WO2017071180A1

WO2017071180A1 - Modified nanometer titanium dioxide composite material coated with halamine antibacterial agent and preparation method therefor

Info

Publication number: WO2017071180A1
Application number: PCT/CN2016/082289
Authority: WO
Inventors: 任学宏; 李琳; 马维; 成晓莉
Original assignee: 江南大学
Priority date: 2015-10-28
Filing date: 2016-05-17
Publication date: 2017-05-04
Also published as: CN105237681A; CN105237681B

Abstract

Provided is a modified nanometer titanium dioxide composite material coated with a halamine antibacterial agent. A preparation method therefor is: (1) dispersing nanometer titanium dioxide in an aqueous solution containing a dispersing agent, and ultrasonically dispersing same until uniform to obtain an A phase; (2) using a mixture of polymerization monomers, i.e. halamine antibacterial agent precursor allyl hydantoin and methyl methacrylate, as a B phase; (3) slowly adding the B phase dropwise into the A phase under stirring, ultrasonically dispersing same so as to prepare a uniformly dispersed miniemulsion, transferring same into a flask equipped with a reflux condensation and stirring device and adding an initiator in a dropwise manner so as to carry out a reaction; and (4) after the reaction is finished, performing washing, drying and chlorinating so as to prepare a finished product. In the present invention, the surface of the nanometer titanium dioxide is coated with a layer of halamine antibacterial agent precursor and methyl methacrylate polymerization monomers to form a nanometer composite particle having a core-shell structure, and a composite material capable of enabling a halamine antibacterial agent to be resistant to ultraviolet and also improving the antibacterial performance of the nanometer titanium dioxide in the absence of light is prepared, this being of great importance.

Description

Title: a g-amine antibacterial agent coated modified nano titanium dioxide composite material and preparation method thereof

Technical field

[0001] The present invention relates to the field of nanomaterial science and technology, and in particular, to a method for preparing a nanocomposite with a nano titanium dioxide as a core and a double bond haloamine antibacterial agent precursor as a shell.

Background technique

[0002] Nano titanium dioxide has high oxidation activity, strong stability, non-toxic, tasteless, harmless to the body, rich in resources, cheap, chemically stable, UV resistant, antibacterial, self-cleaning, etc. Nano titanium dioxide is widely used in In different fields, including textiles, cosmetics, ceramics, plastics and coatings. Under the condition of ultraviolet light irradiation, the valence band electrons transition into the conduction band, and the generated valence band holes have strong oxidation performance, which can decompose most organic pollutants such as bacteria and fungi into inorganic substances. Harmless substances such as carbon dioxide and water.

[0003] However, nano titanium dioxide cannot undergo photocatalytic reaction under dark conditions, and thus cannot produce an antibacterial active component. In addition, nano titanium dioxide itself does not have an antibacterial effect, but bacteria grows easily under conditions of no light and humidity. And reproduction, so improving the antibacterial culture of nano titanium dioxide in the absence of light conditions, and thus improving its practicability, is an important research direction.

[0004] 3⁄4 amine antibacterial agent has the advantages of high-efficiency broad-spectrum, long-lasting antibacterial property and antibacterial regenerability, but it has been found that some 3⁄4 amine antibacterial agents are unstable under UVA irradiation, and are prone to breakage, thereby causing the substrate to lose ring shape. The 3⁄4 amine compound reduces the antibacterial properties.

technical problem

[0005] In view of the above problems existing in the prior art, the present applicant provides a 3⁄4 amine antibacterial agent coated modified nano titanium dioxide composite material and a preparation method thereof. The invention coats the surface of the nano titanium dioxide with a 3⁄4 amine antibacterial agent precursor and a methyl methacrylate polymer monomer to form a nanocomposite particle having a core-shell structure, which is prepared to make the 3⁄4 amine antibacterial agent have ultraviolet resistance, and It is of great significance to improve the antibacterial properties of nanometer titanium dioxide in the absence of light.

Problem solution Technical solution

The technical solution of the present invention is as follows:

[0007] A 3⁄4 amine antibacterial agent coated modified nano titanium dioxide composite material, the preparation method thereof is:

[0008] (1) Dispersing 2-20 g of nano-titanium dioxide in an aqueous solution containing a dispersant having a mass of 10-50% of the mass of the nano-titanium dioxide, and filling 100 g with water, in a cell pulverizer Ultrasonic dispersion is uniform, as phase A;

[0009] (2) a mass of nano-titanium dioxide mass of 30-150% of the polymerized monomeric haloamine antibacterial agent precursor propylene glycol and methyl methacrylate mixture as a phase B;

[0010] (3) Slowly drip phase B into phase A under mechanical agitation, and then ultrasonically disperse in an ultrasonic cell pulverizer to form a uniformly dispersed fine emulsion, and transfer the fine emulsion to have a condensed reflux In the flask of the stirring device, the reaction is carried out by adding 0.5-5% initiator of the total mass of the polymerizable monomer 3⁄4 amine antibacterial agent precursor allyl hydantoin and methyl methacrylate;

[0011] (4) After the reaction is completed, washing, drying, and chlorination are carried out to obtain a finished product.

[0012] The halogenated amine antibacterial agent precursor allyl sea is represented by the formula (I).

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(I)

In the formula, X is selected from chlorine or bromine.

[0015] The dispersant is a nonionic surfactant.

[0016] Preferably, the dispersing agent is a polyoxyethylene fatty alcohol condensate flat plus 0-10, flat plus 0-20, polyoxyethylene alkyl phenol condensate OP-10, OP-15, polyoxyethylene multiple One of the alcohol ether fatty acid esters Twee _n 40, Tween 80. [0017] The amount of the polymerized monomeric haloamine antibacterial agent precursor allylhydantoin is 5-30% of the total mass of the polymerized monomeric haloamine antibacterial agent precursors allylhydantoin and methyl methacrylate.

[0018] The initiator is a water-soluble initiator potassium persulfate, sodium persulfate or ammonium persulfate.

[0019] The temperature of the reaction in the step (3) is 60-80 ° C, and the reaction time is 1-5 h.

[0020] The solution obtained after the end of the reaction in the step (4) was centrifuged at 8000 rpm for 20 min, and the obtained powder was washed three times with ethanol and distilled water, respectively, and chlorinated with a 0.5 wt% sodium hypochlorite solution for 1 h, and the solid particles were taken out. After thoroughly washing with distilled water, and then drying in an oven at 45 ° C for 2 h, the desired double-bonded 3⁄4 amine antibacterial agent is coated with nano-titanium dioxide.

Advantageous effects of the invention

Beneficial effect

[0021] The beneficial technical effects of the present invention are:

[0022] The method used in the invention has few kinds of raw materials, simple operation method, simple process and short reaction time, and the prepared nano titanium dioxide has an antibacterial function of high-efficiency and reproducible regeneration, and the same can improve the ultraviolet stability of the 3⁄4 amine compound. Has a high practical value.

[0023] In the present invention, the organic/inorganic nanocomposite particles are prepared by a method of miniemulsion polymerization, and the advantages between the organic material and the inorganic material are complemented. The miniemulsion polymerization is divided into two processes: 1. Fine emulsification process, oil The monomer of the phase is added to the aqueous phase containing the dispersant, and the monomer is dispersed by ultrasonic waves into uniform nano- or sub-micron droplets. 2. The polymerization process, raising the reaction temperature, the initiator adsorbed by the small droplets generates free radicals, and then initiates polymerization in the droplets.

[0024] The organic phase of the present invention employs a functional monomer allylhydantoin having an antibacterial property and a comonomer thereof, which is caused by the "self-blocking polymerization" effect of allyl radicals on allylhydantoin. It is difficult to form a high molecular weight homopolymer, so the addition of the comonomer methyl methacrylate and the like is advantageous for the chain growth reaction. The inorganic phase uses nano-titanium dioxide with UV shielding function to prepare a nanocomposite which can improve the UV stability of the 3⁄4 amine antibacterial agent and can compensate the antibacterial function of titanium dioxide in the absence of light. At the same time, the nanostructure has a higher specific surface area, and this high specific surface area nanostructure can improve the antibacterial properties of the prepared nanocomposite compared to the conventional size of the 3⁄4 amine antibacterial agent.

[0025] The invention adopts the method of miniemulsion polymerization, the reaction is stable, the method is simple, and the coating efficiency is high. The coated nano-titanium dioxide prepared by the method has a spherical shape and a uniform size distribution, and the particle diameter is between 60-290 nm. Ben The coated nano titanium dioxide prepared by the invention has excellent antibacterial property and high antibacterial efficiency, and the effective chlorine content thereof can reach 1.59%. After contact with the inoculated bacteria, Staphylococcus aureus and Escherichia coli are respectively in 10 min and 30 min respectively. The sterilization rate reaches 100%. The coated nano titanium dioxide prepared by the invention has excellent ultraviolet resistance. After 72 hours of ultraviolet irradiation, only 42% of the available chlorine content is lost, and after rechlorination, the chlorine content is restored to 73%. The coated nano titanium dioxide prepared by the invention has excellent biocompatibility.

Brief description of the drawing

DRAWINGS

Figure 1 is a transmission electron micrograph of the present invention, the scale of the figure is 100 nm;

2 is a graph showing the results of ultraviolet stability test of the present invention.

Embodiments of the invention

[0028] The present invention will be specifically described below in conjunction with the embodiments and the accompanying drawings and tables.

Embodiment 1

[0030] 5 g of nano titanium dioxide was added to 95 g of an aqueous solution containing 1.5 g of a nonionic surfactant polyoxyethylene fatty alcohol condensate (flattened with O-10), and placed in an ultrasonic cell pulverizer for 30 min, as Phase A; mix 0.25 g of the haloamine antibacterial agent precursor allyl hydantoin and 2.25 g of methyl methacrylate as phase B; slowly add phase B to phase A under mechanical agitation, then After ultrasonic dispersion for 10 min, a finely dispersed fine emulsion was prepared, and the fine emulsion was transferred to a flask equipped with a condensing reflux and stirring device, and 0.03 g of an initiator sodium persulfate was added thereto, and the temperature was raised to 70 ° C.

h. After the reaction, the obtained solution was centrifuged at SOOO rpm for 20 min, and the obtained powder was washed three times with ethanol and distilled water, and chlorinated with a 0.5 wt% sodium hypochlorite solution for 1 h, and the solid particles were taken out and thoroughly washed with distilled water, and then It is placed in an oven and dried at 45 ° C for 2 h to obtain the desired haloamine antibacterial agent coated with nano titanium dioxide. The coated nano-titanium dioxide was determined to have a chlorine content of 1.59%.

Embodiment 2

[0032] 10 g of nano titanium dioxide was added to 90 g of an aqueous solution containing 4 g of a nonionic surfactant polyoxyethylene polyol ether fatty acid ester (Tw _een 80), and then ultrasonically dispersed in an ultrasonic cell pulverizer for 30 min. Phase A; mix 1.5 g of the haloamine antibacterial agent precursor allyyl hydantoin and 8.5 g of methyl methacrylate It is phase B; under the action of mechanical agitation, phase B is slowly added dropwise to phase A, then ultrasonically dispersed for 10 minutes to prepare a uniformly dispersed fine emulsion, and the fine emulsion is transferred to a flask with a condensing reflux and stirring device. Add 0.25 g of initiator potassium persulfate, raise the temperature to 65 ° C, and react for 5 h. After the reaction is completed, the obtained solution is centrifuged at 8000 φηι 20

Min, the obtained powder was washed three times with ethanol and distilled water, and chlorinated with 0.5% by weight of sodium hypochlorite solution for 1 hour. The solid particles were taken out and washed thoroughly with distilled water, then placed in an oven and dried at 45 ° C for 2 h, ie The desired 3⁄4 amine antibacterial agent is coated with nano titanium dioxide. The coated nano-titanium dioxide was determined to have a chlorine content of 2.26 < 3⁄4.

Example 3

[0034] 15 g of nano titanium dioxide is added to 85

g contains 2.5g of nonionic surfactant polyoxyethylene fatty alcohol condensate (flattened with O-20) in an aqueous solution, and then placed in an ultrasonic cell pulverizer for ultrasonic dispersion for 30 min, as phase A; 4.5 g of haloamine antibacterial The precursor precursor allylhydantoin and 13.5 g of methyl methacrylate were uniformly mixed as phase B. Under mechanical agitation, phase B was slowly added dropwise to phase A, and then ultrasonically dispersed for 10 min to make a uniform dispersion. The miniemulsion, the fine emulsion was transferred to a flask with a condensing reflux and stirring device, 0.9 g of the initiator ammonium persulfate was added, and the temperature was raised to 75 ° C for 3 h. After the reaction was completed, the obtained solution was centrifuged at 8000 rpm for 20 min, and the obtained powder was washed three times with ethanol and distilled water, and chlorinated with a 0.5 wt% sodium hypochlorite solution for 1 h, and the solid particles were taken out and thoroughly washed with distilled water. Then, it was baked in an oven at 45 ° C for 2 h to obtain the desired 3⁄4 amine antibacterial agent coated with nano titanium dioxide. The coated nano-titanium dioxide was determined to have a chlorine content of 1.77 < 3⁄4.

[0035] Example 4

[0036] will 20

g nano-titanium dioxide was added to 80 g of an aqueous solution containing 2 g of a nonionic surfactant polyoxyethylene alkylphenol condensate (OP-10), and then ultrasonically dispersed in an ultrasonic cell pulverizer for 30 min, as phase A; 1 g of halogen The amine antibacterial agent precursor allylhydantoin and 11 g of methyl methacrylate were uniformly mixed as phase B; under the action of mechanical agitation, phase B was slowly added dropwise to phase A, and then ultrasonically dispersed for 10 min. The uniformly dispersed fine emulsion was transferred to a flask equipped with a condensing reflux and a stirring device, 0.2 g of an initiator potassium persulfate was added, and the temperature was raised to 80 ° C for 1.5 h. After the reaction is over, the resulting solution is separated at 8000 rpm. After 20 min, the obtained powder was washed three times with ethanol and distilled water, and chlorinated with 0.5 wt% sodium hypochlorite solution for 1 h. The solid particles were taken out and washed thoroughly with distilled water, then placed in an oven and dried at 45 ° C for 2 h. That is, the desired 3⁄4 amine antibacterial agent is coated with nano titanium dioxide. The coated nano-titanium dioxide was determined to have a chlorine content of 1.01%.

As shown in FIG. 1, the haloamine antibacterial agent obtained in Examples 1-4 was coated with nano-titanium dioxide, and the prepared coated nano-titanium dioxide had a core-shell structure by conventional transmission electron microscopy.

[0038]

[0039] Test Example 1 : UV-stability test of nano-titanium dioxide coated with 3⁄4 amine antibacterial agent

[0040] The test was carried out using an ultraviolet light accelerated weathering tester. The test sample 3⁄4 amine antibacterial agent coated with nano-type scorpion moss is placed in the ultraviolet irradiation chamber for 1-72 h, and the effective chlorine content is tested or re-chlorinated to test the effective chlorine content. The test results are shown in Figure 2.

[0041] It can be obtained from the analysis of FIG. 2 that the chlorine content of the nanometer titanium dioxide coated by the halogen amine antibacterial agent decreases rapidly in several small crucibles immediately after the irradiation, and the effective chlorine content decreases slowly with the prolongation of the crucible. . After 72 h of irradiation, the prepared nano-titanium dioxide lost only 42% of the chlorine content, and the chlorine content returned to the original 73% after rechlorination. Compared to previous studies on 3⁄4 amine antibacterial agents, the UV stability of the prepared coated nano-titanium dioxide has been significantly improved, indicating that titanium dioxide can protect the structure of the haloamine compound by ultraviolet shielding under ultraviolet irradiation.

Test Example 2: Antibacterial property test of nanometer titanium dioxide coated with a halogen amine antibacterial agent

[0043] Test sample: Prepared as described in Example 2; Control sample: Prepared as described in Example 2 without chlorination and preparation of unreacted nano-titanium dioxide. The above test and control samples were inoculated separately with S. aureus and E. coli 0157: H7, and a certain amount of bacteria was diluted to prepare a bacterial suspension in 100 μL phosphate buffer solution, and then 100 μL of the bacterial suspension was added to contain O. In the phosphate buffer of the .lg test sample, after contact at 37 ° C for 10 min, 30 min, 60 min, 90 min and 120 min, the sample was quenched with 0.5 mL of 0.05 N sterile sodium thiosulfate solution. All oxidized chlorine was removed. The above sodium thiosulfate had no effect on any of the bacteria in the control test. The quenched sample was serially diluted with ρΗ7.0, ΙΟΟμΜ phosphate buffer solution, and then 10 (VL was placed. Incubate in sterile medium for 24 h at 37 ° C. The test results are shown in Table 1.

[0044] Table 1 3⁄4 amine antibacterial agent coated nano titanium dioxide antibacterial performance test

[0045] ^a inoculation concentration was 5.00 x 10 ⁵ CFU/mL _; ^b inoculation concentration was 1.80 x 10 ⁶ CFU/mL

[0046] The data shown in Table 1 shows that the 3⁄4 amine antibacterial agent prepared by the invention has excellent antibacterial property and high antibacterial efficiency, and the test sample is in contact with the inoculated bacteria, and the test sample is against Staphylococcus aureus within 10 min. The antibacterial rate reached 100%, and the antibacterial rate against Escherichia coli reached 100% within 30 min.

[0047] The raw materials and actual materials involved in the above embodiments are all commercially available products, and the industrial equipment used is a conventional equipment in the art.

Claims

Claim

[Claim 1] A 3⁄4 amine antibacterial agent coated modified nano titanium dioxide composite material, characterized in that the preparation method is:

(1) Dispersing 2-20 g of nano-titanium dioxide in an aqueous solution containing a dispersant having a mass of 10-50% of the mass of the nano-titanium dioxide, filling 100 g with water, and uniformly dispersing ultrasonically in a cell pulverizer , as phase A;

(2) a mixture of 30-150% of a polymeric monomeric haloamine antibacterial agent having a mass of nano-titanium dioxide as a precursor phase of a mixture of allyl hydantoin and methyl methacrylate;

(3) Slowly add the phase B to the phase A under mechanical agitation, then ultrasonically disperse in an ultrasonic cell pulverizer to prepare a uniformly dispersed fine emulsion, and transfer the fine emulsion to a condensing reflux and stirring device. In the flask, the reaction is carried out by adding 0.5-5% initiator of the total mass of the polymerizable monomer 3⁄4 amine antibacterial agent precursor allyyl hydantoin and methyl methacrylate;

(4) After the reaction is completed, the product is washed, dried, and chlorinated.

[Claim 2] The composite material according to claim 1, wherein the 3⁄4 amine antibacterial agent precursor allylic sea is a structure represented by the formula (I).

Wherein X is selected from chlorine or bromine.

[Claim 3] The complex according to claim 1, wherein the dispersing agent is a nonionic surfactant.

[Claim 4] The composition according to claim 1 characterized in that the dispersing agent is polyoxyethylene The fatty alcohol condensate is uniformly added with 0-10, flat plus 0-20, polyoxyethylene alkylphenol condensate OP-10, OP-15, polyoxyethylene polyol ether fatty acid ester Tween40, Tween80

[Claim 5] The composite material according to claim 1, wherein the amount of the polymerized monomer 3⁄4 amine antibacterial agent precursor allyl hydantoin is a polymerizable monomer 3⁄4 amine antibacterial agent precursor allyl sea Due to the total mass of methyl methacrylate 5-30%.

[Clasion 6] The composite material according to claim 1, characterized in that the initiator is a water-soluble initiator potassium persulfate, sodium persulfate or ammonium persulfate.

[Claim 7] The composite material according to claim 1, wherein the reaction temperature in the step (3) is 60-80 ° C, and the reaction time is 1-5 h.

[Claim 8] The composite material according to claim 1, wherein the solution obtained after the reaction in the step (4) is centrifuged at 8000 rpm for 20 min, and the obtained powder is washed with ethanol and distilled water, respectively. Three times, chlorinated with 0.5% by weight of sodium hypochlorite solution for 1 hour, the solid particles were taken out and washed thoroughly with distilled water, and then dried in an oven at 45 ° C for 2 h to obtain the desired 3⁄4 amine antibacterial agent containing double bonds. Coating nano titanium dioxide.