CN115197527A - Preparation method of silver ion titanium dioxide/L type molecular sieve antibacterial plastic - Google Patents

Preparation method of silver ion titanium dioxide/L type molecular sieve antibacterial plastic Download PDF

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Publication number
CN115197527A
CN115197527A CN202210911463.8A CN202210911463A CN115197527A CN 115197527 A CN115197527 A CN 115197527A CN 202210911463 A CN202210911463 A CN 202210911463A CN 115197527 A CN115197527 A CN 115197527A
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molecular sieve
type molecular
silver ion
tio
titanium dioxide
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刘振中
应佳蕾
徐鑫磊
何广宇
马春新
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Research Institute of Zhejiang University Taizhou
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Research Institute of Zhejiang University Taizhou
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide

Abstract

The invention provides a preparation method of silver ion titanium dioxide/L type molecular sieve antibacterial plastic, which comprises the following steps: (1) Weighing KOH and Al (OH) 3 Uniformly mixing silica sol and deionized water to form sol, placing the sol in a reaction kettle for reaction at the temperature of 120-200 ℃ for 36-52 hours, and then performing suction filtration, washing, drying and grinding to form an L-shaped molecular sieve; (2) Adding an L-type molecular sieve into a mixed solution of ethanol and ammonia water, adding tetrabutyl titanate, uniformly mixing, keeping the temperature at 40-80 ℃ for 4-24 hours, and treating to obtain TiO 2 type/L isSieving; (3) Adding TiO into the mixture 2 Soaking the/L type molecular sieve into silver nitrate solution for adsorption and treatment to obtain silver ion TiO 2 Molecular sieve type/L; and (4) mixing the ABS plastic and then melting and blending to obtain the product. The product prepared by the invention has the advantage of good antibacterial effect.

Description

Preparation method of silver ion titanium dioxide/L type molecular sieve antibacterial plastic
Technical Field
The invention belongs to the field of inorganic materials, and particularly relates to a preparation method of silver ion titanium dioxide/L type molecular sieve antibacterial plastic.
Background
With the continuous improvement of living standard, the requirements of people on health and environmental protection are gradually improved, so the requirements on antibacterial materials and antibacterial products are higher and higher. The antibacterial material is a material capable of killing and inhibiting the growth of microorganisms, and has wide application in the fields of medical treatment, health, industrial production and the like. Common antimicrobial materials include antimicrobial fibers, antimicrobial ceramics, antimicrobial metals, and antimicrobial plastics, among others. In order to inhibit bacteria growing on the outer surface of the plastic product in the storage and use processes, the material capable of inhibiting the growth of microorganisms is added into the plastic, so that the corrosion of the bacteria on the outer surface of the plastic product can be effectively inhibited, and the service life of the product is prolonged.
Currently, common antibacterial agents include inorganic antibacterial agents, organic antibacterial agents, natural antibacterial agents, complex antibacterial agents, and the like. Chitosan and other natural antibacterial agents are simple and convenient to use, but have limited antibacterial action and cannot have broad-spectrum long-acting effect. The organic antibacterial agents such as quaternary ammonium salt compounds and the like have high sterilization speed and mature technology, but have poor stability and long-acting property. The metal ions in the metal such as silver, zinc, copper and the like or the metal oxides and the like are important parts, particularly, the silver-based antibacterial agent has good antibacterial effect, and the antibacterial functional component of the silver-based antibacterial agent is the silver ions. The composite antibacterial agent is an antibacterial agent compounded by the antibacterial agents in a certain form, and can fully exert the advantages of various antibacterial agents.
The molecular sieve is an adsorbent with a uniform microporous structure, and the diameter of pores of the molecular sieve is uniform, so that molecules smaller than the diameter of the pores can be adsorbed into the inner parts of the pores. Wherein, the L-shaped molecular sieve is an artificially synthesized sieve, the main channel of the L-shaped molecular sieve is a one-dimensional pore channel consisting of twelve-membered rings, and consists of two secondary structure units of a cancrinite cage and a hexagonal column cage, has extremely high adsorption performance, and can be used for purifying and purifying the calcium-doped calcium carbonateCan adsorb water molecules and oxygen in air, and can be used as carrier of antibacterial agent. TiO 2 2 The material is an inorganic functional material with stable chemical properties, photochemical resistance, acid and alkali corrosion resistance, and has the advantages of low cost, no toxicity, no harm, high catalytic activity, strong oxidation capability, no pollution and the like. Aiming at the problems of the prior composite antibacterial agent and antibacterial plastic technology, how to combine TiO 2 And silver ions are loaded on the L-type molecular sieve, and the antibacterial performance is endowed to plastics in any blending mode, which is a technical problem to be solved in the field at present.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of silver ion titanium dioxide/L type molecular sieve antibacterial plastic, and the silver ion titanium dioxide/L type molecular sieve antibacterial plastic prepared by the method has high antibacterial rate and long antibacterial effective period by adding a composite antibacterial agent with silver ions and titanium dioxide in a synergistic manner into an ABS plastic matrix.
In order to solve the problems, the invention adopts the technical scheme that:
a preparation method of silver ion titanium dioxide/L type molecular sieve antibacterial plastic comprises the following steps:
(1) Weighing KOH and Al (OH) 3 Uniformly mixing silica sol and deionized water to form sol, placing the sol in a reaction kettle for reaction at the temperature of 120-200 ℃ for 36-52 h, cooling to room temperature, performing suction filtration, washing, drying and grinding to form an L-shaped molecular sieve;
(2) Adding an L-type molecular sieve into a mixed solution of ethanol and ammonia water, adding tetrabutyl titanate, uniformly mixing, reacting at the temperature of 40-80 ℃ for 4-24 h, centrifuging, washing, drying and grinding after the reaction is finished to obtain TiO 2 Molecular sieves of type/L;
(3) Mixing TiO with 2 Soaking the/L type molecular sieve in silver nitrate solution for adsorption, filtering and drying to obtain silver ion TiO 2 An L-type molecular sieve antibacterial agent;
(4) Weighing ABS plastic and mixing the ABS plastic with silver ion TiO 2 the/L type molecular sieve is evenly mixed and then melted and blended to obtain the silver ion dioxidetitanium/L type molecular sieve antibacterial plastic.
Further, in the step (1), firstly, KOH is dissolved in the partially deionized water to form KOH solution, and then Al (OH) is added 3 Dissolved in KOH solution and heated until the solution is clear, then silica sol and the remaining deionized water are added to form a sol.
Further, the reaction temperature of the reaction kettle in the step (1) is 180 ℃, and the reaction time is 48 hours.
Further, in the step (1), the ratio of KOH: al (OH) 3 ：SiO 2 ：H 2 The molar ratio of O is 1:1:2.5:50 to 3:1:10:200.
further, the molecular sieve in L form in the step (2): ammonia water: the mass ratio of tetrabutyl titanate is 1:0.01:0.05 to 1:0.2:0.7.
further, the reaction temperature of the step (2) is 40 ℃, and the reaction time is 24h.
Further, silver nitrate in the step (3): tiO 2 2 The mass concentration of the/L type molecular sieve is 3:2000 to 3:20.
further, silver nitrate in the step (3): tiO 2 2 The mass concentration of the/L type molecular sieve is 3:2000, the adsorption temperature is 80 ℃, and the adsorption time is 2h.
Further, in the step (4), silver ion TiO 2 Molecular sieve type/L: the mass ratio of the ABS plastic is 1:100 to 1:19.
further, the melt blending temperature in the step (4) is 170-230 ℃, and the rotation speed of a main machine is 150-300rpm.
The silver ion titanium dioxide/L type molecular sieve antibacterial plastic is prepared by the preparation method of the silver ion titanium dioxide/L type molecular sieve antibacterial plastic.
The application of the silver ion titanium dioxide/L type molecular sieve antibacterial plastic in the field of home decoration is provided.
The invention has the beneficial effects that:
1. the invention solves the problem that the TiO 2 The difference in polarity with ABS resin, resulting in TiO 2 Can agglomerate in ABS resin and expose TiO on the outer surface of the plastic 2 Low content of L-type molecular sieve and TiO 2 In combination, tiO due to the larger volume effect of the L-type molecular sieve 2 The L-shaped molecular sieve is loaded on the L-shaped molecular sieve, and then is fused and blended with ABS plastic, so that the contact area of the outer surface of the exposed plastic of the L-shaped molecular sieve and air is larger, and the silver compound and TiO wrapped on the outer layer of the L-shaped molecular sieve 2 The area is larger, and simultaneously, the problem that TiO is caused by the fact that the outer surface of ABS plastic is smooth and hydrophobic is solved 2 The problem that water and oxygen cannot be contacted, and the antibacterial effect cannot be exerted even under the irradiation of ultraviolet light; secondly, because the silver-based antibacterial agent can generate free silver ions under the condition of water molecules, the ABS plastic outer surface is hydrophobic, and the silver ions can not completely play the antibacterial action of the ABS plastic, the antibacterial material prepared by the invention can fully play the antibacterial action of the silver ions, and solves the problem that TiO is not completely used for preparing the antibacterial material 2 And silver ions and common plastics cannot effectively endow the plastics with high antibacterial performance after being compounded.
2. After the silver ion titanium dioxide/L-type molecular sieve prepared by the invention is compounded with ABS plastic, the antibacterial rate is as high as 99%, and the composite material has the advantages of good antibacterial effect, low cost, short preparation period, long storage time and long service life, and meanwhile, the preparation method is simple, the operation safety is high, and the large-scale production is convenient.
Drawings
FIG. 1 is a scanning electron micrograph of an L-type molecular sieve of example 1;
FIG. 2 is a scanning electron micrograph of a titanium dioxide/L type molecular sieve according to example 1;
FIG. 3 is a scanning electron micrograph of the silver ion titanium dioxide/L type molecular sieve antibacterial plastic of example 2;
FIG. 4 is a scanning electron microscope image of the antibacterial plastic of silver ion titanium dioxide/L type molecular sieve in example 3;
FIG. 5 is a graph showing the results of X-ray energy spectrum analysis of the silver ion L-type molecular sieve in comparative example 3.
Detailed Description
In order to describe the present invention more specifically, the following detailed description of the present invention is made with reference to the accompanying drawings and the detailed description of the present invention. These descriptions are merely illustrative of how the invention may be carried into effect and do not limit the specific scope of the invention. The scope of the invention is defined in the claims.
The present invention is further illustrated below by means of specific embodiments, but the embodiments of the present invention are not limited thereto.
Example 1
The preparation method of the silver ion titanium dioxide/L type molecular sieve antibacterial plastic provided by the embodiment comprises the following steps:
1. 31.68g deionized water, 7.82g KOH was added to a portion of the deionized water to prepare a KOH solution, 4.16g Al (OH) 3 Dissolving in KOH solution, putting the KOH solution into a hydrothermal kettle, heating the KOH solution to be clear at 80 ℃, adding 40g of silica sol and the rest deionized water, carrying out ultrasonic treatment, uniformly mixing to form sol, putting the sol into a reaction kettle, and reacting for 48 hours at 180 ℃. After the reaction is finished, washing the product to be neutral by deionized water, filtering the product, drying the product for 8 hours at 110 ℃, and grinding the product to obtain an L-shaped molecular sieve;
2. adding 2mg of L-type molecular sieve into a mixed solution of 60 mu L of ammonia water and 10mL of ethanol, adding 375 mu L of tetrabutyl titanate, performing ultrasonic treatment until the mixture is uniformly mixed, reacting for 24 hours at 40 ℃, performing centrifugal washing by using ethanol and deionized water after the reaction is finished, filtering, taking a solid product, drying at 110 ℃, and grinding to obtain TiO 2 Molecular sieve type/L;
3. weighing 2mg of TiO 2 Adding the/L type molecular sieve and 0.19mL silver nitrate solution (0.01 mM) into 9.8mL deionized water, heating at 80 ℃, stirring, adsorbing for 2h, cooling to room temperature, filtering and drying to obtain the silver ion TiO 2 Molecular sieves of type/L;
4. make silver ion TiO 2 the/L type molecular sieve and the ABS plastic are prepared according to the following weight ratio of 1:100, melt blending through a double-screw extruder at the temperature of 170 ℃ and the rotating speed of a main machine of 150rpm to obtain the silver ion TiO 2 The L-type molecular sieve composite antibacterial plastic.
This exampleThe scanning electron micrograph of the prepared L-type molecular sieve obtained in the step 1 is shown in figure 1, and the L-type molecular sieve A can be seen to be in a cylindrical structure and has the size of about 2 microns; the scanning electron micrograph of the titanium dioxide/L-type molecular sieve obtained in the step 2 is shown in figure 2, and TiO can be seen from the micrograph 2 The antibacterial and adsorptive capacity of the composite material is improved by successfully compounding the composite material on the surface of the L-shaped molecular sieve.
Example 2
The preparation method of the silver ion titanium dioxide/L type molecular sieve antibacterial plastic provided by the embodiment comprises the following steps:
1. 31.68g deionized water, 7.82g KOH was added to a portion of the deionized water to prepare a KOH solution, 4.16g Al (OH) 3 Dissolving in KOH solution, putting the KOH solution into a hydrothermal kettle, heating the KOH solution to be clear at 80 ℃, then adding 40g of silica sol and the rest deionized water, carrying out ultrasonic treatment, uniformly mixing to form sol, putting the sol into a reaction kettle, and reacting for 48 hours at 180 ℃. After the reaction is finished, washing the mixture to be neutral by deionized water, filtering the mixture, drying the mixture for 8 hours at 110 ℃, and grinding the mixture to obtain an L-shaped molecular sieve;
2. adding 2mg of L-type molecular sieve into a mixed solution of 60 mu L of ammonia water and 10mL of ethanol, adding 375 mu L of tetrabutyl titanate, performing ultrasonic treatment until the mixture is uniformly mixed, reacting for 24 hours at 40 ℃, performing centrifugal washing by using ethanol and deionized water after the reaction is finished, filtering, taking a solid product, drying at 110 ℃, and grinding to obtain TiO 2 Molecular sieve type/L;
3. weighing 2mg of TiO 2 Adding the/L type molecular sieve and 0.19mL silver nitrate solution (0.01 mM) into 9.8mL deionized water, heating at 80 ℃, stirring, adsorbing for 1h, cooling to room temperature, filtering and drying to obtain silver ion TiO 2 L type molecular sieve
4. TiO 2 silver ion 2 the/L type molecular sieve and the ABS plastic are mixed according to the proportion of 1:49, melt blending by a double-screw extruder at the temperature of 200 ℃ and the rotating speed of a main engine of 170rpm to obtain the silver ion TiO 2 the/L type molecular sieve composite antibacterial plastic.
An SEM image of the Ag ion TiO/L type molecular sieve antibacterial plastic prepared in this example is shown in FIG. 3, from which it can be seen that the lower content of Ag ion TiO 2 After the/L type molecular sieve antibacterial agent and the ABS plastic are blended, the antibacterial plastic is successfully compounded together.
Example 3
The preparation method of the silver ion titanium dioxide/L type molecular sieve antibacterial plastic provided by the embodiment comprises the following steps:
1. 31.68g deionized water, 7.82g KOH was added to a portion of the deionized water to prepare a KOH solution, 4.16g Al (OH) 3 Dissolving in KOH solution, putting into a hydrothermal kettle, heating to be clear at 80 ℃, then adding 40g of silica sol and the rest deionized water, carrying out ultrasonic treatment, uniformly mixing to form sol, putting the sol into a reaction kettle, and reacting for 48 hours at 180 ℃. After the reaction is finished, washing the mixture to be neutral by deionized water, filtering the mixture, drying the mixture for 8 hours at 110 ℃, and grinding the mixture to obtain an L-shaped molecular sieve;
2. adding 2mg of L-shaped molecular sieve into a mixed solution of 200 mu L of ammonia water and 10mL of ethanol, adding 375 mu L of tetrabutyl titanate, performing ultrasonic treatment until the mixture is uniformly mixed, reacting for 24 hours at 40 ℃, performing centrifugal washing by using ethanol and deionized water after the reaction is finished, filtering, taking a solid product, drying at 110 ℃, and grinding to obtain TiO 2 Molecular sieves of type/L;
3. weighing 2mg of TiO 2 Adding the/L type molecular sieve and 0.19mL silver nitrate solution (0.01 mM) into 9.8mL deionized water, heating at 80 ℃, stirring, adsorbing for 2h, cooling to room temperature, filtering and drying to obtain silver ion TiO 2 Molecular sieves of type/L;
4. make silver ion TiO 2 the/L type molecular sieve and the ABS plastic are mixed according to the proportion of 1:19, uniformly mixing, and performing melt blending by a double-screw extruder at the temperature of 230 ℃ and the rotating speed of a main machine of 300rpm to obtain the silver ion TiO 2 The L-type molecular sieve composite antibacterial plastic.
An SEM image of the Ag ion TiO/L type molecular sieve antibacterial plastic prepared in this example is shown in FIG. 4, from which it can be seen that a higher content of Ag ion TiO is present 2 After the/L type molecular sieve antibacterial agent and the ABS plastic are blended, the antibacterial agent and the ABS plastic are successfully compounded together, the exposed area is larger, and the antibacterial effect is stronger.
Example 4
The preparation method of the silver ion titanium dioxide/L type molecular sieve antibacterial plastic provided by the embodiment comprises the following steps:
1. 31.68g deionized water, 7.82g KOH was added to a portion of the deionized water to prepare a KOH solution, 4.16g Al (OH) 3 Dissolving in KOH solution, putting into a hydrothermal kettle, heating to be clear at 80 ℃, then adding 40g of silica sol and the rest deionized water, carrying out ultrasonic treatment, uniformly mixing to form sol, putting the sol into a reaction kettle, and reacting for 52 hours at 120 ℃. After the reaction is finished, washing the product to be neutral by deionized water, filtering the product, drying the product for 8 hours at 110 ℃, and grinding the product to obtain an L-shaped molecular sieve;
2. adding 2mg of L-type molecular sieve into a mixed solution of 60 mu L of ammonia water and 10mL of ethanol, adding 375 mu L of tetrabutyl titanate, performing ultrasonic treatment until the mixture is uniformly mixed, reacting for 24 hours at 40 ℃, performing centrifugal washing by using ethanol and deionized water after the reaction is finished, filtering, taking a solid product, drying at 110 ℃, and grinding to obtain TiO 2 Molecular sieve type/L;
3. weighing 2mg of TiO 2 Adding the/L type molecular sieve and 0.19mL silver nitrate solution (0.01 mM) into 9.8mL deionized water, heating at 80 ℃, stirring, adsorbing for 2h, cooling to room temperature, filtering and drying to obtain silver ion TiO 2 Molecular sieve type/L;
4. TiO 2 silver ion 2 the/L type molecular sieve and the ABS plastic are prepared according to the following weight ratio of 1:19, uniformly mixing, and performing melt blending through a double-screw extruder at the temperature of 230 ℃ and the rotating speed of a main machine of 300rpm to obtain the silver ion TiO 2 The L-type molecular sieve composite antibacterial plastic.
Example 5
The preparation method of the silver ion titanium dioxide/L type molecular sieve antibacterial plastic provided by the embodiment comprises the following steps:
1. 31.68g deionized water, 7.82g KOH was weighed, a part of the deionized water was added to prepare a KOH solution, 4.16g Al (OH) 3 Dissolving in KOH solution, putting into a hydrothermal kettle, heating to be clear at 80 ℃, then adding 40g of silica sol and the rest deionized water, carrying out ultrasonic treatment, uniformly mixing to form sol, putting the sol into a reaction kettle, and reacting for 36 hours at 200 ℃. After the reaction is finished, washing the mixture to be neutral by deionized water, filtering the mixture, and drying the mixture at 110 DEG CGrinding for 8 hours to obtain an L-shaped molecular sieve;
2. adding 2mg of L-type molecular sieve into a mixed solution of 60 mu L of ammonia water and 10mL of ethanol, adding 375 mu L of tetrabutyl titanate, performing ultrasonic treatment until the mixture is uniformly mixed, reacting for 24 hours at 40 ℃, performing centrifugal washing by using ethanol and deionized water after the reaction is finished, filtering, taking a solid product, drying at 110 ℃, and grinding to obtain TiO 2 Molecular sieve type/L;
3. weighing 2mg of TiO 2 Adding the/L type molecular sieve and 0.19mL silver nitrate solution (0.01 mM) into 9.8mL deionized water, heating at 80 ℃, stirring, adsorbing for 2h, cooling to room temperature, filtering and drying to obtain silver ion TiO 2 Molecular sieves of type/L;
4. make silver ion TiO 2 the/L type molecular sieve and the ABS plastic are mixed according to the proportion of 1:19, uniformly mixing, and performing melt blending by a double-screw extruder at the temperature of 230 ℃ and the rotating speed of a main machine of 300rpm to obtain the silver ion TiO 2 the/L type molecular sieve composite antibacterial plastic.
Example 6
The preparation method of the silver ion titanium dioxide/L type molecular sieve antibacterial plastic provided by the embodiment comprises the following steps:
1. 31.68g deionized water, 7.82g KOH was added to a portion of the deionized water to prepare a KOH solution, 4.16g Al (OH) 3 Dissolving in KOH solution, putting into a hydrothermal kettle, heating to be clear at 80 ℃, then adding 40g of silica sol and the rest deionized water, carrying out ultrasonic treatment, uniformly mixing to form sol, putting the sol into a reaction kettle, and reacting for 48 hours at 180 ℃. After the reaction is finished, washing the mixture to be neutral by deionized water, filtering the mixture, drying the mixture for 8 hours at 110 ℃, and grinding the mixture to obtain an L-shaped molecular sieve;
2. adding 2mg of L-shaped molecular sieve into a mixed solution of 60 mu L of ammonia water and 10mL of ethanol, adding 375 mu L of tetrabutyl titanate, performing ultrasonic treatment until the mixture is uniformly mixed, reacting for 12 hours at 60 ℃, performing centrifugal washing by using ethanol and deionized water after the reaction is finished, filtering, taking a solid product, drying at 110 ℃, and grinding to obtain TiO 2 Molecular sieves of type/L;
3. weighing 2mg of TiO 2 the/L form of molecular sieves and 0.19mL of silver nitrate solution (0.01 mM) were added to 9.8mL of deionized waterHeating at 80 deg.C, stirring, adsorbing for 2h, cooling to room temperature, filtering, and oven drying to obtain silver ion TiO 2 Molecular sieve type/L;
4. TiO 2 silver ion 2 the/L type molecular sieve and the ABS plastic are prepared according to the following weight ratio of 1:19, uniformly mixing, and performing melt blending through a double-screw extruder at the temperature of 230 ℃ and the rotating speed of a main machine of 300rpm to obtain the silver ion TiO 2 the/L type molecular sieve composite antibacterial plastic.
Example 7
The preparation method of the silver ion titanium dioxide/L type molecular sieve antibacterial plastic provided by the embodiment comprises the following steps:
1. 31.68g deionized water, 7.82g KOH was weighed, a part of the deionized water was added to prepare a KOH solution, 4.16g Al (OH) 3 Dissolving in KOH solution, putting the KOH solution into a hydrothermal kettle, heating the KOH solution to be clear at 80 ℃, then adding 40g of silica sol and the rest deionized water, carrying out ultrasonic treatment, uniformly mixing to form sol, putting the sol into a reaction kettle, and reacting for 48 hours at 180 ℃. After the reaction is finished, washing the mixture to be neutral by deionized water, filtering the mixture, drying the mixture for 8 hours at 110 ℃, and grinding the mixture to obtain an L-shaped molecular sieve;
2. adding 2mg of L-type molecular sieve into a mixed solution of 60 mu L of ammonia water and 10mL of ethanol, adding 375 mu L of tetrabutyl titanate, performing ultrasonic treatment until the mixture is uniformly mixed, reacting for 6 hours at 80 ℃, performing centrifugal washing by using ethanol and deionized water after the reaction is finished, filtering, taking a solid product, drying at 110 ℃, and grinding to obtain TiO 2 Molecular sieve type/L;
3. weighing 2mg of TiO 2 Adding the/L type molecular sieve and 0.19mL silver nitrate solution (0.01 mM) into 9.8mL deionized water, heating at 80 ℃, stirring, adsorbing for 2h, cooling to room temperature, filtering and drying to obtain silver ion TiO 2 Molecular sieves of type/L;
4. TiO 2 silver ion 2 the/L type molecular sieve and the ABS plastic are mixed according to the proportion of 1:19, uniformly mixing, and performing melt blending by a double-screw extruder at the temperature of 230 ℃ and the rotating speed of a main machine of 300rpm to obtain the silver ion TiO 2 The L-type molecular sieve composite antibacterial plastic.
Example 8
The preparation method of the silver ion titanium dioxide/L type molecular sieve antibacterial plastic provided by the embodiment comprises the following steps:
1. 31.68g deionized water, 7.82g KOH was weighed, a part of the deionized water was added to prepare a KOH solution, 4.16g Al (OH) 3 Dissolving in KOH solution, putting the KOH solution into a hydrothermal kettle, heating the KOH solution to be clear at 80 ℃, then adding 40g of silica sol and the rest deionized water, carrying out ultrasonic treatment, uniformly mixing to form sol, putting the sol into a reaction kettle, and reacting for 48 hours at 180 ℃. After the reaction is finished, washing the mixture to be neutral by deionized water, filtering the mixture, drying the mixture for 8 hours at 110 ℃, and grinding the mixture to obtain an L-shaped molecular sieve;
2. adding 2mg of L-type molecular sieve into a mixed solution of 60 mu L of ammonia water and 10mL of ethanol, adding 375 mu L of tetrabutyl titanate, performing ultrasonic treatment until the mixture is uniformly mixed, reacting for 6 hours at 80 ℃, performing centrifugal washing by using ethanol and deionized water after the reaction is finished, filtering, taking a solid product, drying at 110 ℃, and grinding to obtain TiO 2 Molecular sieve type/L;
3. weighing 2mg of TiO 2 Adding the/L type molecular sieve and 0.19mL silver nitrate solution (0.01 mM) into 9.8mL deionized water, heating at 80 ℃, stirring, adsorbing for 2h, cooling to room temperature, filtering and drying to obtain silver ion TiO 2 Molecular sieve type/L;
4. make silver ion TiO 2 the/L type molecular sieve and the ABS plastic are prepared according to the following weight ratio of 1:19, uniformly mixing, and performing melt blending through a double-screw extruder at the temperature of 230 ℃ and the rotating speed of a main machine of 300rpm to obtain the silver ion TiO 2 the/L type molecular sieve composite antibacterial plastic.
Example 9
The preparation method of the silver ion titanium dioxide/L type molecular sieve antibacterial plastic provided by the embodiment comprises the following steps:
1. 50.79g of deionized water, 8.78g of KOH and a portion of deionized water were weighed to prepare a KOH solution, 4.07g of Al (OH) 3 Dissolving in KOH solution, putting into a hydrothermal kettle, heating to be clear at 80 ℃, then adding 40g of silica sol and the rest deionized water, carrying out ultrasonic treatment, uniformly mixing to form sol, putting the sol into a reaction kettle, and reacting for 48 hours at 180 ℃. After the reaction is finished, washing the product to be neutral by deionized water, filtering the product, drying the product for 8 hours at 110 ℃, and grinding the product to obtain an L-shaped molecular sieve;
2. adding 2mg of L-type molecular sieve into a mixed solution of 60 mu L of ammonia water and 10mL of ethanol, adding 750 mu L of tetrabutyl titanate, performing ultrasonic treatment until the mixture is uniformly mixed, reacting for 6 hours at 80 ℃, performing centrifugal washing by using ethanol and deionized water after the reaction is finished, filtering, taking a solid product, drying at 110 ℃, and grinding to obtain TiO 2 Molecular sieve type/L;
3. weighing 2mg of TiO 2 Adding the/L type molecular sieve and 0.57mL silver nitrate solution (0.01 mM) into 9.6mL deionized water, heating at 80 ℃, stirring, adsorbing for 2h, cooling to room temperature, filtering and drying to obtain silver ion TiO 2 Molecular sieve type/L;
4. TiO 2 silver ion 2 the/L type molecular sieve and the ABS plastic are prepared according to the following weight ratio of 1:19, uniformly mixing, and performing melt blending by a double-screw extruder at the temperature of 230 ℃ and the rotating speed of a main machine of 300rpm to obtain the silver ion TiO 2 The L-type molecular sieve composite antibacterial plastic.
The X-ray energy spectrum analysis of the titanium dioxide/L-type molecular sieve containing silver ions prepared in this example is shown in fig. 5, from which the peaks of silver ions can be seen in addition to potassium, aluminum, silicon and oxygen, which proves that silver ions are successfully loaded on the L-type molecular sieve.
Comparative example 1
Pure ABS plastic is melted and blended by a double screw extruder at 200 ℃, extruded and granulated, and pressed into a plastic plate with the thickness of 50mm multiplied by 4mm at 210 ℃ for an antibacterial test.
Comparative example 2
The preparation method of the titanium dioxide/L type molecular sieve antibacterial plastic provided by the comparative example comprises the following steps:
1. 31.68g deionized water, 7.82g KOH was weighed, a part of the deionized water was added to prepare a KOH solution, 4.16g Al (OH) 3 Dissolving in KOH solution, putting into a hydrothermal kettle, heating to be clear at 80 ℃, then adding 40g of silica sol and the rest deionized water, carrying out ultrasonic treatment, uniformly mixing to form sol, putting the sol into a reaction kettle, and reacting for 48 hours at 180 ℃. After the reaction is finished, washing the mixture to be neutral by deionized water, filtering the mixture, drying the mixture for 8 hours at 110 ℃, and grinding the mixture to obtain an L-shaped molecular sieve;
2. adding 50mg of L-type molecular sieve into a mixed solution of 200 mu L of ammonia water and 10mL of ethanol, adding 375 mu L of tetrabutyl titanate, performing ultrasonic treatment until the mixture is uniformly mixed, reacting for 24 hours at 40 ℃, performing centrifugal washing by using ethanol and deionized water after the reaction is finished, filtering, taking a solid product, drying at 110 ℃, and grinding to obtain TiO 2 Molecular sieves of type/L;
3. mixing TiO with 2 the/L type molecular sieve and the ABS plastic are mixed according to the proportion of 1:19, uniformly mixing, and performing melt blending by a double-screw extruder at the temperature of 230 ℃ and the rotating speed of a main machine of 300rpm to obtain the silver ion TiO 2 the/L type molecular sieve composite antibacterial plastic.
Comparative example 3
The preparation method of the silver ion titanium dioxide/L type molecular sieve antibacterial plastic provided by the comparative example comprises the following steps:
1. 31.68g deionized water, 7.82g KOH was weighed, a part of the deionized water was added to prepare a KOH solution, 4.16g Al (OH) 3 Dissolving in KOH solution, putting the KOH solution into a hydrothermal kettle, heating the KOH solution to be clear at 80 ℃, then adding 40g of silica sol and the rest deionized water, carrying out ultrasonic treatment, uniformly mixing to form sol, putting the sol into a reaction kettle, and reacting for 48 hours at 180 ℃. After the reaction is finished, washing the mixture to be neutral by deionized water, filtering the mixture, drying the mixture for 8 hours at 110 ℃, and grinding the mixture to obtain an L-shaped molecular sieve;
2. weighing 176.4mg of L-shaped molecular sieve and 19.6mg of silver nitrate, adding the L-shaped molecular sieve and the silver nitrate into 75mL of deionized water, adsorbing for 6 hours at room temperature, filtering and drying to obtain a silver ion/L-shaped molecular sieve;
3. mixing silver ion/L type molecular sieve and ABS plastic according to the proportion of 1:19, uniformly mixing, and performing melt blending through a double-screw extruder at the temperature of 230 ℃ and the rotating speed of a main machine of 300rpm to obtain the silver ion TiO 2 the/L type molecular sieve composite antibacterial plastic.
The X-ray energy spectrum analysis of the silver ion titanium dioxide/L-type molecular sieve prepared in this example is shown in fig. 5, from which the peak of silver ion can be seen in addition to potassium, aluminum, silicon and oxygen, which proves that silver ion is successfully loaded on the L-type molecular sieve.
Test for antibacterial Effect
The test method comprises the following steps: and pressing the obtained silver ion titanium dioxide/L type molecular sieve antibacterial plastic into a plastic plate at 210 ℃, wherein the size of the plastic plate is 50mm multiplied by 4mm, and selecting escherichia coli and staphylococcus aureus according to the antibacterial performance of a test sample and a comparison sample of the standard GB/T31402-2015. Each of the above samples was tested in duplicate for 5 specimens, and the average was taken. The results of the antibacterial ratio (%) are shown in the following table:
categories Escherichia coli Staphylococcus aureus
Example 1 68.4 65.2
Example 2 92.4 90.4
Example 3 99.3 99.2
Example 4 78.3 75.7
Example 5 87.2 84.4
Example 6 95.3 91.7
Example 7 97.0 94.9
Example 8 71.4 70.9
Example 9 88.5 82.9
Comparative example 1 0.1 0.1
Comparative example 2 24.7 22.4
Comparative example 3 40.5 35.9
From the above table it can be seen that: examples 1 to 9 show the preparation of silver ion TiO according to the invention 2 the/L type molecular sieve antibacterial plastic has excellent antibacterial rate, wherein the experimental results of the composite materials with different antibacterial agent contents in the examples 1-3 show that the composite materials have good antibacterial effect on escherichia coli and staphylococcus aureus, and when the composite materials contain silver ions TiO 2 The higher the content of the/L type molecular sieve, i.e. when the silver ion is TiO 2 the/L type molecular sieve and the ABS plastic are prepared according to the following weight ratio of 1:19 hours, the composite resistsThe better the bacteria rate is, the highest can reach 99%. This is because the L-type molecular sieve has a larger volume effect, and the higher the content of the antibacterial agent is, the silver nitrate and TiO exposed on the outer surface of the ABS plastic 2 More, in addition, the L-shaped molecular sieve has very large specific surface area and excellent adsorption performance, is favorable for adsorbing water vapor and oxygen from air and is TiO 2 The photocatalytic antibacterial provides the required raw material, and the existence of water vapor helps the outer surface of the plastic to generate free silver ions.
Examples 3 to 5 show that the antibacterial effect is the best when the reaction temperature of step 1 is 180 ℃ and the reaction time is 48 hours; examples 3, 6 and 7 show that the antibacterial effect is best when the reaction temperature of step 2 is 40 ℃ and the reaction time is 24 hours;
comparative example 1 is an antibacterial effect test of pure ABS, and comparative examples 2 to 3 are single TiO respectively 2 Comparative examples of type/L molecular sieves and single silver ion type/L molecular sieves, it can be seen from comparative example 1 that pure ABS without an added antibacterial agent has substantially no antibacterial effect, while comparative examples 2 and 3 show that TiO alone has little antibacterial effect 2 the/L type molecular sieve or the single silver ion/L type molecular sieve serving as the antibacterial agent is compounded with ABS, so that the ABS cannot be endowed with excellent antibacterial performance. The silver ion TiO prepared by the invention 2 the/L type molecular sieve solves the problem of TiO 2、 And the silver ions and the common plastic can not effectively endow the plastic with high antibacterial performance after being compounded, so that the antibacterial effects of the silver ions and the common plastic are effectively exerted.

Claims (10)

1. A preparation method of silver ion titanium dioxide/L type molecular sieve antibacterial plastic is characterized by comprising the following steps:
(1) Weighing KOH and Al (OH) 3 Uniformly mixing silica sol and deionized water to form sol, placing the sol in a reaction kettle for reaction at the reaction temperature of 120-200 ℃ for 36-52 hours, cooling to room temperature, and performing suction filtration, washing, drying and grinding to form an L-shaped molecular sieve;
(2) Adding an L-type molecular sieve into a mixed solution of ethanol and ammonia water, adding tetrabutyl titanate, uniformly mixing, reacting at the temperature of between 40 and 80 ℃, and reacting4-24 h, centrifuging, washing, drying and grinding after the reaction is finished to obtain TiO 2 Molecular sieve type/L;
(3) Adding TiO into the mixture 2 Soaking the/L type molecular sieve in silver nitrate solution for adsorption, filtering and drying to obtain silver ion TiO 2 Molecular sieves of type/L;
(4) Weighing ABS plastic and mixing the ABS plastic with silver ion TiO 2 And uniformly mixing the/L type molecular sieve, and then melting and blending to obtain the silver ion titanium dioxide/L type molecular sieve antibacterial plastic.
2. The method for preparing silver ion titanium dioxide/L type molecular sieve antibacterial plastic according to claim 1, wherein in the step (1), KOH is first dissolved in partially deionized water to form a KOH solution, and then Al (OH) is added 3 Dissolved in KOH solution and heated until the solution is clear, then added to silica sol and the remaining deionized water to form a sol.
3. The preparation method of the silver ion titanium dioxide/L type molecular sieve antibacterial plastic according to claim 1, wherein the reaction temperature of the reaction kettle in the step (1) is 180 ℃, and the reaction time is 48h.
4. The method for preparing silver ion titanium dioxide/L type molecular sieve antibacterial plastic according to claim 1, wherein in the step (1), KOH: al (OH) 3 ：SiO 2 ：H 2 The molar ratio of O is 1:1:2.5:50 to 3:1:10:200.
5. the method for preparing the silver ion titanium dioxide/L type molecular sieve antibacterial plastic according to claim 1, wherein in the step (2), the ratio of the L type molecular sieve: ammonia water: the mass ratio of tetrabutyl titanate is 1:0.01:0.05 to 1:0.2:0.7.
6. the method for preparing the silver ion titanium dioxide/L type molecular sieve antibacterial plastic according to claim 1, wherein the reaction temperature in the step (2) is 40 ℃, and the reaction time is 24h.
7. The method for preparing silver ion titanium dioxide/L type molecular sieve antibacterial plastic according to claim 1, characterized in that in the step (3), silver nitrate: tiO 2 2 The mass concentration of the/L type molecular sieve is 3:2000 to 3:20.
8. the method for preparing silver ion titanium dioxide/L type molecular sieve antibacterial plastic according to claim 7, characterized in that in the step (3), silver nitrate: tiO 2 2 The mass concentration of the/L type molecular sieve is 3:2000, the adsorption temperature is 80 ℃, and the adsorption time is 2h.
9. The method for preparing silver ion titanium dioxide/L type molecular sieve antibacterial plastic according to claim 1, wherein in the step (4), silver ion TiO is used 2 Molecular sieve type/L: the mass ratio of the ABS plastic is 1:100 to 1:19.
10. the method for preparing the silver ion titanium dioxide/L type molecular sieve antibacterial plastic according to claim 1, wherein the temperature of the melt blending in the step (4) is 170-230 ℃, and the rotation speed of a main engine is 150-300rpm.
CN202210911463.8A 2022-07-30 2022-07-30 Preparation method of silver ion titanium dioxide/L type molecular sieve antibacterial plastic Pending CN115197527A (en)

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