CN111235687A - Antibacterial multilayer composite hollow fiber membrane material and preparation method thereof - Google Patents
Antibacterial multilayer composite hollow fiber membrane material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an antibacterial multilayer composite hollow fiber membrane material and a preparation method thereof. The novel modified antibacterial agent is prepared by adopting graphene/chitosan intercalation zirconium phosphate, and then the antibacterial agent is melted and blended with PP resin, PVB resin, PVDF resin, compatilizer, lubricant, antioxidant and other processing aids to obtain the antibacterial multilayer composite hollow fiber membrane material. The prepared antibacterial multilayer composite hollow fiber membrane material overcomes the problems of failure of the antibacterial agent and the like caused by high temperature in the processing process of the traditional antibacterial material. The purposes of long-acting antibiosis and bacteriostasis of the composite material are realized by delaying the release speed of the antibacterial agent.
Description
Technical Field
The invention relates to a high polymer material, in particular to an antibacterial multilayer composite hollow fiber membrane material and a preparation method thereof.
Background
The composite hollow fiber membrane has the advantages of impact resistance, wear resistance, corrosion resistance, large unit membrane area, high separation efficiency and the like, so that the composite hollow fiber membrane is widely applied to the fields of water treatment, membrane distillation, gas separation, biological medicine and the like. However, the flux of the membrane is often emphasized in the process of the traditional composite hollow fiber membrane, and the antibacterial property of the membrane is neglected, so that bacteria are bred in the use process of the membrane, and secondary pollution is caused.
Chitosan is used as a broad-spectrum bacteriostatic agent, forms a cationic polymer with positive charge after being protonated by self amino, adsorbs cell walls with negative charge, and ensures that bacterial cells aggregate, thereby effectively inhibiting the growth and proliferation of bacteria and fungi, and has the advantages of broad spectrum, high efficiency, good biocompatibility, small toxic action on the natural environment and the like. However, the mechanical property and heat resistance of the pure chitosan film have great defects, which greatly limits the application range of the material, and in order to better apply the material, the material needs to be effectively improved.
Graphene (Graphene) is formed from carbon atoms in sp2The two-dimensional crystal composed of hybrid orbitals is a planar thin film composed of hexagonal honeycomb lattices, and the literature shows that: the sharp edge of the graphene can effectively damage cell membranes of bacteria, cytoplasm outflows, and cells cannot exist completely and die, so that the graphene has remarkable antibacterial performance. However, the graphene structure surface is easy to agglomerate due to strong van der waals force, and the defects severely limit the application of the graphene structure surface in various fields.
Therefore, in view of the above considerations, the present invention provides an antibacterial multilayer composite hollow fiber membrane material and a method for preparing the same.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide an antibacterial multilayer composite hollow fiber membrane material and a preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
an antibacterial multilayer composite hollow fiber membrane material is characterized in that: the composition is characterized by comprising the following raw materials in parts by weight:
PP resin: 30 to 50 portions of
PVB resin: 5 to 10 parts of
PVDF resin: 5 to 10 parts of
A compatilizer: 3 to 8 portions of
Antibacterial agents: 1 to 5 portions of
Lubricant: 0.5 to 2 portions of
Antioxidant: 0.1 to 0.5 portion.
As a further improvement of the present invention,
the antibacterial agent is modified graphene/chitosan intercalation zirconium phosphate.
The modified graphene/chitosan intercalation zirconium phosphate antibacterial agent is prepared by the following method:
(1) preparation of modified graphene
Preparing graphene oxide by adopting an improved Hummers method, weighing 5-10 g of graphene oxide, adding the graphene oxide into a three-necked flask filled with 100mL of acetone, adding 0.1-1 g of coupling agent while stirring, reacting for 1-3 h at the temperature of 50-70 ℃, performing suction filtration, and drying to obtain the modified graphene.
(2) Preparation of modified graphene/chitosan
Accurately weighing 1-3 g of chitosan, adding 300mL of deionized water, stirring, slowly dropping 10-20 g of acetic acid solution with the concentration of 5-10%, and fully stirring for 1-2 h to obtain the chitosan solution. And (2) weighing 1-3 g of the modified graphene prepared in the step (1), slowly adding the modified graphene into the chitosan solution, fully stirring to obtain a uniformly mixed modified graphene/chitosan solution, and putting the solution into a vacuum oven for vacuum drying to obtain the modified graphene/chitosan material.
(3) Preparation of graphene/chitosan intercalation zirconium phosphate antibacterial agent
Weighing 5-10 g of zirconium phosphate, adding 500mL of deionized water, stirring and dispersing uniformly at normal temperature, slowly adding 10-20 g of small molecular amine pre-intercalation agent while stirring, fully reacting for 2-4 h, then performing ultrasonic treatment for 30-60 min to obtain pre-intercalated zirconium phosphate suspension, weighing 1-3 g of the modified graphene/chitosan material prepared in the step (2), adding into the pre-intercalated zirconium phosphate suspension, heating to 50-100 ℃, rapidly and mechanically stirring for 5-10 h to obtain graphene/chitosan intercalated zirconium phosphate suspension, and filtering, washing and drying to obtain the graphene/chitosan intercalated zirconium phosphate antibacterial agent.
As a further improvement of the present invention,
the improved Hummers method in the step (1) comprises the following specific steps: 5-10 g of graphite powder is weighed and added into a 500mL flask, and the flask is placed in a water bath at 0-5 ℃. Slowly adding 100-200 mL of concentrated sulfuric acid, stirring for 2-5 h, slowly adding 10-30 g of potassium permanganate, raising the reaction temperature to 20-60 ℃, stirring for 1-3 h, slowly adding 50-200 mL of deionized water, filtering, ultrasonically washing for three times by using 100-200 mL of 5-10% dilute hydrochloric acid and deionized water, and drying in vacuum at 40-80 ℃ for 24-48 h to obtain graphene oxide.
The coupling agent in the step (1) is at least one of silane coupling agent, aluminate coupling agent and titanate coupling agent;
the micromolecule amine pre-intercalation agent in the step (3) is at least one of ethylenediamine, hexamethylenediamine, aniline and diethylenetriamine;
as a further improvement of the present invention,
the PP resin is isotactic polypropylene, the melt flow rate is 6-15 g/min, and the density is 0.8-0.95 g/mL; the compatilizer is at least one of PP-g-MAH and PP-g-AA;
the lubricant is at least one of MBS and PP wax; the antioxidant is composed of 1010 and 168 according to a mass ratio of 1-5: 1;
as another object of the present invention, there is provided a method for preparing an antibacterial multilayer composite hollow fiber membrane material, comprising:
the method comprises the following steps: weighing PP resin, PVB resin, PVDF resin, a compatilizer, an antibacterial agent, a lubricant and an antioxidant according to the proportion, adding the mixture into a high-speed mixer, uniformly mixing, and discharging to obtain an antibacterial multilayer composite hollow fiber membrane material premix;
step two: adding the antibacterial multilayer composite hollow fiber membrane material premix prepared in the step one into a double-screw extruder, and performing extrusion granulation to prepare the special material for the antibacterial multilayer composite hollow fiber membrane material;
step three: and (3) adding the special material for the antibacterial multilayer composite hollow fiber membrane material prepared in the step two into an extruder to be melted at a certain temperature, extruding and molding the melt into a hollow fiber shape through a spinning nozzle, condensing the hollow fiber shape through a cooling water area with a certain temperature gradient, and winding the hollow fiber shape through a traction device rotating at a high speed to prepare the antibacterial multilayer composite hollow fiber membrane material.
As a further improvement of the present invention,
the working parameters of the hollow fiber membrane material in the third step are as follows:
the spinning temperature is as follows: 175-190 ℃ in the first area, 185-200 ℃ in the second area and 205-215 ℃ in the third area,
in the fourth zone, the temperature is 210-220 ℃, the pipeline is 190-205 ℃, the box body is 200-220 ℃, the screw rotation speed is as follows: 10-20 r/min, rotating speed of a metering pump: 15-30 r/min, winding speed: the extrusion rate of the melt at 400-600 r/min is as follows: 0.1-0.5 cm/s, and the temperature of the condensed water area is as follows: 10 to 30 ℃.
The preparation method has the beneficial effects that the novel modified antibacterial agent is prepared by adopting the graphene/chitosan intercalated zirconium phosphate, and then the antibacterial agent is mixed with PP resin, PVB resin, PVDF resin,
And other processing aids such as a compatilizer, a lubricant, an antioxidant and the like are melted and blended to obtain the antibacterial multilayer composite hollow fiber membrane material. Compared with the traditional multilayer composite hollow fiber membrane material, the method has the following obvious advantages:
(1) the zirconium phosphate intercalation of the antibacterial agent can effectively enhance the thermal stability of the antibacterial agent and overcome the problems of failure of the antibacterial agent and the like caused by high temperature in the material processing process.
(2) The intercalation technology is utilized to intercalate the antibacterial agent into the intercalated zirconium phosphate, so that the migration speed of the antibacterial agent can be effectively reduced, and the thermal stability of the antibacterial agent in the multilayer composite hollow fiber membrane material is improved. The release speed of the antibacterial agent is delayed, and the purposes of long-acting antibiosis and bacteriostasis of the composite material are achieved.
(3) The antibacterial agent is prepared by the graphene/chitosan intercalation zirconium phosphate, the dispersibility of the antibacterial agent in the matrix resin can be effectively improved, and the problems that the dispersibility of the single-component antibacterial agent of graphene or chitosan in the matrix resin is poor, and the material performance is influenced due to the easy occurrence of agglomeration are solved.
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Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a schematic flow diagram of the preparation of an antibacterial multilayer composite hollow fiber membrane material;
fig. 2 is an SEM image of the antibacterial multilayer composite hollow fiber membrane material prepared in example 4.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
An antibacterial multilayer composite hollow fiber membrane material is composed of the following raw materials in parts by weight:
PP resin: 30 portions of
PVB resin: 5 portions of
PVDF resin: 5 portions of
A compatilizer: 3 portions of
Antibacterial agents: 1 part of
Lubricant: 0.5 portion
Antioxidant: 0.1 part.
The antibacterial agent is modified graphene/chitosan intercalation zirconium phosphate.
The modified graphene/chitosan intercalation zirconium phosphate antibacterial agent is prepared by the following method:
(1) preparation of modified graphene
Preparing graphene oxide by adopting an improved Hummers method, weighing 5g of graphene oxide, adding the graphene oxide into a three-neck flask filled with 100mL of acetone, adding 0.1g of silane coupling agent while stirring, reacting for 1h at the temperature of 50 ℃, performing suction filtration, and drying to obtain the modified graphene.
(2) Preparation of modified graphene/chitosan
Accurately weighing 1g of chitosan, adding 300mL of deionized water, stirring, slowly dripping 10g of 5% acetic acid solution, and fully stirring for 1h to obtain the chitosan solution. Weighing 1g of the modified graphene prepared in the step (1), slowly adding the modified graphene into the chitosan solution, fully stirring to obtain a uniformly mixed modified graphene/chitosan solution, and putting the solution into a vacuum oven for vacuum drying to obtain the modified graphene/chitosan material.
(3) Preparation of graphene/chitosan intercalation zirconium phosphate antibacterial agent
Weighing 5g of zirconium phosphate, adding 500mL of deionized water, stirring and dispersing uniformly at normal temperature, slowly adding 10g of ethylenediamine and hexamethylenediamine pre-intercalation agent while stirring, fully reacting for 2h, then performing ultrasonic treatment for 30min to obtain a pre-intercalated zirconium phosphate suspension, weighing 1g of the modified graphene/chitosan material prepared in the step (2), adding the modified graphene/chitosan material into the pre-intercalated zirconium phosphate suspension, heating to 50 ℃, performing rapid mechanical stirring for 5h to obtain a graphene/chitosan intercalated zirconium phosphate suspension, and filtering, washing and drying to obtain the graphene/chitosan intercalated zirconium phosphate antibacterial agent.
The improved Hummers method in the step (1) comprises the following specific steps: 5g of graphite powder was weighed into a 500mL flask, and the flask was placed in a water bath at 0 ℃. Slowly adding 100mL of concentrated sulfuric acid, stirring for 2h, slowly adding 10g of potassium permanganate, raising the reaction temperature to 20 ℃, stirring for 1h, slowly adding 50mL of deionized water, filtering, finally ultrasonically washing for three times by using 100mL of 5% dilute hydrochloric acid and deionized water, and drying for 24h under vacuum at the temperature of 40 ℃ to obtain the graphene oxide.
The PP resin is isotactic polypropylene, the melt flow rate is 15 g/min, and the density is 0.95 g/mL;
the compatilizer is PP-g-MAH;
the lubricant is MBS;
the antioxidant is composed of 1010 and 168 according to the mass ratio of 1: 1;
the preparation method of the antibacterial multilayer composite hollow fiber membrane material comprises the following steps:
the method comprises the following steps: weighing PP resin, PVB resin, PVDF resin, a compatilizer, an antibacterial agent, a lubricant and an antioxidant according to the proportion, adding the mixture into a high-speed mixer, uniformly mixing, and discharging to obtain an antibacterial multilayer composite hollow fiber membrane material premix;
step two: adding the antibacterial multilayer composite hollow fiber membrane material premix prepared in the step one into a double-screw extruder, and performing extrusion granulation to prepare the special material for the antibacterial multilayer composite hollow fiber membrane material;
step three: and (3) adding the special material for the antibacterial multilayer composite hollow fiber membrane material prepared in the step two into an extruder to be melted at a certain temperature, extruding and molding the melt into a hollow fiber shape through a spinning nozzle, condensing the hollow fiber shape through a cooling water area with a certain temperature gradient, and winding the hollow fiber shape through a traction device rotating at a high speed to prepare the antibacterial multilayer composite hollow fiber membrane material. The working parameters are as follows: the spinning temperature is as follows: 175 ℃ in the first zone, 185 ℃ in the second zone, 205 ℃ in the third zone, 210 ℃ in the fourth zone, 190 ℃ in the pipe, 200 ℃ in the box, screw speed: 10r/min, rotating speed of a metering pump: 15r/min, winding speed: the extrusion rate of the 400r/min melt was: 0.1cm/s, the temperature of a condensation water area is as follows: 10 ℃.
Through inspection, the antibacterial multilayer composite hollow fiber membrane material prepared by the embodiment has the bacteriostasis rate of 97.4 percent on escherichia coli for 24 hours and staphylococcus aureus after being washed by water for 50 times, 94.7 percent on the escherichia coli for 24 hours and the staphylococcus aureus after being washed by water for 70 mu W/cm2After 12 hours of ultraviolet irradiation with intensity, the bacteriostasis rate to escherichia coli for 24 hours and staphylococcus aureus is 97.1%, and after 200 times of water washing, the bacteriostasis rate to escherichia coli for 24 hours and staphylococcus aureus is 94.3%.
Example 2
An antibacterial multilayer composite hollow fiber membrane material is composed of the following raw materials in parts by weight:
PP resin: 35 portions of
PVB resin: 6.5 parts of
PVDF resin: 7 portions of
A compatilizer: 4.5 parts of
Antibacterial agents: 2 portions of
Lubricant: 0.9 portion
Antioxidant: 0.2 part.
The antibacterial agent is modified graphene/chitosan intercalation zirconium phosphate.
The modified graphene/chitosan intercalation zirconium phosphate antibacterial agent is prepared by the following method:
(1) preparation of modified graphene
Preparing graphene oxide by adopting an improved Hummers method, weighing 7g of graphene oxide, adding the graphene oxide into a three-neck flask filled with 100mL of acetone, adding 0.35g of aluminate coupling agent while stirring, reacting for 1.5h at the temperature of 55 ℃, performing suction filtration, and drying to obtain the modified graphene.
(2) Preparation of modified graphene/chitosan
Accurately weighing 1.5g of chitosan, adding 300mL of deionized water, stirring, slowly dripping 15g of acetic acid solution with the concentration of 7.5%, and fully stirring for 1.5h to obtain the chitosan solution. Weighing 2g of the modified graphene prepared in the step (1), slowly adding the modified graphene into the chitosan solution, fully stirring to obtain a uniformly mixed modified graphene/chitosan solution, and putting the solution into a vacuum oven for vacuum drying to obtain the modified graphene/chitosan material.
(3) Preparation of graphene/chitosan intercalation zirconium phosphate antibacterial agent
Weighing 7g of zirconium phosphate, adding 500mL of deionized water, stirring and dispersing uniformly at normal temperature, slowly adding 14g of hexamethylenediamine and aniline pre-intercalation agent while stirring, fully reacting for 2.5h, then performing ultrasonic treatment for 40min to obtain a pre-intercalated zirconium phosphate suspension, weighing 1.5g of the modified graphene/chitosan material prepared in the step (2), adding the modified graphene/chitosan material into the pre-intercalated zirconium phosphate suspension, heating to 70 ℃, performing rapid mechanical stirring for 6h to obtain a graphene/chitosan intercalated zirconium phosphate suspension, and filtering, washing and drying to obtain the graphene/chitosan intercalated zirconium phosphate antibacterial agent.
The improved Hummers method in the step (1) comprises the following specific steps: 6g of graphite powder was weighed into a 500mL flask, and the flask was placed in a water bath at 1 ℃. And slowly adding 130 mL of concentrated sulfuric acid, stirring for 2.5h, slowly adding 15g of potassium permanganate, raising the reaction temperature to 30 ℃, stirring for 1.5h, slowly adding 150mL of deionized water, filtering, ultrasonically washing for three times by using 120 mL of dilute hydrochloric acid with the concentration of 6.5% and deionized water, and drying for 36h in vacuum at the temperature of 55 ℃ to obtain the graphene oxide.
The PP resin is isotactic polypropylene, the melt flow rate is 8g/min, and the density is 0.85 g/mL; the compatilizer is PP-g-AA;
the lubricant is at least one of PP wax;
the antioxidant is composed of 1010 and 168 according to the mass ratio of 2: 1;
a preparation method of an antibacterial multilayer composite hollow fiber membrane material comprises the following steps:
the method comprises the following steps: weighing PP resin, PVB resin, PVDF resin, a compatilizer, an antibacterial agent, a lubricant and an antioxidant according to the proportion, adding the mixture into a high-speed mixer, uniformly mixing, and discharging to obtain an antibacterial multilayer composite hollow fiber membrane material premix;
step two: adding the antibacterial multilayer composite hollow fiber membrane material premix prepared in the step one into a double-screw extruder, and performing extrusion granulation to prepare the special material for the antibacterial multilayer composite hollow fiber membrane material;
step three: and (3) adding the special material for the antibacterial multilayer composite hollow fiber membrane material prepared in the step two into an extruder to be melted at a certain temperature, extruding and molding the melt into a hollow fiber shape through a spinning nozzle, condensing the hollow fiber shape through a cooling water area with a certain temperature gradient, and winding the hollow fiber shape through a traction device rotating at a high speed to prepare the antibacterial multilayer composite hollow fiber membrane material. The working parameters are as follows: the spinning temperature is as follows: 185 ℃ in the first zone, 190 ℃ in the second zone, 210 ℃ in the third zone, 215 ℃ in the fourth zone, 195 ℃ in the pipeline, 205 ℃ in the box body, and the rotation speed of the screw: 13r/min, rotating speed of a metering pump: 18r/min, winding speed: the extrusion rate of the 450r/min melt was: 0.2cm/s, the temperature of a condensation water area is as follows: at 18 ℃.
Through inspection, the antibacterial multilayer composite hollow fiber membrane material prepared by the embodiment has the bacteriostasis rate of 98.0 percent on escherichia coli for 24 hours and staphylococcus aureus after being washed by water for 50 times, 96.9 percent on the escherichia coli for 24 hours and the staphylococcus aureus after being washed by water for 70 mu W/cm2After 12 hours of ultraviolet irradiation with intensity, the bacteriostasis rate to escherichia coli for 24 hours and staphylococcus aureus is 97.8%, and after 200 times of water washing, the bacteriostasis rate to escherichia coli for 24 hours and staphylococcus aureus is 96.5%.
Example 3
An antibacterial multilayer composite hollow fiber membrane material is composed of the following raw materials in parts by weight:
PP resin: 40 portions of
PVB resin: 7.5 parts of
PVDF resin: 7 portions of
A compatilizer: 6 portions of
Antibacterial agents: 3 portions of
Lubricant: 2.3 parts of
Antioxidant: 0.38 portion.
The antibacterial agent is modified graphene/chitosan intercalation zirconium phosphate.
The modified graphene/chitosan intercalation zirconium phosphate antibacterial agent is prepared by the following method:
(1) preparation of modified graphene
Preparing graphene oxide by adopting an improved Hummers method, weighing 7g of graphene oxide, adding the graphene oxide into a three-neck flask filled with 100mL of acetone, adding 0.4g of titanate coupling agent while stirring, reacting for 2h at the temperature of 60 ℃, performing suction filtration, and drying to obtain the modified graphene.
(2) Preparation of modified graphene/chitosan
Accurately weighing 2g of chitosan, adding 300mL of deionized water, stirring, slowly dripping 19g of acetic acid solution with the concentration of 7.5%, and fully stirring for 2h to obtain the chitosan solution. Weighing 2g of the modified graphene prepared in the step (1), slowly adding the modified graphene into the chitosan solution, fully stirring to obtain a uniformly mixed modified graphene/chitosan solution, and putting the solution into a vacuum oven for vacuum drying to obtain the modified graphene/chitosan material.
(3) Preparation of graphene/chitosan intercalation zirconium phosphate antibacterial agent
Weighing 8g of zirconium phosphate, adding 500mL of deionized water, stirring and dispersing uniformly at normal temperature, slowly adding 18g of ethylenediamine and diethylenetriamine pre-intercalation agent while stirring, fully reacting for 3h, then performing ultrasonic treatment for 50min to obtain a pre-intercalated zirconium phosphate suspension, weighing 2g of the modified graphene/chitosan material prepared in the step (2), adding the modified graphene/chitosan material into the pre-intercalated zirconium phosphate suspension, heating to 85 ℃, performing rapid mechanical stirring for 8h to obtain a graphene/chitosan intercalated zirconium phosphate suspension, and filtering, washing and drying to obtain the graphene/chitosan intercalated zirconium phosphate antibacterial agent.
The improved Hummers method in the step (1) comprises the following specific steps: 7g of graphite powder was weighed into a 500mL flask, and the flask was placed in a water bath at 2 ℃. Slowly adding 180mL of concentrated sulfuric acid, stirring for 3 hours, slowly adding 28g of potassium permanganate, raising the reaction temperature to 50 ℃, stirring for 1-3 hours, slowly adding 190mL of deionized water, filtering, finally ultrasonically washing three times by using 175 mL of 8% dilute hydrochloric acid and deionized water, and drying for 28 hours in vacuum at the temperature of 70 ℃ to obtain the graphene oxide.
The PP resin is isotactic polypropylene, the melt flow rate is 10 g/min, and the density is 0.92 g/mL; the compatilizer is PP-g-MAH;
the lubricant is MBS;
the antioxidant is composed of 1010 and 168 according to the mass ratio of 3: 1;
a preparation method of an antibacterial multilayer composite hollow fiber membrane material comprises the following steps:
the method comprises the following steps: weighing PP resin, PVB resin, PVDF resin, a compatilizer, an antibacterial agent, a lubricant and an antioxidant according to the proportion, adding the mixture into a high-speed mixer, uniformly mixing, and discharging to obtain an antibacterial multilayer composite hollow fiber membrane material premix;
step two: adding the antibacterial multilayer composite hollow fiber membrane material premix prepared in the step one into a double-screw extruder, and performing extrusion granulation to prepare the special material for the antibacterial multilayer composite hollow fiber membrane material;
step three: and (3) adding the special material for the antibacterial multilayer composite hollow fiber membrane material prepared in the step two into an extruder to be melted at a certain temperature, extruding and molding the melt into a hollow fiber shape through a spinning nozzle, condensing the hollow fiber shape through a cooling water area with a certain temperature gradient, and winding the hollow fiber shape through a traction device rotating at a high speed to prepare the antibacterial multilayer composite hollow fiber membrane material. The working parameters are as follows: the spinning temperature is as follows: first zone 185 ℃, second zone 200 ℃, third zone 215 ℃, fourth zone 215 ℃, pipeline 205 ℃, box 210 ℃, screw speed: 18r/min, metering pump rotation speed: 27r/min, winding speed: the melt extrusion rate at 580r/min was: 0.45cm/s, the temperature of a condensation water area is as follows: at 25 ℃.
Through inspection, the antibacterial multilayer composite hollow fiber membrane material prepared by the embodiment has the bacteriostasis rate of 98.8% to escherichia coli for 24 hours and staphylococcus aureus after being washed by water for 50 times, 97.3% to escherichia coli for 24 hours and staphylococcus aureus and 70 muW/cm2The bacteriostasis rate of the ultraviolet ray with the intensity on escherichia coli for 24 hours and staphylococcus aureus after 12 hours of irradiation is 98.7 percentAfter 200 times of water washing, the antibacterial rate of the antibacterial agent to escherichia coli for 24 hours and staphylococcus aureus is 97.0%.
Example 4
An antibacterial multilayer composite hollow fiber membrane material is composed of the following raw materials in parts by weight:
PP resin: 45 portions of
PVB resin: 9 portions of
PVDF resin: 8 portions of
A compatilizer: 6 portions of
Antibacterial agents: 4.5 parts of
Lubricant: 1.8 parts of
Antioxidant: 0.45 part.
The antibacterial agent is modified graphene/chitosan intercalation zirconium phosphate.
The modified graphene/chitosan intercalation zirconium phosphate antibacterial agent is prepared by the following method:
(1) preparation of modified graphene
Preparing graphene oxide by adopting an improved Hummers method, weighing 9g of graphene oxide, adding the graphene oxide into a three-neck flask filled with 100mL of acetone, adding 0.85g of silane coupling agent while stirring, reacting for 2.5h at the temperature of 66 ℃, performing suction filtration, and drying to obtain the modified graphene.
(2) Preparation of modified graphene/chitosan
2.8g of chitosan is accurately weighed, added into 300mL of deionized water and stirred, and then 17g of acetic acid solution with the concentration of 7% is slowly dropped into the mixture and fully stirred for 1.5h to prepare the chitosan solution. And (2.7) g of the modified graphene prepared in the step (1) is weighed and slowly added into the chitosan solution, the modified graphene/chitosan solution is obtained after full stirring, and the solution is placed into a vacuum oven for vacuum drying to obtain the modified graphene/chitosan material.
(3) Preparation of graphene/chitosan intercalation zirconium phosphate antibacterial agent
Weighing 8.5g of zirconium phosphate, adding 500mL of deionized water, stirring and dispersing uniformly at normal temperature, slowly adding 19g of ethylenediamine and diethylenetriamine pre-intercalation agent while stirring, fully reacting for 3.5h, then performing ultrasonic treatment for 55min to obtain a pre-intercalated zirconium phosphate suspension, weighing 2.6g of the modified graphene/chitosan material prepared in the step (2), adding the modified graphene/chitosan material into the pre-intercalated zirconium phosphate suspension, heating to 90 ℃, performing rapid mechanical stirring for 9h to obtain a graphene/chitosan intercalated zirconium phosphate suspension, and filtering, washing and drying to obtain the graphene/chitosan intercalated zirconium phosphate antibacterial agent.
The improved Hummers method in the step (1) comprises the following specific steps: 9g of graphite powder was weighed into a 500mL flask, and the flask was placed in a water bath at 3 ℃. Slowly adding 195mL of concentrated sulfuric acid, stirring for 4h, slowly adding 27g of potassium permanganate, raising the reaction temperature to 50 ℃, stirring for 2h, slowly adding 180mL of deionized water, filtering, finally ultrasonically washing three times with 165mL of 9% dilute hydrochloric acid and deionized water, and drying for 40h under vacuum at the temperature of 70 ℃ to obtain the graphene oxide.
The PP resin is isotactic polypropylene, the melt flow rate is 8g/min, and the density is 0.93 g/mL; the compatilizer is PP-g-AA;
the lubricant is MBS;
the antioxidant is composed of 1010 and 168 according to a mass ratio of 5: 1;
a preparation method of an antibacterial multilayer composite hollow fiber membrane material comprises the following steps:
the method comprises the following steps: weighing PP resin, PVB resin, PVDF resin, a compatilizer, an antibacterial agent, a lubricant and an antioxidant according to the proportion, adding the mixture into a high-speed mixer, uniformly mixing, and discharging to obtain an antibacterial multilayer composite hollow fiber membrane material premix;
step two: adding the antibacterial multilayer composite hollow fiber membrane material premix prepared in the step one into a double-screw extruder, and performing extrusion granulation to prepare the special material for the antibacterial multilayer composite hollow fiber membrane material;
step three: and (3) adding the special material for the antibacterial multilayer composite hollow fiber membrane material prepared in the step two into an extruder to be melted at a certain temperature, extruding and molding the melt into a hollow fiber shape through a spinning nozzle, condensing the hollow fiber shape through a cooling water area with a certain temperature gradient, and winding the hollow fiber shape through a traction device rotating at a high speed to prepare the antibacterial multilayer composite hollow fiber membrane material. The working parameters are as follows: the spinning temperature is as follows: first zone 180 ℃, second zone 195 ℃, third zone 210 ℃, fourth zone 210 ℃, pipe 200 ℃, box 215 ℃, screw speed: 18r/min, metering pump rotation speed: 26r/min, winding speed: the melt extrusion rate at 580r/min was: 0.35cm/s, the temperature of the condensed water area is as follows: an electron microscope scanning image of the prepared antibacterial multilayer composite hollow fiber membrane material at 15 ℃ is shown in figure 2.
Through inspection, the antibacterial multilayer composite hollow fiber membrane material prepared by the embodiment has 99.6% of inhibition rate on escherichia coli for 24 hours and staphylococcus aureus, 98.9% of inhibition rate on escherichia coli for 24 hours and staphylococcus aureus after being washed by water for 50 times, and 70 muW/cm2After 12 hours of ultraviolet irradiation with intensity, the bacteriostasis rate to escherichia coli for 24 hours and staphylococcus aureus is 99.3%, and after 200 times of water washing, the bacteriostasis rate to escherichia coli for 24 hours and staphylococcus aureus is 98.5%.
Example 5
An antibacterial multilayer composite hollow fiber membrane material is composed of the following raw materials in parts by weight:
PP resin: 50 portions of
PVB resin: 10 portions of
PVDF resin: 10 portions of
A compatilizer: 8 portions of
Antibacterial agents: 5 portions of
Lubricant: 2 portions of
Antioxidant: 0.5 part.
The antibacterial agent is modified graphene/chitosan intercalation zirconium phosphate.
The modified graphene/chitosan intercalation zirconium phosphate antibacterial agent is prepared by the following method:
(1) preparation of modified graphene
Preparing graphene oxide by adopting an improved Hummers method, weighing 10g of graphene oxide, adding the graphene oxide into a three-neck flask filled with 100mL of acetone, adding 1g of aluminate coupling agent while stirring, reacting for 3h at the temperature of 70 ℃, performing suction filtration, and drying to obtain the modified graphene.
(2) Preparation of modified graphene/chitosan
Accurately weighing 3g of chitosan, adding 300mL of deionized water, stirring, slowly dripping 20g of 10% acetic acid solution, and fully stirring for 2h to obtain the chitosan solution. Weighing 3g of the modified graphene prepared in the step (1), slowly adding the modified graphene into the chitosan solution, fully stirring to obtain a uniformly mixed modified graphene/chitosan solution, and putting the solution into a vacuum oven for vacuum drying to obtain the modified graphene/chitosan material.
(3) Preparation of graphene/chitosan intercalation zirconium phosphate antibacterial agent
Weighing 10g of zirconium phosphate, adding 500mL of deionized water, stirring and dispersing uniformly at normal temperature, slowly adding 20g of ethylenediamine and aniline pre-intercalation agent while stirring, fully reacting for 4h, then performing ultrasonic treatment for 60min to obtain a pre-intercalated zirconium phosphate suspension, weighing 3g of the modified graphene/chitosan material prepared in the step (2), adding the modified graphene/chitosan material into the pre-intercalated zirconium phosphate suspension, heating to 100 ℃, performing rapid mechanical stirring for 10 h to obtain a graphene/chitosan intercalated zirconium phosphate suspension, and filtering, washing and drying to obtain the graphene/chitosan intercalated zirconium phosphate antibacterial agent.
The improved Hummers method in the step (1) comprises the following specific steps: 10g of graphite powder was weighed into a 500mL flask, and the flask was placed in a water bath at 5 ℃. Slowly adding 200mL of concentrated sulfuric acid, stirring for 5h, slowly adding 30g of potassium permanganate, raising the reaction temperature to 60 ℃, stirring for 3h, slowly adding 200mL of deionized water, filtering, finally ultrasonically washing for three times by 200mL of 10% dilute hydrochloric acid and deionized water, and drying for 48h under vacuum at the temperature of 80 ℃ to obtain the graphene oxide.
The PP resin is isotactic polypropylene, the melt flow rate is 6 g/min, and the density is 0.95 g/mL; the compatilizer is PP-g-AA;
the lubricant is PP wax;
the antioxidant is composed of 1010 and 168 according to a mass ratio of 4: 1;
a preparation method of an antibacterial multilayer composite hollow fiber membrane material comprises the following steps:
the method comprises the following steps: weighing PP resin, PVB resin, PVDF resin, a compatilizer, an antibacterial agent, a lubricant and an antioxidant according to the proportion, adding the mixture into a high-speed mixer, uniformly mixing, and discharging to obtain an antibacterial multilayer composite hollow fiber membrane material premix;
step two: adding the antibacterial multilayer composite hollow fiber membrane material premix prepared in the step one into a double-screw extruder, and performing extrusion granulation to prepare the special material for the antibacterial multilayer composite hollow fiber membrane material;
step three: and (3) adding the special material for the antibacterial multilayer composite hollow fiber membrane material prepared in the step two into an extruder to be melted at a certain temperature, extruding and molding the melt into a hollow fiber shape through a spinning nozzle, condensing the hollow fiber shape through a cooling water area with a certain temperature gradient, and winding the hollow fiber shape through a traction device rotating at a high speed to prepare the antibacterial multilayer composite hollow fiber membrane material. The working parameters are as follows: the spinning temperature is as follows: 190 ℃ in the first zone, 200 ℃ in the second zone, 215 ℃ in the third zone, 220 ℃ in the fourth zone, 205 ℃ in the pipeline, 220 ℃ in the box body, and the rotation speed of the screw: 20r/min, rotating speed of a metering pump: 30r/min, winding speed: the extrusion rate of the 600r/min melt was: 0.5cm/s, the temperature of the condensation water area is as follows: at 30 ℃.
Through inspection, the antibacterial multilayer composite hollow fiber membrane material prepared by the embodiment has 99.3% of inhibition rate on escherichia coli for 24 hours and staphylococcus aureus, 98.4% of inhibition rate on escherichia coli for 24 hours and staphylococcus aureus after being washed by water for 50 times, and 70 muW/cm2After 12 hours of ultraviolet irradiation with intensity, the bacteriostasis rate to escherichia coli for 24 hours and staphylococcus aureus is 99.2%, and after 200 times of water washing, the bacteriostasis rate to escherichia coli for 24 hours and staphylococcus aureus is 98.1%.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (10)
1. An antibacterial multilayer composite hollow fiber membrane material is characterized in that: the composition is characterized by comprising the following raw materials in parts by weight:
PP resin: 30 to 50 portions of
PVB resin: 5 to 10 parts of
PVDF resin: 5 to 10 parts of
A compatilizer: 3 to 8 portions of
Antibacterial agents: 1 to 5 portions of
Lubricant: 0.5 to 2 portions of
Antioxidant: 0.1 to 0.5 portion.
2. The antibacterial multilayer composite hollow fiber membrane material as claimed in claim 1, characterized in that: the antibacterial agent is modified graphene/chitosan intercalation zirconium phosphate.
3. The graphene oxide/chitosan intercalated zirconium phosphate antibacterial agent according to claim 2, wherein the modified graphene/chitosan intercalated zirconium phosphate antibacterial agent is prepared by a method comprising:
(1) preparation of modified graphene
Preparing graphene oxide by adopting an improved Hummers method, weighing 5-10 g of graphene oxide, adding the graphene oxide into a three-necked flask filled with 100mL of acetone, adding 0.1-1 g of coupling agent while stirring, reacting for 1-3 h at the temperature of 50-70 ℃, performing suction filtration, and drying to obtain modified graphene;
(2) preparation of modified graphene/chitosan
Accurately weighing 1-3 g of chitosan, adding 300mL of deionized water, stirring, slowly dropping 10-20 g of acetic acid solution with the concentration of 5-10%, and fully stirring for 1-2 h to obtain a chitosan solution; weighing 1-3 g of the modified graphene prepared in the step (1), slowly adding the modified graphene into a chitosan solution, fully stirring to obtain a uniformly mixed modified graphene/chitosan solution, and putting the solution into a vacuum oven for vacuum drying to obtain a modified graphene/chitosan material;
(3) preparation of graphene/chitosan intercalation zirconium phosphate antibacterial agent
Weighing 5-10 g of zirconium phosphate, adding 500mL of deionized water, stirring and dispersing uniformly at normal temperature, slowly adding 10-20 g of small molecular amine pre-intercalation agent while stirring, fully reacting for 2-4 h, then performing ultrasonic treatment for 30-60 min to obtain pre-intercalated zirconium phosphate suspension, weighing 1-3 g of the modified graphene/chitosan material prepared in the step (2), adding into the pre-intercalated zirconium phosphate suspension, heating to 50-100 ℃, rapidly and mechanically stirring for 5-10 h to obtain graphene/chitosan intercalated zirconium phosphate suspension, and filtering, washing and drying to obtain the graphene/chitosan intercalated zirconium phosphate antibacterial agent.
4. The preparation method of the modified graphene/chitosan intercalated zirconium phosphate antibacterial agent according to claim 3, characterized by comprising the following steps: the improved Hummers method in the step (1) comprises the following specific steps: weighing 5-10 g of graphite powder, adding the graphite powder into a 500mL flask, and placing the flask in a water bath at 0-5 ℃; slowly adding 100-200 mL of concentrated sulfuric acid, stirring for 2-5 h, slowly adding 10-30 g of potassium permanganate, raising the reaction temperature to 20-60 ℃, stirring for 1-3 h, slowly adding 50-200 mL of deionized water, filtering, ultrasonically washing for three times by using 100-200 mL of 5-10% dilute hydrochloric acid and deionized water, and drying in vacuum at 40-80 ℃ for 24-48 h to obtain graphene oxide.
5. The preparation method of the modified graphene/chitosan intercalated zirconium phosphate antibacterial agent according to claim 3, characterized by comprising the following steps: the coupling agent in the step (1) is at least one of silane coupling agent, aluminate coupling agent and titanate coupling agent.
6. The preparation method of the modified graphene/chitosan intercalated zirconium phosphate antibacterial agent according to claim 3, characterized by comprising the following steps: the micromolecule amine pre-intercalation agent in the step (3) is at least one of ethylenediamine, hexamethylenediamine, aniline and diethylenetriamine.
7. The antibacterial multilayer composite hollow fiber membrane material as claimed in claim 1, characterized in that: the PP resin is isotactic polypropylene, the melt flow rate is 6-15 g/min, and the density is 0.8-0.95 g/mL; the compatilizer is at least one of PP-g-MAH and PP-g-AA.
8. The antibacterial multilayer composite hollow fiber membrane material as claimed in claim 1, characterized in that: the antibacterial multilayer composite hollow fiber membrane material as claimed in claim 1, characterized in that: the lubricant is at least one of MBS and PP wax; the antioxidant is composed of 1010 and 168 according to the mass ratio of 1-5: 1.
9. The preparation method of the antibacterial multilayer composite hollow fiber membrane material according to claims 1 to 8, characterized in that:
the method comprises the following steps: weighing PP resin, PVB resin, PVDF resin, a compatilizer, an antibacterial agent, a lubricant and an antioxidant according to the proportion, adding the mixture into a high-speed mixer, uniformly mixing, and discharging to obtain an antibacterial multilayer composite hollow fiber membrane material premix;
step two: adding the antibacterial multilayer composite hollow fiber membrane material premix prepared in the step one into a double-screw extruder, and performing extrusion granulation to prepare the special material for the antibacterial multilayer composite hollow fiber membrane material;
step three: and (3) adding the special material for the antibacterial multilayer composite hollow fiber membrane material prepared in the step two into an extruder to be melted at a certain temperature, extruding and molding the melt into a hollow fiber shape through a spinning nozzle, condensing the hollow fiber shape through a cooling water area with a certain temperature gradient, and winding the hollow fiber shape through a traction device rotating at a high speed to prepare the antibacterial multilayer composite hollow fiber membrane material.
10. The preparation method of the antibacterial multilayer composite hollow fiber membrane material according to claim 9, characterized in that: the working parameters of the hollow fiber membrane material in the third step are as follows:
the spinning temperature is as follows: 175-190 ℃ in the first area, 185-200 ℃ in the second area and 205-215 ℃ in the third area,
in the fourth zone, the temperature is 210-220 ℃, the pipeline is 190-205 ℃, the box body is 200-220 ℃, the screw rotation speed is as follows: 10-20 r/min, rotating speed of a metering pump: 15-30 r/min, winding speed: the extrusion rate of the melt at 400-600 r/min is as follows: 0.1-0.5 cm/s, and the temperature of the condensed water area is as follows: 10 to 30 ℃.
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