CN111763293A - Ag-doped nano TiO2Antibacterial material of grafted polyacrylate and its preparing process - Google Patents
Ag-doped nano TiO2Antibacterial material of grafted polyacrylate and its preparing process Download PDFInfo
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- CN111763293A CN111763293A CN202010652095.0A CN202010652095A CN111763293A CN 111763293 A CN111763293 A CN 111763293A CN 202010652095 A CN202010652095 A CN 202010652095A CN 111763293 A CN111763293 A CN 111763293A
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- 238000000034 method Methods 0.000 title description 11
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 21
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 18
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims abstract description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 12
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims abstract description 12
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- 238000001035 drying Methods 0.000 claims description 25
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- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 21
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 13
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 230000001678 irradiating effect Effects 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
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- 239000000203 mixture Substances 0.000 description 33
- 239000010936 titanium Substances 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 7
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 230000010355 oscillation Effects 0.000 description 5
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F33/00—Other mixers; Mixing plants; Combinations of mixers
- B01F33/45—Magnetic mixers; Mixers with magnetically driven stirrers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/10—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to inorganic materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
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Abstract
The invention relates to the technical field of antibacterial materials, and discloses Ag-doped nano TiO2The antibacterial material of grafted polyacrylate is prepared with tetrabutyl titanate and silver nitrate as material and through ageing to obtain Ag-Ti precursor,treating with boiling water, and calcining to obtain Ag-doped nano TiO2Porous spheres, Ag doping to TiO2Absorb band edge red shift and reduce TiO2Forbidden band width, Ag+Can capture photoproduction electrons and reduce the photoproduction electron-hole recombination rate, Ag-Ti precursors are processed by boiling water to form a large number of pore channels, and Ag is doped with nano TiO2A large amount of hydroxyl on the surface of the porous ball reacts with gamma-mercaptopropyl trimethoxy silane to obtain the thiolated Ag doped nano TiO2Porous ball, benzophenone as photoinitiator, methacrylic acid and other monomers as raw materials, and through mercapto-olefin photopolymerization to obtain Ag doped nanometer TiO2Grafting polyacrylate and improving Ag-doped nano TiO2The dispersion and compatibility in the polyacrylate endow the polyacrylate with excellent photocatalytic antibacterial performance.
Description
Technical Field
The invention relates to the technical field of antibacterial materials, in particular to Ag-doped nano TiO2An antibacterial material of grafted polyacrylate and its preparation method are disclosed.
Background
With the development of science and technology, people can go out in the world conveniently, and the possibility of spreading various epidemic diseases in the world is increased, on the other hand, the problem of water pollution is increasingly serious, so that more and more pathogenic bacteria are generated in the environment, new infectious diseases can be caused, and more threats are generated to the health of people, so that people pay more and more attention to the research of antibacterial materials, and a large number of scientists are exploring an effective sterilization method, including ultraviolet irradiation, ozonization, photocatalysis and the like, wherein the photocatalytic sterilization is considered to be one of the most sustainable and cost-effective sterilization modes.
At present, a common mode is that a certain amount of proper antibacterial material with good stability is added into a coating to prepare the antibacterial coating, the antibacterial coating can be directly coated on the surfaces of various materials, the use is very convenient, the traditional coating has poor mildew-proof and antibacterial effects, and the research and popularization of the antibacterial coating are very necessary from the aspects of environmental protection and health.
The acrylic acid coating has the advantages of pollution resistance, acid resistance and alkali resistance, so that the acrylic acid coating is widely applied, but polyacrylate does not have an antibacterial effect, so that acrylic acid needs to be subjected to chemical modification treatment to enable the acrylic acid to have the antibacterial effect, and TiO in a plurality of photocatalysts2The titanium dioxide has the functions of sterilization, antivirus and degradation of bacteria and organic matters under visible light and ultraviolet rays, has the advantages of strong photocatalytic power, low price, rich raw materials, stable performance, no pollution and the like, is widely applied in the field of photocatalysis, but has the defects of wide band gap, easy recombination of photogenerated electrons and holes and narrow light absorption range, and seriously restricts the application of the titanium dioxide in the field of photocatalysis, so that the Ag-doped nano TiO is adopted2The way of grafting the polyacrylate solves the above problems.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides Ag-doped nano TiO2The antibacterial material of grafted polyacrylate and its preparation process solve the problem of no antibacterial performance of acrylic acid and TiO2Wide band gap, easy recombination of photo-generated electrons and holes, and narrow light absorption range.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: ag-doped nano TiO2Antibacterial material of grafted polyacrylate, Ag doped nanometer TiO2The preparation method of the antibacterial material of the grafted polyacrylate comprises the following steps:
(1) adding ethylene glycol, tetrabutyl titanate and silver nitrate into a beaker, placing the beaker in a magnetic stirring device, stirring the beaker in a closed manner at normal temperature for 8 to 12 hours, adding deionized water and acetone, stirring the mixture for 20 to 40 minutes, aging the obtained mixed solution for 0.5 to 2 hours, centrifuging the mixed solution and drying the mixed solution to obtain an Ag-Ti precursor product;
(2) placing the obtained Ag-Ti precursor product in deionized water, uniformly oscillating with ultrasonic wave, placing in a magnetic stirring device, stirring for 1-3h at 80-120 ℃, centrifuging, washing and drying, placing the dried product in a tubular furnace, calcining for 1-3h at 280-320 ℃ to obtain the Ag-doped nano TiO2A porous ball;
(3) adding toluene, triethylamine, gamma-mercaptopropyl trimethoxy silane and Ag-doped nano TiO into a beaker2Placing the porous ball in ice-water bath, performing ultrasonic treatment for 20-40min to disperse uniformly, placing the porous ball at the temperature of 100 ℃ and 120 ℃, irradiating the porous ball by an ultraviolet lamp, performing reflux stirring reaction for 2-6h, cooling, performing low-pressure suction filtration and drying to obtain the thiolated Ag doped nano TiO2A porous ball;
(4) adding a photoinitiator benzophenone, methacrylic acid, methyl methacrylate, n-butyl methacrylate and sulfhydrylation Ag doped nano TiO into a beaker2Introducing nitrogen into the porous ball in the dark, stirring for 5-15min under the irradiation of ultraviolet lamp, filtering, dissolving with dry tetrahydrofuran to obtain product, adding n-hexane, repeating the above steps for three times, filtering, and drying to obtain Ag-doped nanometer TiO2Antibacterial grafted polyacrylateA material.
Preferably, the mass ratio of tetrabutyl titanate to silver nitrate in the step (1) is 100: 0.8-1.5.
Preferably, magnetic stirring device includes the main part in step (2), and the right side swing joint of main part has the motor, and the top swing joint of motor has the driving shaft, and the centre swing joint of driving shaft has the action wheel, and the top swing joint of driving shaft has the connecting rod, and the left side swing joint of connecting rod has driven shaft, and the bottom swing joint of driven shaft has the driven wheel, and the top swing joint of driven shaft has the end cover, and the bottom swing joint of main part has the magnetic stirring module, and the right side swing joint of main part has control module.
Preferably, in the step (3), gamma-mercaptopropyltrimethoxysilane and Ag are doped with nano TiO2The mass ratio of the porous ball is 100: 70-100.
Preferably, benzophenone, methacrylic acid, methyl methacrylate, n-butyl methacrylate and thiolated Ag in the step (4) are doped with nano TiO2The mass ratio of the porous ball is 10-15:15-25:50-70:100: 0.5-3.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the Ag-doped nano TiO2An antibacterial material grafted with polyacrylate is prepared from tetrabutyl titanate and silver nitrate through ageing to obtain Ag-Ti precursor, treating in boiling water, calcining to obtain Ag doped nano TiO2Porous spheres, doping of Ag to TiO2Red shift of absorption band edge and reduced TiO2The forbidden band width of the Ag-Ag alloy can expand the spectral response range of the Ag-Ag alloy, and is beneficial to absorbing sunlight+The method has the advantages that photoproduction electrons can be effectively captured, reduction reaction is carried out to generate simple substance Ag, the number of photoproduction holes is relatively increased, so that the recombination rate of photoproduction electrons and holes is reduced, the service life of carriers is prolonged, when the Ag-Ti precursor is treated by boiling water, hydrolysis is simultaneously carried out inside and outside the Ag-Ti precursor, a large number of pore channels and rough surfaces are formed, the specific surface area is increased, more surface photoreactive active sites are introduced, and the photocatalytic antibacterial efficiency is improved.
The Ag-doped nano TiO2Antibacterial material of grafted polyacrylate, Ag doped nanometer TiO2Porous ball as raw material is irradiated by ultraviolet ray and TiO2Electrons are excited from the valence band to the conduction band and electrons and holes migrate to the surface, thereby forming electron-hole pairs, which electrons cause Ti4+To Ti3+The holes react with surface oxygen ions to form oxygen vacancies, adsorb dissociated water molecules, and the adsorbed water molecules are adsorbed on TiO2A large amount of hydroxyl groups are formed on the surface to promote the reaction with silicon methoxyl of gamma-mercaptopropyl trimethoxy silane, and the mercapto Ag doped nano TiO is obtained2The Ag-doped nano TiO is obtained by carrying out an addition reaction on sulfydryl and alkenyl, taking benzophenone as a photoinitiator, methacrylic acid and other monomers as raw materials and carrying out a sulfydryl-olefin photopolymerization method2Grafting polyacrylate to improve Ag doping of nano TiO2The dispersion and compatibility in the polyacrylate endow the polyacrylate with excellent photocatalytic antibacterial performance.
Drawings
FIG. 1 is a front sectional structural schematic view of a magnetic stirring apparatus;
fig. 2 is a schematic view of a gear transmission structure.
1. A main body; 2. a motor; 3. a drive shaft; 4. a driving wheel; 5. a connecting rod; 6. a driven shaft; 7. a driven wheel; 8. an end cap; 9. a magnetic stirring module; 10. and a control module.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: ag-doped nano TiO2Antibacterial material of grafted polyacrylate, Ag doped nano TiO2The preparation method of the antibacterial material of the grafted polyacrylate comprises the following steps:
(1) adding ethylene glycol, tetrabutyl titanate and silver nitrate into a beaker, wherein the mass ratio of the ethylene glycol to the tetrabutyl titanate to the silver nitrate is 100:0.8-1.5, placing the beaker in a magnetic stirring device, stirring the beaker at normal temperature for 8-12h in a closed manner, adding deionized water and acetone, stirring the mixture for 20-40min, aging the obtained mixed solution for 0.5-2h, centrifuging and drying the mixed solution to obtain an Ag-Ti precursor product;
(2) placing the obtained Ag-Ti precursor product in deionized water, performing ultrasonic oscillation uniformly, and then placing the product in a magnetic stirring device, wherein the magnetic stirring device comprises a main body, the right side of the main body is movably connected with a motor, the top of the motor is movably connected with a driving shaft, the middle of the driving shaft is movably connected with a driving wheel, the top of the driving shaft is movably connected with a connecting rod, the left side of the connecting rod is movably connected with a driven shaft, the bottom of the driven shaft is movably connected with a driven wheel, the top of the driven shaft is movably connected with an end cover, the bottom of the main body is movably connected with a magnetic stirring module, the right side of the main body is movably connected with a control module, stirring is performed for 1-3h at 80-120 ℃, centrifuging, washing and drying are performed, a dried product is placed in a2A porous ball;
(3) adding toluene, triethylamine, gamma-mercaptopropyl trimethoxy silane and Ag-doped nano TiO into a beaker2Placing the porous ball with the mass ratio of 100:70-100 in an ice water bath, performing ultrasonic treatment for 20-40min to disperse uniformly, placing the porous ball at the temperature of 100 ℃ and 120 ℃, irradiating the porous ball by an ultraviolet lamp, performing reflux stirring reaction for 2-6h, cooling, performing low-pressure suction filtration and drying to obtain the thiolated Ag doped nano TiO2A porous ball;
(4) adding a photoinitiator benzophenone, methacrylic acid, methyl methacrylate, n-butyl methacrylate and sulfhydrylation Ag doped nano TiO into a beaker2The weight ratio of the five porous spheres is 10-15:15-25:50-70:100:0.5-3, nitrogen is introduced under the condition of keeping out of the sun, stirring is carried out for 5-15min under the irradiation of an ultraviolet lamp, filtering is carried out, then a product obtained by dissolving dried tetrahydrofuran is added, n-hexane is added, the processes are repeated for three times, filtering and drying are carried out, and the Ag-doped nano TiO is obtained2Antibacterial material grafted with polyacrylate.
Example 1
(1) Adding ethylene glycol, tetrabutyl titanate and silver nitrate into a beaker, wherein the mass ratio of the ethylene glycol to the tetrabutyl titanate to the silver nitrate is 100:0.8, placing the beaker into a magnetic stirring device, stirring the beaker at normal temperature for 8 hours in a closed manner, adding deionized water and acetone, stirring the mixture for 20 minutes, aging the obtained mixed solution for 0.5 hour, centrifuging the mixed solution, and drying the mixed solution to obtain an Ag-Ti precursor product;
(2) the obtained Ag-Ti precursor product is placed in deionized water, ultrasonic oscillation is uniform, and then the product is placed in a magnetic stirring device, the magnetic stirring device comprises a main body, the right side of the main body is movably connected with a motor, the top of the motor is movably connected with a driving shaft, the middle of the driving shaft is movably connected with a driving wheel, the top of the driving shaft is movably connected with a connecting rod, the left side of the connecting rod is movably connected with a driven shaft, the bottom of the driven shaft is movably connected with a driven wheel, the top of the driven shaft is movably connected with an end cover, the bottom of the main body is movably connected with a magnetic stirring module, the right side of the main body is movably connected with a control module, stirring is carried out for 1h at 80 ℃, centrifuging, washing and drying are2A porous ball;
(3) adding toluene, triethylamine, gamma-mercaptopropyl trimethoxy silane and Ag-doped nano TiO into a beaker2Placing the porous ball and the porous ball in an ice-water bath at a mass ratio of 100:70, performing ultrasonic treatment for 20min to disperse the porous ball uniformly, placing the porous ball and the porous ball at 100 ℃, irradiating the porous ball by using an ultraviolet lamp, performing reflux stirring reaction for 2h, cooling, performing low-pressure suction filtration and drying to obtain the thiolated Ag-doped nano TiO2A porous ball;
(4) adding a photoinitiator benzophenone, methacrylic acid, methyl methacrylate, n-butyl methacrylate and sulfhydrylation Ag doped nano TiO into a beaker2The weight ratio of the five is 10:15:50:100:0.5, nitrogen is introduced under the condition of keeping out of the sun, the mixture is stirred for 5min under the irradiation of an ultraviolet lamp, the mixture is filtered, then a product obtained by dissolving dry tetrahydrofuran is added, normal hexane is added, the processes are repeated for three times, and the mixture is filtered and dried to obtain the Ag-doped nano TiO2Antibacterial material grafted with polyacrylate.
Example 2
(1) Adding ethylene glycol, tetrabutyl titanate and silver nitrate into a beaker, wherein the mass ratio of the ethylene glycol to the tetrabutyl titanate to the silver nitrate is 100:1.2, placing the beaker into a magnetic stirring device, stirring the beaker at normal temperature for 10 hours in a closed manner, adding deionized water and acetone, stirring the mixture for 30 minutes, aging the obtained mixed solution for 1.3 hours, centrifuging the mixed solution, and drying the mixed solution to obtain an Ag-Ti precursor product;
(2) putting the obtained Ag-Ti precursor product into deionized water, and uniformly oscillating by ultrasonicThe magnetic stirring device is arranged in the magnetic stirring device again, the magnetic stirring device comprises a main body, the right side swing joint of main body has the motor, the top swing joint of motor has the driving shaft, the middle swing joint of driving shaft has the action wheel, the top swing joint of driving shaft has the connecting rod, the left side swing joint of connecting rod has the driven shaft, the bottom swing joint of driven shaft has the driven wheel, the top swing joint of driven shaft has the end cover, the bottom swing joint of main body has the magnetic stirring module, the right side swing joint of main body has control module, stir 2h under 100 ℃, it is centrifugal, wash and dry, arrange the dry product in the tube furnace, calcine 2h under 300 ℃, obtain Ag and mix nanometer TiO 2h2A porous ball;
(3) adding toluene, triethylamine, gamma-mercaptopropyl trimethoxy silane and Ag-doped nano TiO into a beaker2Placing the porous ball and the porous ball in an ice-water bath at a mass ratio of 100:85, performing ultrasonic treatment for 30min to disperse uniformly, placing the mixture at 110 ℃, irradiating the mixture by using an ultraviolet lamp, performing reflux stirring reaction for 4h, cooling, performing low-pressure suction filtration and drying to obtain the thiolated Ag doped nano TiO2A porous ball;
(4) adding a photoinitiator benzophenone, methacrylic acid, methyl methacrylate, n-butyl methacrylate and sulfhydrylation Ag doped nano TiO into a beaker2The weight ratio of the five porous spheres is 13:20:60:100:1.8, nitrogen is introduced under the condition of keeping out of the sun, the mixture is stirred for 10min under the irradiation of an ultraviolet lamp, the mixture is filtered, then a product obtained by dissolving dry tetrahydrofuran is added, normal hexane is added, the processes are repeated for three times, and the mixture is filtered and dried to obtain the Ag-doped nano TiO2Antibacterial material grafted with polyacrylate.
Example 3
(1) Adding ethylene glycol, tetrabutyl titanate and silver nitrate into a beaker, wherein the mass ratio of the ethylene glycol to the tetrabutyl titanate to the silver nitrate is 100:1, placing the beaker into a magnetic stirring device, stirring the beaker at normal temperature for 9 hours in a closed manner, adding deionized water and acetone, stirring the mixture for 20 minutes, aging the obtained mixed solution for 1 hour, centrifuging the mixed solution, and drying the mixed solution to obtain an Ag-Ti precursor product;
(2) putting the obtained Ag-Ti precursor product into deionized water, uniformly performing ultrasonic oscillation, and then putting the product into a magnetic stirring device, wherein the magnetic stirring device comprises a main bodyThe body, the right side swing joint of main part has the motor, the top swing joint of motor has the driving shaft, the centre swing joint of driving shaft has the action wheel, the top swing joint of driving shaft has the connecting rod, the left side swing joint of connecting rod has driven shaft, the bottom swing joint of driven shaft has the driven wheel, the top swing joint of driven shaft has the end cover, the bottom swing joint of main part has magnetic stirring module, the right side swing joint of main part has control module, stir 2h under 90 ℃, it is centrifugal, washing and drying, arrange the dry product in the tube furnace, calcine 1h under 290 ℃, obtain Ag doping nanometer TiO2A porous ball;
(3) adding toluene, triethylamine, gamma-mercaptopropyl trimethoxy silane and Ag-doped nano TiO into a beaker2Placing the porous ball and the porous ball in an ice-water bath at a mass ratio of 100:80, performing ultrasonic treatment for 20min to disperse uniformly, placing the mixture at 100 ℃, irradiating the mixture by using an ultraviolet lamp, performing reflux stirring reaction for 6h, cooling, performing low-pressure suction filtration and drying to obtain the thiolated Ag doped nano TiO2A porous ball;
(4) adding a photoinitiator benzophenone, methacrylic acid, methyl methacrylate, n-butyl methacrylate and sulfhydrylation Ag doped nano TiO into a beaker2The weight ratio of the five is 12:18:55:100:1.7, nitrogen is introduced under the condition of keeping out of the sun, the mixture is stirred for 10min under the irradiation of an ultraviolet lamp, the mixture is filtered, then a product obtained by dissolving dry tetrahydrofuran is added, normal hexane is added, the processes are repeated for three times, and the mixture is filtered and dried to obtain the Ag-doped nano TiO2Antibacterial material grafted with polyacrylate.
Example 4
(1) Adding ethylene glycol, tetrabutyl titanate and silver nitrate into a beaker, wherein the mass ratio of the ethylene glycol to the tetrabutyl titanate to the silver nitrate is 100:1.5, placing the beaker into a magnetic stirring device, stirring the beaker at normal temperature for 12 hours in a closed manner, adding deionized water and acetone, stirring the mixture for 40 minutes, aging the obtained mixed solution for 2 hours, centrifuging the mixed solution, and drying the mixed solution to obtain an Ag-Ti precursor product;
(2) placing the obtained Ag-Ti precursor product in deionized water, performing ultrasonic oscillation uniformly, and placing in a magnetic stirring device, wherein the magnetic stirring device comprises a main body, the right side of the main body is movably connected with a motor, and the top of the motor is connected with a motorThe device comprises a driving shaft, a driving wheel, a connecting rod, a driven shaft, a driven wheel, an end cover, a magnetic stirring module, a control module, a centrifugal machine, a washing machine and a drying machine, wherein the driving shaft is movably connected with the middle of the driving shaft, the top of the driving shaft is movably connected with the connecting rod, the left side of the connecting rod is movably connected with the driven shaft, the bottom of the driven shaft is movably connected with the driven wheel, the top of the driven shaft is movably connected with the end cover, the bottom of the main body is movably connected with the magnetic stirring module, the right side of the main body is movably connected2A porous ball;
(3) adding toluene, triethylamine, gamma-mercaptopropyl trimethoxy silane and Ag-doped nano TiO into a beaker2Placing the porous ball and the porous ball in an ice-water bath at a mass ratio of 100:100, performing ultrasonic treatment for 40min to disperse uniformly, placing the mixture at 120 ℃, irradiating the mixture by using an ultraviolet lamp, performing reflux stirring reaction for 6h, cooling, performing low-pressure suction filtration and drying to obtain the thiolated Ag doped nano TiO2A porous ball;
(4) adding a photoinitiator benzophenone, methacrylic acid, methyl methacrylate, n-butyl methacrylate and sulfhydrylation Ag doped nano TiO into a beaker2The weight ratio of the five is 15:25:70:100:3, nitrogen is introduced under the condition of keeping out of the sun, the mixture is stirred for 15min under the irradiation of an ultraviolet lamp, the mixture is filtered, then a product obtained by dissolving the mixture with dry tetrahydrofuran is added with n-hexane, the process is repeated for three times, and the mixture is filtered and dried to obtain the Ag-doped nano TiO2Antibacterial material grafted with polyacrylate.
Comparative example 1
(1) Adding ethylene glycol, tetrabutyl titanate and silver nitrate into a beaker, wherein the mass ratio of the ethylene glycol to the tetrabutyl titanate to the silver nitrate is 100:0.5, placing the beaker into a magnetic stirring device, stirring the beaker at normal temperature for 8 hours in a closed manner, adding deionized water and acetone, stirring the mixture for 40 minutes, aging the obtained mixed solution for 0.5 hour, centrifuging the mixed solution, and drying the mixed solution to obtain an Ag-Ti precursor product;
(2) placing the obtained Ag-Ti precursor product in deionized water, performing ultrasonic oscillation uniformly, and placing in a magnetic stirring device, wherein the magnetic stirring device comprises a main body, the right side of the main body is movably connected with a motor, the top of the motor is movably connected with a driving shaft, and the middle of the driving shaft is movably connected with a driving shaftThe device comprises a driving wheel, a connecting rod is movably connected to the top of a driving shaft, a driven shaft is movably connected to the left side of the connecting rod, a driven wheel is movably connected to the bottom of the driven shaft, an end cover is movably connected to the top of the driven shaft, a magnetic stirring module is movably connected to the bottom of a main body, a control module is movably connected to the right side of the main body, the main body is stirred for 1 hour at 120 ℃, centrifuged, washed and dried, a dried product is placed in a tube furnace and calcined for 1 hour at 320 ℃, and Ag-doped nano TiO is obtained2A porous ball;
(3) adding toluene, triethylamine, gamma-mercaptopropyl trimethoxy silane and Ag-doped nano TiO into a beaker2Placing the porous ball and the porous ball in an ice-water bath at a mass ratio of 100:60, performing ultrasonic treatment for 40min to disperse uniformly, placing the mixture at 100 ℃, irradiating the mixture by using an ultraviolet lamp, performing reflux stirring reaction for 6h, cooling, performing low-pressure suction filtration and drying to obtain the thiolated Ag doped nano TiO2A porous ball;
(4) adding a photoinitiator benzophenone, methacrylic acid, methyl methacrylate, n-butyl methacrylate and sulfhydrylation Ag doped nano TiO into a beaker2The weight ratio of the five is 8:10:40:100:4, nitrogen is introduced under the condition of keeping out of the sun, the mixture is stirred for 15min under the irradiation of an ultraviolet lamp, the mixture is filtered, then a product obtained by dissolving the mixture with dry tetrahydrofuran is added with n-hexane, the process is repeated for three times, and the mixture is filtered and dried to obtain the Ag-doped nano TiO2Antibacterial material grafted with polyacrylate.
Ag-doped nano TiO obtained in the examples and the comparative examples2Pouring the antibacterial material of grafted polyacrylate into a mold to be cured into a film, irradiating with ultraviolet for 60min, and diluting 100ul to 106Inoculating CFU/ml test bacterial liquid on the front surface of the sample membrane irradiated by ultraviolet, culturing at constant temperature for 12h, eluting bacteria on the surface of the sample membrane with physiological saline, and adding the eluted bacteria at a ratio of 1:106Diluting with normal saline, culturing with proper amount of bacterial liquid and solid culture medium, observing with microscope, calculating the concentration, and calculating the antibacterial rate, with test standard GB/T23763-one 2009.
Claims (5)
1. Ag-doped nano TiO2The antibacterial material of grafted polyacrylate is characterized in that: the Ag is doped with nano TiO2The preparation method of the antibacterial material of the grafted polyacrylate comprises the following steps:
(1) adding tetrabutyl titanate and silver nitrate into ethylene glycol, placing the ethylene glycol in a magnetic stirring device, stirring for 8-12h at normal temperature in a closed manner, adding deionized water and acetone, stirring for 20-40min, aging the obtained mixed solution for 0.5-2h, centrifuging and drying to obtain an Ag-Ti precursor product;
(2) placing the obtained Ag-Ti precursor product in deionized water, uniformly oscillating with ultrasonic wave, placing in a magnetic stirring device, stirring for 1-3h at 80-120 ℃, centrifuging, washing and drying, placing the dried product in a tubular furnace, calcining for 1-3h at 280-320 ℃ to obtain the Ag-doped nano TiO2A porous ball;
(3) adding triethylamine, gamma-mercaptopropyl trimethoxy silane and Ag-doped nano TiO into toluene2Placing the porous ball in ice-water bath, performing ultrasonic treatment for 20-40min to disperse uniformly, placing the porous ball at the temperature of 100 ℃ and 120 ℃, irradiating the porous ball by an ultraviolet lamp, performing reflux stirring reaction for 2-6h, cooling, performing low-pressure suction filtration and drying to obtain the thiolated Ag doped nano TiO2A porous ball;
(4) adding methacrylic acid, methyl methacrylate, n-butyl methacrylate and sulfhydrylation Ag doped nano TiO into photoinitiator benzophenone2Introducing nitrogen into the porous ball in the dark, stirring for 5-15min under the irradiation of ultraviolet lamp, filtering, dissolving with dry tetrahydrofuran to obtain product, adding n-hexane, repeating the above steps for three times, filtering, and drying to obtain Ag-doped nanometer TiO2Antibacterial material grafted with polyacrylate.
2. Ag-doped nano TiO according to claim 12The antibacterial material of grafted polyacrylate is characterized in that: the mass ratio of tetrabutyl titanate to silver nitrate in the step (1) is 100: 0.8-1.5.
3. Ag-doped nano TiO according to claim 12The antibacterial material of grafted polyacrylate is characterized in that: magnetic stirring device includes the main part in step (2), and the right side swing joint of main part has the motor, and the top swing joint of motor has the driving shaft, and the centre swing joint of driving shaft has the action wheel, and the top swing joint of driving shaft has the connecting rod, and the left side swing joint of connecting rod has the driven shaft, and the bottom swing joint of driven shaft has the follower, and the top swing joint of driven shaft has the end cover, and the bottom swing joint of main part has the magnetic stirring module, and the right side swing joint of main part has control module.
4. Ag-doped nano TiO according to claim 12The antibacterial material of grafted polyacrylate is characterized in that: in the step (3), the gamma-mercaptopropyl trimethoxysilane and the Ag-doped nano TiO are added2The mass ratio of the porous ball is 100: 70-100.
5. Ag-doped nano TiO according to claim 12The antibacterial material of grafted polyacrylate is characterized in that: in the step (4), benzophenone, methacrylic acid, methyl methacrylate, n-butyl methacrylate and sulfhydrylation Ag are doped with nano TiO2The mass ratio of the porous ball is 10-15:15-25:50-70:100: 0.5-3.
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CN112915816A (en) * | 2021-01-22 | 2021-06-08 | 广州大学 | MXene separation membrane capable of simultaneously separating oil and dye and preparation method and application thereof |
CN113402721A (en) * | 2021-05-24 | 2021-09-17 | 杭州余芯新型材料有限公司 | Mixed crystal phase TiO2Grafted polymethyl methacrylate denture base resin and preparation method thereof |
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CN112915816A (en) * | 2021-01-22 | 2021-06-08 | 广州大学 | MXene separation membrane capable of simultaneously separating oil and dye and preparation method and application thereof |
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CN113402721B (en) * | 2021-05-24 | 2022-09-23 | 杭州华粹义齿制作有限公司 | Mixed crystal phase TiO 2 Grafted polymethyl methacrylate denture base resin and preparation method thereof |
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