing agent is stearic acid monoglyceride, and the porous medium material is montmorillonite.
Preparation of antibacterial master batch
Adding the coupling agent into the ethanol solution, and stirring at room temperature for 5min to obtain a hydrolyzed coupling agent; the mass concentration of the ethanol solution is 80%;
adding the bacteriostatic agent into the hydrolyzed coupling agent, stirring for 30min at the stirring speed of 1200r/min to obtain a mixed solution, and drying the mixed solution at 90 ℃ to obtain a bacteriostatic agent compound;
adding the bacteriostatic agent compound, the polypropylene resin A, the antioxidant and the dispersing agent into a feeding barrel of a double-screw extruder, setting a feeding speed and a screw rotating speed, air-cooling, granulating, and drying to obtain bacteriostatic master batch;
and thirdly, mechanically and uniformly mixing the antibacterial master batch, the cellulose, the polypropylene resin B, the compatilizer and the porous medium material, adding the mixture into a feeding barrel of a double-screw extruder, setting the feeding speed and the screw rotating speed, carrying out air cooling granulation, drying to obtain composite granules, and carrying out injection molding to obtain the antibacterial cellulose/polypropylene composite material.
In the second step, the feeding rotating speed is 200r/min, and the screw rotating speed is 250 r/min.
In the second step, the temperature of each area of the double-screw extruder is set as follows: the melt temperatures of the first zone, the second zone, the third zone, the fourth zone, the fifth zone, the sixth zone and the machine head are respectively 150 ℃, 155 ℃, 165 ℃, 155 ℃, 150 ℃ and 165 ℃.
In the third step, the feeding speed is 200r/min, and the screw rotating speed is 250 r/min.
The temperature of each area of the double-screw extruder in the third step is set as follows: the melt temperatures of the first zone, the second zone, the third zone, the fourth zone, the fifth zone, the sixth zone and the machine head are respectively 150 ℃, 155 ℃, 165 ℃, 155 ℃, 150 ℃ and 165 ℃.
The conditions of injection molding in the third step are as follows: the temperature is 170 ℃, the pressure is 80MPa, and the injection molding speed is 65 mm/s.
The antibacterial cellulose/polypropylene composite material prepared in the above embodiment is detected as follows:
mechanical property test:
TABLE 1 mechanical property test data of antibacterial cellulose/polypropylene composite material
| Sample set | Tensile strength MPa | Bending strength MPa |
| Examples1 | 24.56 | 29.61 |
| Example 2 | 25.71 | 29.92 |
| Example 3 | 31.45 | 35.54 |
Compared with the examples 1 to 3, under the condition that the addition amount of all the raw materials is consistent in percentage by mass, the bacteriostatic cellulose/polypropylene composite material in the example 3 has the best mechanical property, namely the mechanical property of the bacteriostatic cellulose/polypropylene composite material added with the 3-amino-1, 2, 4-triazole and zinc oxide combined bacteriostatic agent is better than that of the bacteriostatic agent added with a single bacteriostatic agent.
(II) testing bacteriostatic performance:
the bacteriostatic properties of the bacteriostatic cellulose/polypropylene composite materials prepared in examples 1-3 were tested by conventional microbiological bactericidal activity tests, i.e., escherichia coli, numbered 8099 and staphylococcus aureus, numbered ATCC6538, were purchased.
TABLE 2 antibacterial property test data of antibacterial cellulose/polypropylene composite material
| Sample set | The sterilization rate of Escherichia coli% | Staphylococcus aureus sterilizing rate% |
| Example 1 | 83.28 | 84.36 |
| Example 2 | 83.25 | 82.30 |
| Example 3 | 97.88 | 96.56 |
Compared with the examples 1 to 3, under the condition that the addition amounts of all the raw materials are consistent in mass percentage, the bacteriostatic property of the bacteriostatic cellulose/polypropylene composite material in the example 3 is the best, namely the bacteriostatic property of the combined bacteriostatic agent of 3-amino-1, 2, 4-triazole and zinc oxide is better than that of a single bacteriostatic agent.
Compared with the examples 1 to 3, under the condition that the addition amounts of all the raw materials are consistent in mass percentage, the bacteriostatic cellulose/polypropylene composite material of the example 3 has the best bacteriostatic performance, namely, the bacteriostatic agent prepared by combining 3-amino-1, 2, 4-triazole and zinc oxide has better bacteriostatic performance than a single bacteriostatic agent. Because the azole bacteriostatic agent is a bioactive aromatic heterocyclic compound and has the effects of broad-spectrum bacteriostasis, inflammation resistance, virus resistance and the like, when triazole acts with microbial cells, the azole bacteriostatic agent not only can block the synthesis of bacterial DNA, but also can destroy the structure of the bacterial cells and a substance transmission system, and cause the destruction of the survival function of the bacteria to cause death. Zinc oxide belongs to a photocatalytic inorganic bacteriostatic agent, and can generate highly active hole electron pairs after illumination, further generate strong-oxidative OH free radicals and kill bacteria in contact with the zinc oxide in a short time. Therefore, the 3-amino-1, 2, 4-triazole/zinc oxide combined bacteriostatic agent is added into the material to play a stronger role in inhibiting bacteria and fungi, and meanwhile, the mechanical property of the material is better than that of the material added with a single bacteriostatic agent.
Claims (10)
1. The antibacterial cellulose/polypropylene composite material is characterized by comprising, by weight, 10.00-74.00 parts of cellulose, 11.00-87.00 parts of polypropylene resin, 0.50-5.00 parts of an antibacterial agent, 2.00-7.00 parts of a compatilizer, 0.10-2.00 parts of a coupling agent, 0.10-2.00 parts of an antioxidant, 0.10-2.00 parts of a dispersing agent and 0.50-3.00 parts of a porous medium material; the bacteriostatic agent comprises an inorganic bacteriostatic agent and an organic bacteriostatic agent; the inorganic bacteriostatic agent is zinc oxide, and the organic bacteriostatic agent is one or a mixture of more of 3-amino-1, 2, 4-triazole, 4-amino-1, 2, 4-triazole and 3, 5-diamino-1, 2, 4-triazole.
2. The bacteriostatic cellulose/polypropylene composite material according to claim 1, wherein the cellulose is one or more of microcrystalline cellulose, cellulose whisker and nanocellulose.
3. A bacteriostatic cellulose/polypropylene composite according to claim 1 or 2, wherein the polypropylene resin is a random copolymer polypropylene resin.
4. The bacteriostatic cellulose/polypropylene composite material according to claim 3, wherein the compatilizer is one or a combination of maleic anhydride grafted polypropylene and glycidyl methacrylate grafted polypropylene.
5. The bacteriostatic cellulose/polypropylene composite material according to claim 1, 2 or 4, wherein the coupling agent is one or a combination of silane coupling agent, aluminate coupling agent and titanate coupling agent.
6. The bacteriostatic cellulose/polypropylene composite material according to claim 5, wherein the antioxidant is one or a combination of two of phosphite antioxidants and hindered phenol antioxidants.
7. The bacteriostatic cellulose/polypropylene composite material according to claim 6, wherein the dispersant is one or a combination of ethylene bis stearamide, glyceryl monostearate and glyceryl tristearate.
8. The antibacterial cellulose/polypropylene composite material according to claim 7, wherein the porous medium material is one or more of nano-silica, montmorillonite, 4A molecular sieve, 5A molecular sieve, anatase titanium dioxide, and diatomite.
9. The method of claim 1, wherein the method comprises the steps of:
weighing 10.00-74.00 parts of cellulose, 11.00-87.00 parts of polypropylene resin, 0.50-5.00 parts of bacteriostatic agent, 2.00-7.00 parts of compatilizer, 0.10-2.00 parts of coupling agent, 0.10-2.00 parts of antioxidant, 0.10-2.00 parts of dispersing agent and 0.50-3.00 parts of porous medium material by weight; dividing the polypropylene resin into 2 parts, namely a polypropylene resin A and a polypropylene resin B, wherein the mass ratio of the polypropylene resin A to the polypropylene resin B is 3: 7;
the bacteriostatic agent comprises an inorganic bacteriostatic agent and an organic bacteriostatic agent; the inorganic bacteriostatic agent is zinc oxide, and the organic bacteriostatic agent is one or a mixture of more of 3-amino-1, 2, 4-triazole, 4-amino-1, 2, 4-triazole and 3, 5-diamino-1, 2, 4-triazole;
preparation of antibacterial master batch
Adding a coupling agent into an ethanol solution, and stirring at room temperature for 5-10 min to obtain a hydrolyzed coupling agent; the mass concentration of the ethanol solution is 80-90%;
adding the bacteriostatic agent into the hydrolyzed coupling agent, stirring for 30-40 min at the stirring speed of 800-1200 r/min to obtain a mixed solution, and drying the mixed solution at 80-90 ℃ to obtain a bacteriostatic agent compound;
adding the bacteriostatic agent compound, the polypropylene resin A, the antioxidant and the dispersing agent into a feeding barrel of a double-screw extruder, setting a feeding speed and a screw rotating speed, air-cooling, granulating, and drying to obtain bacteriostatic master batch;
and thirdly, mechanically and uniformly mixing the antibacterial master batch, the cellulose, the polypropylene resin B, the compatilizer and the porous medium material, adding the mixture into a feeding barrel of a double-screw extruder, setting the feeding speed and the screw rotating speed, carrying out air cooling granulation, drying to obtain composite granules, and carrying out injection molding to obtain the antibacterial cellulose/polypropylene composite material.
10. The method of claim 1, wherein the method comprises the steps of:
weighing 10.00-74.00 parts of cellulose, 11.00-87.00 parts of polypropylene resin, 0.50-5.00 parts of bacteriostatic agent, 2.00-7.00 parts of compatilizer, 0.10-2.00 parts of coupling agent, 0.10-2.00 parts of antioxidant, 0.10-2.00 parts of dispersing agent and 0.50-3.00 parts of porous medium material by weight;
and secondly, adding the raw materials weighed in the step one into a feeding barrel of a double-screw extruder, setting a feeding speed and a screw rotating speed, carrying out air cooling, granulating, drying to obtain composite granules, and carrying out injection molding to obtain the antibacterial cellulose/polypropylene composite material.
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| CN112796038B (en) * | 2020-12-30 | 2023-04-11 | 中纳联达(北京)科技有限公司 | Antibacterial melt-blown fabric and manufacturing method thereof |
| CN113912865A (en) * | 2021-11-08 | 2022-01-11 | 潍坊科技学院 | Preparation method of fiber composite material |
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