CN117362834A - Antibacterial flame-retardant plastic, preparation method thereof and prepared food bottle - Google Patents

Antibacterial flame-retardant plastic, preparation method thereof and prepared food bottle Download PDF

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CN117362834A
CN117362834A CN202311480036.XA CN202311480036A CN117362834A CN 117362834 A CN117362834 A CN 117362834A CN 202311480036 A CN202311480036 A CN 202311480036A CN 117362834 A CN117362834 A CN 117362834A
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weight
parts
expanded graphite
flame retardant
antibacterial flame
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CN117362834B (en
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邓志辉
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Dongguan Guanyi Plastic Container Co ltd
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Dongguan Guanyi Plastic Container Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • 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
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/10—Applications used for bottles

Abstract

The invention providesAn antibacterial flame-retardant plastic, a preparation method thereof and a prepared food bottle belong to the technical field of plastics. Preparing Cu-N-S doped TiO through sol-gel reaction 2 And (3) carrying out hydrogenation treatment on MgO deposition expanded graphite, then carrying out surface modification on polydopamine, fixing urea and phosphate, preparing a modified antibacterial flame retardant under the modification effect of a silane coupling agent, mixing with an auxiliary agent, polyethylene or polypropylene resin, and carrying out melt extrusion granulation to obtain the antibacterial flame retardant plastic. The antibacterial flame-retardant plastic prepared by the invention has good antibacterial and flame-retardant properties, is low in toxicity, safe and environment-friendly, has a certain enhancement of mechanical properties, has good processability, can be widely applied to packaging plastics, has good usability, and has wide application prospect.

Description

Antibacterial flame-retardant plastic, preparation method thereof and prepared food bottle
Technical Field
The invention relates to the technical field of plastics, in particular to an antibacterial flame-retardant plastic, a preparation method thereof and a prepared food bottle.
Background
Along with the continuous improvement of living standard, the health consciousness of people is gradually enhanced, and the requirements on the living environment of people are also higher. In particular, in the fields of food, medicine and agricultural product packaging, and daily necessities such as pens, mobile phones, computers, toothbrushes, furniture and the like, the sanitary requirements on materials used by the products are higher and higher. In public places such as stations, squares, parks and the like, the flow of people is very large, public facilities are frequently used, germs are easy to generate, and the public health is affected. Plastic articles are currently being used more and more in these fields with their characteristic properties. Since plastics themselves have no antibacterial property, when used as packaging materials for foods, medicines and the like, under the specific temperature and humidity conditions for preserving foods and medicines, microorganisms such as bacteria harmful to human health are easy to grow on the surfaces of the plastics, and the preserved foods or medicines are polluted by the growth and reproduction of the microorganisms, so that the foods or medicines are deteriorated, moldy and even rotten; daily necessities such as toothbrushes and tableware are easy to generate germs in the use process, and the health of human bodies is directly affected.
In addition, plastics are required to have some flame retardancy. The added flame retardant comprises a brominated flame retardant, a phosphorus flame retardant, a silicon flame retardant and a sulfonate flame retardant. The brominated flame retardant has higher flame retardant efficiency, but contains halogen elements which are easy to color, and meanwhile, the brominated flame retardant does not meet the environmental protection requirement, so that the application of the brominated flame retardant is limited; the addition of the phosphorus flame retardant has a certain effect, but can lead to the rapid decrease of the performance of the modified material; the sulfonate flame retardant has higher efficiency, has smaller influence on the physical properties of the modified material and has lower influence on the light transmittance of the polycarbonate, so that the sulfonate flame retardant is favored by researchers; the silicon flame retardant is expensive, has better synergistic flame retardant effect, has little influence on material performance, and does not change transparency when the liquid silicon flame retardant is used.
Therefore, developing a plastic for high-performance food packaging with economical price, safe use and antibacterial and flame-retardant properties has wide application prospect.
Disclosure of Invention
The invention aims to provide an antibacterial flame-retardant plastic, a preparation method thereof and a prepared food bottle, wherein the prepared antibacterial flame-retardant plastic has good antibacterial and flame-retardant properties, is low in toxicity, safe and environment-friendly, has a certain enhanced mechanical property, has good processability, can be widely applied to packaging plastics, and has good usability and wide application prospect.
The technical scheme of the invention is realized as follows:
the invention provides a preparation method of an antibacterial flame-retardant plastic, which prepares Cu-N-S doped TiO through sol-gel reaction 2 And (3) carrying out hydrogenation treatment on MgO deposition expanded graphite, then carrying out surface modification on polydopamine, fixing urea and phosphate, preparing a modified antibacterial flame retardant under the modification effect of a silane coupling agent, mixing with an auxiliary agent, polyethylene or polypropylene resin, and carrying out melt extrusion granulation to obtain the antibacterial flame retardant plastic.
As a further improvement of the invention, the method comprises the following steps:
s1.Cu-N-S doped TiO 2 Preparation of MgO-deposited expanded graphite: dissolving tetrabutyl titanate and magnesium salt in ethanol, adding glacial acetic acid and expanded graphite, and uniformly dispersing to obtain a suspension A; dissolving copper salt and thiourea in ethanol water solution to obtain solution B; dropwise adding the solution B into the suspension A, stirring and reacting to form sol, aging to form gel, drying, calcining to obtain Cu-N-S doped TiO 2 MgO deposition of expanded graphite;
s2, hydrogenation Cu-N-S doped TiO 2 Preparation of MgO-deposited expanded graphite: doping the Cu-N-S prepared in the step S1 with TiO 2 Adding MgO deposition expanded graphite into a high-pressure reaction kettle, introducing high-purity hydrogen, heating, stirring, reacting, naturally cooling and deflating to obtain hydrogenated Cu-N-S doped TiO 2 MgO deposition of expanded graphite;
s3, modifying polydopamine: adding hydrogenated Cu-N-S doped TiO prepared in the step S2 2 Adding MgO deposition expanded graphite into water, adding dopamine hydrochloride and a catalyst, heating and stirring for reaction, centrifuging, washing and drying to obtain modified hydrogenated Cu-N-S doped TiO 2 MgO deposition expansionGraphite;
s4, fixing a synergistic flame retardant: dissolving urea and phosphate in ethanol, and adding modified hydrogenated Cu-N-S doped TiO prepared in the step S3 2 MgO deposition expanded graphite, heating and stirring for reaction, centrifuging, washing and drying to obtain the antibacterial flame retardant;
s5, modification: dissolving a composite silane coupling agent in ethanol, adding the antibacterial flame retardant prepared in the step S4, heating, stirring, reacting, centrifuging, washing, and drying to obtain a modified antibacterial flame retardant;
s6, preparing an auxiliary agent: uniformly mixing an antioxidant, a lubricant, a plasticizer, talcum powder and nano calcium carbonate to prepare an auxiliary agent;
s7, preparation of antibacterial flame-retardant plastic: adding the auxiliary agent prepared in the step S6 into a mixer for uniform mixing, adding the auxiliary agent and the modified antibacterial flame retardant prepared in the step S5 into a double-screw extruder for stirring and mixing, heating and melting, extruding and granulating to obtain the antibacterial flame retardant plastic.
As a further improvement of the invention, in the step S1, the mass ratio of tetrabutyl titanate, magnesium salt, glacial acetic acid, expanded graphite, copper salt and thiourea is 10-12:7-10:5-7:22-27:1-2:3-5, the concentration of the ethanol aqueous solution is 30-50wt%, the stirring reaction time is 1-3 hours, the aging time is 7-10 hours, the calcining temperature is 450-500 ℃ and the time is 2-4 hours, the magnesium salt is at least one of magnesium chloride, magnesium sulfate and magnesium nitrate, and the copper salt is at least one of copper chloride, copper sulfate and copper nitrate.
As a further improvement of the invention, the purity of the high-purity hydrogen in the step S2 is more than 99.9 percent, the high-purity hydrogen with the pressure of 2-3MPa is introduced, the temperature of the heating and stirring reaction is 150-170 ℃, and the time is 12-15 hours.
As a further improvement of the present invention, the hydrogenated Cu-N-S doped TiO in step S3 2 The mass ratio of the MgO deposition expanded graphite to the dopamine hydrochloride to the catalyst is 10-12:7-10:0.5-1, the catalyst is Tris-HCl solution with pH value of 8.5-9, the temperature of the heating and stirring reaction is 40-50 ℃, and the time is 3-5h.
As a further improvement of the invention, the mass ratio of urea, phosphate and modified hydrogenated Cu-N-S doped TiO2/MgO deposition expanded graphite in the step S4 is 2-4:5-7:40-50, the phosphate is at least one of trimethyl phosphate, triethyl phosphate and tributyl phosphate, the temperature of the heating and stirring reaction is 35-40 ℃ and the time is 1-3h.
As a further improvement of the invention, the composite silane coupling agent in the step S5 is at least two selected from KH570, A151, A171 and A172, preferably, the composite silane coupling agent is a mixture of KH570 and A151, the mass ratio of the composite silane coupling agent to the antibacterial flame retardant is 3-5:12-15, the temperature of the heating and stirring reaction is 45-50 ℃, and the time is 1-2h.
As a further improvement of the invention, in the step S6, the mass ratio of the antioxidant, the lubricant, the plasticizer, the talcum powder and the nano calcium carbonate is 1-2:0.5-1:2-3:3-5:2-4, the antioxidant is at least one of p-phenylenediamine, polyphenol and hydroquinone, the lubricant is polyethylene wax, and the plasticizer is at least one of triethyl citrate, acetyl triethyl citrate and tributyl citrate; in the step S7, the mass ratio of the polyethylene or polypropylene resin, the auxiliary agent and the modified antibacterial flame retardant is 70-90:3-5:2-3, the mixing time in the mixer is 20-30min, and the technological parameters of the double-screw extruder are as follows: first region 155-165 ℃, second region 170-175 ℃, third region 185-190 ℃, and fourth region 165-175 ℃.
The invention further protects the antibacterial flame-retardant plastic prepared by the preparation method.
The invention further protects a food bottle, which is prepared by adopting the antibacterial flame-retardant plastic through melt extrusion and blow molding.
The invention has the following beneficial effects:
the modified antibacterial flame retardant takes the expanded graphite as a carrier, on one hand, the expanded graphite ribbon has larger specific surface area and can well load TiO 2 And MgO, tiO 2 The photocatalysis antibacterial of the composite material provides a wide pore area, and on the other hand, the expanded graphite has good flame retardant property, and can play roles of heat insulation, oxygen insulation, smoke suppression and preventionThe molten drop has the functions of low smoke, low toxicity and no corrosive gas, and when the molten drop is quickly heated to about 300 ℃, the molten drop can expand by hundreds of times along the C-axis direction of a crystal structure, and the original scaly shape is changed into a worm shape with very low density, so that a high-efficiency heat-insulating and oxygen-isolating carbon layer is formed, thereby separating a plastic matrix from a heat source, simultaneously, in the expansion process, a large amount of heat is absorbed, the system temperature is reduced, acid radical ions in an interlayer are released, dehydration carbonization is promoted, and the chain reaction is interrupted by combining free radicals generated by combustion, so that the high-efficiency flame retardant effect is realized. The metal oxide MgO carried on the surface of the invention is used for desorbing the heat of the surface of the combustion product when being heated, simultaneously releasing moisture to dilute the oxygen on the surface of the combustion product, and the active magnesium oxide generated by decomposition is attached to the surface of the matrix, thereby further preventing the combustion.
Meanwhile, the Cu-N-S doped TiO is prepared by the sol-gel reaction 2 At the time, tiO is prepared by adding thiourea 2 In the process of doping N/S element, sulfur element enters TiO in the form of cation 2 In the lattice, electron occupying energy level is formed above the valence band, nitrogen is doped with NH 3 In the form of TiO 2 The valence band (O2 p) forms an unfilled intermediate energy level (N2 p) which, in combination, causes TiO to form 2 Is narrower and the spectral response range is wider. Under the addition of copper salt, the prepared N-S doped TiO 2 On the one hand, the forbidden band width can be further narrowed, the valence band moves upwards, the conduction band moves downwards to the vicinity of the fermi surface, the energy required by exciting electrons in the valence band to the conduction band is reduced, and the corresponding spectrum range is widened after Cu doping. On the other hand, cu ion is also an excellent broad-spectrum antibacterial material, has the advantage of low price and practicality compared with Ag, and has good antibacterial effect, and can directly act on the cell wall of bacteria, be combined with-SH and the like, act on proteins or enzymes of the bacteria; or accumulate on the surface of bacterial cell membrane under the action of electric field adsorption to destroy the permeability of bacterial cell membrane; or can be combined with bacterial cell DNA to inhibit RNA, DNA and cell protein synthesis, reduce bacterial activity, and inhibit bacterial proliferation.
Further, the inventionThe prepared Cu-N-S doped TiO 2 The MgO deposition expanded graphite is hydrogenated under the action of high-pressure hydrogen, and the TiO is enabled by the reduction of the hydrogen 2 The tetravalent titanium in the crystal is reduced to form low-valence titanium, so that the perfect crystal structure is partially destroyed and interrupted, crystal defects are formed, the movement condition of photo-generated electrons and holes is influenced, the distribution state is adjusted or TiO is changed 2 Therefore, the response range of the available absorbed light is further widened, so that the hydrogenated Cu-N-S doped TiO is prepared 2 Can well utilize visible light to exert the effect of formaldehyde pollutant degradation and photocatalysis antibiosis.
The invention prepares the hydrogenated Cu-N-S doped TiO 2 According to the method, on one hand, the nitrogen content in the modified antibacterial flame retardant is improved, so that the nitrogen doped synergistic flame retardant effect is improved, on the other hand, urea and phosphate synergistic flame retardant can be well fixed under the polyamino, carboxyl and hydroxyl structures of polydopamine, urea can be used as an air source for combustion of the expanded graphite, and inert gas compounds are emitted under heating, so that the contact of a base combustible substance and oxygen is blocked, the flame retardance is improved, on the other hand, the phosphate can improve the mechanical property of the base material, on the other hand, the expandable graphite is used in combination with urea, phosphorus compounds and magnesium oxide, residues of carbon are all reserved on the combustion surface to form a complete barrier layer, the residues adsorb molten base resin in the combustion process, the molten drop phenomenon generated in the resin combustion process is thoroughly overcome, the fly ash phenomenon is not generated, a good smoke suppression effect is realized, and the flame retardance can be achieved with little consumption.
After the prepared antibacterial flame retardant is modified by a silane coupling agent with double bonds, the surface of the prepared modified antibacterial flame retardant is provided with double bonds, and the double bonds of a small amount of free radicals in polypropylene or polyethylene resin can be polymerized under a melting condition so as to be fixed on a matrix molecular chain, so that the dispersibility and compatibility of the modified antibacterial flame retardant are improved, on the other hand, si element in the modified antibacterial flame retardant can also play a role in synergistic flame retardance, a carbon-containing silicate layer is formed on the surface of a polymer, the escape of combustible gas and the generation of free radicals are delayed or prevented, and meanwhile, the carbon formation of the polymer is promoted, the degradation speed of the polymer is reduced, and the thermal decomposition of the polymer is not easy to occur at high temperature.
The antibacterial flame-retardant plastic prepared by the invention has good antibacterial and flame-retardant properties, is low in toxicity, safe and environment-friendly, has a certain enhancement of mechanical properties, has good processability, can be widely applied to packaging plastics, has good usability, and has wide application prospect.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Nano calcium carbonate, 5000 mesh, purchased from the chemical raw materials limited company of Rongyue, guangzhou; polypropylene resin, LG chemical H1615, available from Suzhou Rong Xu plasticization Co., ltd; expanded graphite, particle size 50 μm, purity >99.9%, purchased from Qingdao Tianyuan to graphite Co.
Example 1
The embodiment provides a preparation method of antibacterial flame-retardant plastic, which specifically comprises the following steps:
s1.Cu-N-S doped TiO 2 Preparation of MgO-deposited expanded graphite: dissolving 10 parts by weight of tetrabutyl titanate and 7 parts by weight of magnesium chloride in 50 parts by weight of ethanol, adding 5 parts by weight of glacial acetic acid and 22 parts by weight of expanded graphite, and performing 1000W ultrasonic dispersion for 10min to obtain a suspension A; 1 part by weight of copper chloride and 3 parts by weight of thiourea are dissolved in 30 parts by weight of 30wt% ethanol water solution to obtain a solution B; dropwise adding the solution B into the suspension A, stirring and reacting for 1h to form sol, aging for 7h to form gel, drying, calcining at 450 ℃ for 2h to obtain Cu-N-S doped TiO 2 MgO deposition of expanded graphite;
s2, hydrogenation Cu-N-S dopingTiO 2 Preparation of MgO-deposited expanded graphite: doping the Cu-N-S prepared in the step S1 with TiO 2 Adding MgO deposition expanded graphite into a high-pressure reaction kettle, introducing hydrogen with the purity of more than 99.9% under the pressure of 2MPa, heating to 150 ℃, stirring for reacting for 12 hours, naturally cooling and deflating to obtain hydrogenated Cu-N-S doped TiO 2 MgO deposition of expanded graphite;
s3, modifying polydopamine: 10 parts by weight of hydrogenated Cu-N-S doped TiO prepared in step S2 2 Adding MgO deposition expanded graphite into 200 parts by weight of water, adding 7 parts by weight of dopamine hydrochloride and 0.5 part by weight of catalyst, heating to 40 ℃, stirring for reaction for 3 hours, centrifuging, washing and drying to obtain modified hydrogenated Cu-N-S doped TiO 2 MgO deposition of expanded graphite;
the catalyst is Tris-HCl solution with pH=8.5;
s4, fixing a synergistic flame retardant: dissolving 2 parts by weight of urea and 5 parts by weight of trimethyl phosphate in 200 parts by weight of ethanol, and adding 40 parts by weight of modified hydrogenated Cu-N-S doped TiO prepared in the step S3 2 MgO deposition expanded graphite, heating to 35 ℃, stirring and reacting for 1h, centrifuging, washing and drying to obtain the antibacterial flame retardant;
s5, modification: 3 parts by weight of composite silane coupling agent is dissolved in 100 parts by weight of ethanol, 12 parts by weight of the antibacterial flame retardant prepared in the step S4 is added, the mixture is heated to 45 ℃, stirred and reacted for 1 hour, centrifuged, washed and dried, and the modified antibacterial flame retardant is prepared;
the composite silane coupling agent is a mixture of KH570 and A151, and the mass ratio is 10:3;
s6, preparing an auxiliary agent: 1 part by weight of p-phenylenediamine, 0.5 part by weight of polyethylene wax, 2 parts by weight of triethyl citrate, 3 parts by weight of talcum powder and 2 parts by weight of nano calcium carbonate are stirred and mixed for 15min to prepare an auxiliary agent;
S7, preparation of antibacterial flame-retardant plastic: 70 parts by weight of polypropylene resin and 3 parts by weight of the auxiliary agent prepared in the step S6 are added into a mixer to be mixed for 20min, and then are added into a double-screw extruder together with 2 parts by weight of the modified antibacterial flame retardant prepared in the step S5 to be mixed, wherein the technological parameters are as follows: the antibacterial flame-retardant plastic is prepared by heating and melting the materials at 155 ℃ in the first area, 170 ℃ in the second area, 185 ℃ in the third area and 165 ℃ in the fourth area, extruding and granulating.
Example 2
The embodiment provides a preparation method of antibacterial flame-retardant plastic, which specifically comprises the following steps:
s1.Cu-N-S doped TiO 2 Preparation of MgO-deposited expanded graphite: dissolving 12 parts by weight of tetrabutyl titanate and 10 parts by weight of magnesium nitrate in 70 parts by weight of ethanol, adding 7 parts by weight of glacial acetic acid and 27 parts by weight of expanded graphite, and performing 1000W ultrasonic dispersion for 10min to obtain a suspension A; 2 parts by weight of copper nitrate and 5 parts by weight of thiourea are dissolved in 40 parts by weight of 50wt% ethanol water solution to obtain a solution B; dropwise adding the solution B into the suspension A, stirring and reacting for 3 hours to form sol, aging for 10 hours to form gel, drying, calcining at 500 ℃ for 4 hours to prepare Cu-N-S doped TiO 2 MgO deposition of expanded graphite;
s2, hydrogenation Cu-N-S doped TiO 2 Preparation of MgO-deposited expanded graphite: doping the Cu-N-S prepared in the step S1 with TiO 2 Adding MgO deposition expanded graphite into a high-pressure reaction kettle, introducing hydrogen with purity of more than 99.9% under 3MPa, heating to 170 ℃, stirring for reaction for 15h, naturally cooling and deflating to obtain hydrogenated Cu-N-S doped TiO 2 MgO deposition of expanded graphite;
s3, modifying polydopamine: 12 parts by weight of hydrogenated Cu-N-S doped TiO prepared in the step S2 2 Adding MgO deposition expanded graphite into 200 parts by weight of water, adding 10 parts by weight of dopamine hydrochloride and 1 part by weight of catalyst, heating to 50 ℃, stirring for reaction for 5 hours, centrifuging, washing and drying to obtain modified hydrogenated Cu-N-S doped TiO 2 MgO deposition of expanded graphite;
the catalyst is Tris-HCl solution with pH=9;
s4, fixing a synergistic flame retardant: dissolving 4 parts by weight of urea and 7 parts by weight of triethyl phosphate in 200 parts by weight of ethanol, and adding 50 parts by weight of modified hydrogenated Cu-N-S doped TiO prepared in the step S3 2 MgO deposition expanded graphite, heating to 40 ℃, stirring and reacting for 3 hours, centrifuging, washing and drying to obtain the antibacterial flame retardant;
s5, modification: dissolving 5 parts by weight of a composite silane coupling agent in 100 parts by weight of ethanol, adding 15 parts by weight of the antibacterial flame retardant prepared in the step S4, heating to 50 ℃, stirring for reacting for 2 hours, centrifuging, washing and drying to prepare a modified antibacterial flame retardant;
The composite silane coupling agent is a mixture of KH570 and A151, and the mass ratio is 12:5;
s6, preparing an auxiliary agent: 2 parts by weight of p-phenylenediamine, 1 part by weight of polyethylene wax, 3 parts by weight of acetyl triethyl citrate, 5 parts by weight of talcum powder and 4 parts by weight of nano calcium carbonate are stirred and mixed for 15min to prepare an auxiliary agent;
s7, preparation of antibacterial flame-retardant plastic: adding 90 parts by weight of polypropylene resin and 5 parts by weight of the auxiliary agent prepared in the step S6 into a mixer for mixing for 30min, and adding the mixture into a double-screw extruder together with 3 parts by weight of the modified antibacterial flame retardant prepared in the step S5 for stirring and mixing, wherein the technological parameters are as follows: the antibacterial flame-retardant plastic is prepared by heating and melting the materials in a first region 165 ℃, a second region 175 ℃, a third region 190 ℃ and a fourth region 175 ℃ and extruding and granulating the materials.
Example 3
The embodiment provides a preparation method of antibacterial flame-retardant plastic, which specifically comprises the following steps:
s1.Cu-N-S doped TiO 2 Preparation of MgO-deposited expanded graphite: dissolving 11 parts by weight of tetrabutyl titanate and 8.4 parts by weight of magnesium sulfate in 60 parts by weight of ethanol, adding 6 parts by weight of glacial acetic acid and 25 parts by weight of expanded graphite, and performing 1000W ultrasonic dispersion for 10min to obtain a suspension A; 1.5 parts by weight of copper sulfate and 4 parts by weight of thiourea are dissolved in 35 parts by weight of 40wt% ethanol water solution to obtain a solution B; dropwise adding the solution B into the suspension A, stirring and reacting for 2 hours to form sol, aging for 8 hours to form gel, drying, calcining at 470 ℃ for 3 hours to prepare the Cu-N-S doped TiO 2 MgO deposition of expanded graphite;
s2, hydrogenation Cu-N-S doped TiO 2 Preparation of MgO-deposited expanded graphite: doping the Cu-N-S prepared in the step S1 with TiO 2 Adding MgO deposition expanded graphite into a high-pressure reaction kettle, introducing hydrogen with the purity of more than 99.9% under the pressure of 2.5MPa, heating to 160 ℃, stirring for reaction for 13h, naturally cooling and discharging gas to obtain hydrogenated Cu-N-S doped TiO 2 MgO deposition of expanded graphite;
s3, modifying polydopamine: 11 parts by weight of the hydrogenation obtained in step S2Cu-N-S doped TiO 2 Adding MgO deposition expanded graphite into 200 parts by weight of water, adding 8.6 parts by weight of dopamine hydrochloride and 0.7 part by weight of catalyst, heating to 45 ℃, stirring for reacting for 4 hours, centrifuging, washing and drying to obtain modified hydrogenated Cu-N-S doped TiO 2 MgO deposition of expanded graphite;
the catalyst is Tris-HCl solution with pH=8.7;
s4, fixing a synergistic flame retardant: 3 parts by weight of urea and 6 parts by weight of tributyl phosphate are dissolved in 200 parts by weight of ethanol, and 45 parts by weight of modified hydrogenated Cu-N-S doped TiO prepared in the step S3 is added 2 MgO deposition expanded graphite, heating to 37 ℃, stirring and reacting for 2 hours, centrifuging, washing and drying to obtain the antibacterial flame retardant;
s5, modification: dissolving 4 parts by weight of a composite silane coupling agent in 100 parts by weight of ethanol, adding 13 parts by weight of the antibacterial flame retardant prepared in the step S4, heating to 47 ℃, stirring and reacting for 1.5 hours, centrifuging, washing and drying to prepare a modified antibacterial flame retardant;
The composite silane coupling agent is a mixture of KH570 and A151, and the mass ratio is 11:4;
s6, preparing an auxiliary agent: mixing 1.4 parts by weight of hydroquinone, 0.7 part by weight of polyethylene wax, 2.2 parts by weight of tributyl citrate, 4 parts by weight of talcum powder and 3 parts by weight of nano calcium carbonate for 15 minutes to prepare an auxiliary agent;
s7, preparation of antibacterial flame-retardant plastic: adding 80 parts by weight of polypropylene resin and 4 parts by weight of the auxiliary agent prepared in the step S6 into a mixer for mixing for 25min, and adding the mixture into a double-screw extruder together with 2.5 parts by weight of the modified antibacterial flame retardant prepared in the step S5 for stirring and mixing, wherein the technological parameters are as follows: the antibacterial flame-retardant plastic is prepared by heating and melting the materials at 160 ℃ in the first region, 172 ℃ in the second region, 187 ℃ in the third region and 170 ℃ in the fourth region, extruding and granulating.
Example 4
The difference compared to example 3 is that the complex silane coupling agent is a single KH570.
Example 5
The difference compared with example 3 is that the composite silane coupling agent is a single a151.
Comparative example 1
In comparison with example 3, the difference is that magnesium sulfate was not added in step S1.
The method comprises the following steps:
s1.Cu-N-S doped TiO 2 Preparation of MgO-deposited expanded graphite: dissolving 11 parts by weight of tetrabutyl titanate and 8.4 parts by weight of magnesium sulfate in 60 parts by weight of ethanol, adding 6 parts by weight of glacial acetic acid and 25 parts by weight of expanded graphite, and performing 1000W ultrasonic dispersion for 10min to obtain a suspension A; 1.5 parts by weight of copper sulfate and 4 parts by weight of thiourea are dissolved in 35 parts by weight of 40wt% ethanol water solution to obtain a solution B; dropwise adding the solution B into the suspension A, stirring and reacting for 2 hours to form sol, aging for 8 hours to form gel, drying, calcining at 470 ℃ for 3 hours to prepare the Cu-N-S doped TiO 2 MgO deposition of expanded graphite.
Comparative example 2
The difference from example 3 is that copper sulfate is not added in step S1.
The method comprises the following steps:
s1.Cu-N-S doped TiO 2 Preparation of MgO-deposited expanded graphite: dissolving 11 parts by weight of tetrabutyl titanate and 8.4 parts by weight of magnesium sulfate in 60 parts by weight of ethanol, adding 6 parts by weight of glacial acetic acid and 25 parts by weight of expanded graphite, and performing 1000W ultrasonic dispersion for 10min to obtain a suspension A; 1.5 parts by weight of copper sulfate and 4 parts by weight of thiourea are dissolved in 35 parts by weight of 40wt% ethanol water solution to obtain a solution B; dropwise adding the solution B into the suspension A, stirring and reacting for 2 hours to form sol, aging for 8 hours to form gel, drying, calcining at 470 ℃ for 3 hours to prepare the Cu-N-S doped TiO 2 MgO deposition of expanded graphite.
Comparative example 3
In comparison with example 3, the difference is that no thiourea was added in step S1.
The method comprises the following steps:
s1.Cu-N-S doped TiO 2 Preparation of MgO-deposited expanded graphite: dissolving 11 parts by weight of tetrabutyl titanate and 8.4 parts by weight of magnesium sulfate in 60 parts by weight of ethanol, adding 6 parts by weight of glacial acetic acid and 25 parts by weight of expanded graphite, and performing 1000W ultrasonic dispersion for 10min to obtain a suspension A; 1.5 parts by weight of copper sulfate and 4 parts by weight of thiourea were dissolved in35 parts by weight of 40wt% ethanol aqueous solution to obtain a solution B; dropwise adding the solution B into the suspension A, stirring and reacting for 2 hours to form sol, aging for 8 hours to form gel, drying, calcining at 470 ℃ for 3 hours to prepare the Cu-N-S doped TiO 2 MgO deposition of expanded graphite.
Comparative example 4
In comparison with example 3, the difference is that thiourea and copper sulfate are not added in step S1.
The method comprises the following steps:
s1.Cu-N-S doped TiO 2 Preparation of MgO-deposited expanded graphite: dissolving 11 parts by weight of tetrabutyl titanate and 8.4 parts by weight of magnesium sulfate in 60 parts by weight of ethanol, adding 6 parts by weight of glacial acetic acid and 25 parts by weight of expanded graphite, and performing 1000W ultrasonic dispersion for 10min to obtain a suspension A; 1.5 parts by weight of copper sulfate and 4 parts by weight of thiourea are dissolved in 35 parts by weight of 40wt% ethanol water solution to obtain a solution B; dropwise adding the solution B into the suspension A, stirring and reacting for 2 hours to form sol, aging for 8 hours to form gel, drying, calcining at 470 ℃ for 3 hours to prepare the Cu-N-S doped TiO 2 MgO deposition of expanded graphite.
Comparative example 5
In comparison with example 3, the difference is that step S2 is not performed.
The method comprises the following steps:
s1.Cu-N-S doped TiO 2 Preparation of MgO-deposited expanded graphite: dissolving 11 parts by weight of tetrabutyl titanate and 8.4 parts by weight of magnesium sulfate in 60 parts by weight of ethanol, adding 6 parts by weight of glacial acetic acid and 25 parts by weight of expanded graphite, and performing 1000W ultrasonic dispersion for 10min to obtain a suspension A; 1.5 parts by weight of copper sulfate and 4 parts by weight of thiourea are dissolved in 35 parts by weight of 40wt% ethanol water solution to obtain a solution B; dropwise adding the solution B into the suspension A, stirring and reacting for 2 hours to form sol, aging for 8 hours to form gel, drying, calcining at 470 ℃ for 3 hours to prepare the Cu-N-S doped TiO 2 MgO deposition of expanded graphite;
s2, modifying polydopamine: 11 parts by weight of Cu-N-S doped TiO prepared in step S1 2 Adding MgO deposition expanded graphite into 200 weight parts of water, adding 8.6 weight parts of dopamine hydrochloride and 0.7 weight part of catalyst, heating to 45 ℃, stirring for reaction for 4 hours, centrifuging,washing and drying to obtain modified Cu-N-S doped TiO 2 MgO deposition of expanded graphite;
the catalyst is Tris-HCl solution with pH=8.7;
s3, fixing a synergistic flame retardant: 3 parts by weight of urea and 6 parts by weight of tributyl phosphate are dissolved in 200 parts by weight of ethanol, and 45 parts by weight of modified Cu-N-S doped TiO prepared in the step S2 is added 2 MgO deposition expanded graphite, heating to 37 ℃, stirring and reacting for 2 hours, centrifuging, washing and drying to obtain the antibacterial flame retardant;
s4, modification: dissolving 4 parts by weight of a composite silane coupling agent in 100 parts by weight of ethanol, adding 13 parts by weight of the antibacterial flame retardant prepared in the step S4, heating to 47 ℃, stirring and reacting for 1.5 hours, centrifuging, washing and drying to prepare a modified antibacterial flame retardant;
the composite silane coupling agent is a mixture of KH570 and A151, and the mass ratio is 11:4;
s5, preparing an auxiliary agent: mixing 1.4 parts by weight of hydroquinone, 0.7 part by weight of polyethylene wax, 2.2 parts by weight of tributyl citrate, 4 parts by weight of talcum powder and 3 parts by weight of nano calcium carbonate for 15 minutes to prepare an auxiliary agent;
S6, preparation of antibacterial flame-retardant plastic: adding 80 parts by weight of polypropylene resin and 4 parts by weight of the auxiliary agent prepared in the step S5 into a mixer for mixing for 25min, and adding the mixture into a double-screw extruder together with 2.5 parts by weight of the modified antibacterial flame retardant prepared in the step S4 for stirring and mixing, wherein the technological parameters are as follows: the antibacterial flame-retardant plastic is prepared by heating and melting the materials at 160 ℃ in the first region, 172 ℃ in the second region, 187 ℃ in the third region and 170 ℃ in the fourth region, extruding and granulating.
Comparative example 6
In comparison with example 3, the difference is that step S3 is not performed.
The method comprises the following steps:
s1.Cu-N-S doped TiO 2 Preparation of MgO-deposited expanded graphite: dissolving 11 parts by weight of tetrabutyl titanate and 8.4 parts by weight of magnesium sulfate in 60 parts by weight of ethanol, adding 6 parts by weight of glacial acetic acid and 25 parts by weight of expanded graphite, and performing 1000W ultrasonic dispersion for 10min to obtain a suspension A; 1.5 parts by weight of copper sulfate and 4 parts by weight of thiourea are dissolved in 35 parts by weight of 40wt% ethanol waterObtaining a solution B in the solution; dropwise adding the solution B into the suspension A, stirring and reacting for 2 hours to form sol, aging for 8 hours to form gel, drying, calcining at 470 ℃ for 3 hours to prepare the Cu-N-S doped TiO 2 MgO deposition of expanded graphite;
s2, hydrogenation Cu-N-S doped TiO 2 Preparation of MgO-deposited expanded graphite: doping the Cu-N-S prepared in the step S1 with TiO 2 Adding MgO deposition expanded graphite into a high-pressure reaction kettle, introducing hydrogen with the purity of more than 99.9% under the pressure of 2.5MPa, heating to 160 ℃, stirring for reaction for 13h, naturally cooling and discharging gas to obtain hydrogenated Cu-N-S doped TiO 2 MgO deposition of expanded graphite;
s3, fixing a synergistic flame retardant: 3 parts by weight of urea and 6 parts by weight of tributyl phosphate are dissolved in 200 parts by weight of ethanol, and 45 parts by weight of hydrogenated Cu-N-S doped TiO prepared in the step S2 is added 2 MgO deposition expanded graphite, heating to 37 ℃, stirring and reacting for 2 hours, centrifuging, washing and drying to obtain the antibacterial flame retardant;
s4, modification: dissolving 4 parts by weight of a composite silane coupling agent in 100 parts by weight of ethanol, adding 13 parts by weight of the antibacterial flame retardant prepared in the step S3, heating to 47 ℃, stirring and reacting for 1.5 hours, centrifuging, washing and drying to prepare a modified antibacterial flame retardant;
the composite silane coupling agent is a mixture of KH570 and A151, and the mass ratio is 11:4;
s5, preparing an auxiliary agent: mixing 1.4 parts by weight of hydroquinone, 0.7 part by weight of polyethylene wax, 2.2 parts by weight of tributyl citrate, 4 parts by weight of talcum powder and 3 parts by weight of nano calcium carbonate for 15 minutes to prepare an auxiliary agent;
s6, preparation of antibacterial flame-retardant plastic: adding 80 parts by weight of polypropylene resin and 4 parts by weight of the auxiliary agent prepared in the step S5 into a mixer for mixing for 25min, and adding the mixture into a double-screw extruder together with 2.5 parts by weight of the modified antibacterial flame retardant prepared in the step S4 for stirring and mixing, wherein the technological parameters are as follows: the antibacterial flame-retardant plastic is prepared by heating and melting the materials at 160 ℃ in the first region, 172 ℃ in the second region, 187 ℃ in the third region and 170 ℃ in the fourth region, extruding and granulating.
Comparative example 7
The difference from example 3 is that urea is not added in step S4.
The method comprises the following steps:
s4, fixing a synergistic flame retardant: 9 parts by weight of tributyl phosphate is dissolved in 200 parts by weight of ethanol, and 45 parts by weight of modified hydrogenated Cu-N-S doped TiO prepared in the step S3 is added 2 And (3) depositing expanded graphite by MgO, heating to 37 ℃, stirring and reacting for 2 hours, centrifuging, washing and drying to obtain the antibacterial flame retardant.
Comparative example 8
In comparison with example 3, the difference is that tributyl phosphate is not added in step S4.
The method comprises the following steps:
s4, fixing a synergistic flame retardant: 9 parts by weight of urea is dissolved in 200 parts by weight of ethanol, and 45 parts by weight of modified hydrogenated Cu-N-S doped TiO prepared in the step S3 is added 2 And (3) depositing expanded graphite by MgO, heating to 37 ℃, stirring and reacting for 2 hours, centrifuging, washing and drying to obtain the antibacterial flame retardant.
Comparative example 9
In comparison with example 3, the difference is that step S4 is not performed.
The method comprises the following steps:
s1.Cu-N-S doped TiO 2 Preparation of MgO-deposited expanded graphite: dissolving 11 parts by weight of tetrabutyl titanate and 8.4 parts by weight of magnesium sulfate in 60 parts by weight of ethanol, adding 6 parts by weight of glacial acetic acid and 25 parts by weight of expanded graphite, and performing 1000W ultrasonic dispersion for 10min to obtain a suspension A; 1.5 parts by weight of copper sulfate and 4 parts by weight of thiourea are dissolved in 35 parts by weight of 40wt% ethanol water solution to obtain a solution B; dropwise adding the solution B into the suspension A, stirring and reacting for 2 hours to form sol, aging for 8 hours to form gel, drying, calcining at 470 ℃ for 3 hours to prepare the Cu-N-S doped TiO 2 MgO deposition of expanded graphite;
s2, hydrogenation Cu-N-S doped TiO 2 Preparation of MgO-deposited expanded graphite: doping the Cu-N-S prepared in the step S1 with TiO 2 Adding MgO deposition expanded graphite into a high-pressure reaction kettle, introducing hydrogen with the purity of more than 99.9% under the pressure of 2.5MPa, heating to 160 ℃, stirring for reaction for 13h, naturally cooling and discharging gas to obtain hydrogenated Cu-N-S doped TiO 2 MgO deposition of expanded graphite;
s3, DOPAAmine modification: 11 parts by weight of hydrogenated Cu-N-S doped TiO prepared in step S2 2 Adding MgO deposition expanded graphite into 200 parts by weight of water, adding 8.6 parts by weight of dopamine hydrochloride and 0.7 part by weight of catalyst, heating to 45 ℃, stirring for reacting for 4 hours, centrifuging, washing and drying to obtain modified hydrogenated Cu-N-S doped TiO 2 MgO deposition of expanded graphite;
the catalyst is Tris-HCl solution with pH=8.7;
s4, modification: dissolving 4 parts by weight of a composite silane coupling agent in 100 parts by weight of ethanol, and adding 13 parts by weight of modified hydrogenated Cu-N-S doped TiO prepared in the step S3 2 MgO deposition expanded graphite, heating to 47 ℃, stirring and reacting for 1.5 hours, centrifuging, washing and drying to obtain the modified antibacterial flame retardant;
the composite silane coupling agent is a mixture of KH570 and A151, and the mass ratio is 11:4;
s5, preparing an auxiliary agent: mixing 1.4 parts by weight of hydroquinone, 0.7 part by weight of polyethylene wax, 2.2 parts by weight of tributyl citrate, 4 parts by weight of talcum powder and 3 parts by weight of nano calcium carbonate for 15 minutes to prepare an auxiliary agent;
S6, preparation of antibacterial flame-retardant plastic: adding 80 parts by weight of polypropylene resin and 4 parts by weight of the auxiliary agent prepared in the step S5 into a mixer for mixing for 25min, and adding the mixture into a double-screw extruder together with 2.5 parts by weight of the modified antibacterial flame retardant prepared in the step S4 for stirring and mixing, wherein the technological parameters are as follows: the antibacterial flame-retardant plastic is prepared by heating and melting the materials at 160 ℃ in the first region, 172 ℃ in the second region, 187 ℃ in the third region and 170 ℃ in the fourth region, extruding and granulating.
Comparative example 10
In comparison with example 3, the difference is that step S5 is not performed.
The method comprises the following steps:
s1.Cu-N-S doped TiO 2 Preparation of MgO-deposited expanded graphite: dissolving 11 parts by weight of tetrabutyl titanate and 8.4 parts by weight of magnesium sulfate in 60 parts by weight of ethanol, adding 6 parts by weight of glacial acetic acid and 25 parts by weight of expanded graphite, and performing 1000W ultrasonic dispersion for 10min to obtain a suspension A; 1.5 parts by weight of copper sulfate and 4 parts by weight of thiourea are dissolved in 35 parts by weight of 40wt% ethanol water solution to obtain a solution B; the solution is subjected toDropwise adding B into the suspension A, stirring and reacting for 2 hours to form sol, aging for 8 hours to form gel, drying, calcining at 470 ℃ for 3 hours to obtain Cu-N-S doped TiO 2 MgO deposition of expanded graphite;
s2, hydrogenation Cu-N-S doped TiO 2 Preparation of MgO-deposited expanded graphite: doping the Cu-N-S prepared in the step S1 with TiO 2 Adding MgO deposition expanded graphite into a high-pressure reaction kettle, introducing hydrogen with the purity of more than 99.9% under the pressure of 2.5MPa, heating to 160 ℃, stirring for reaction for 13h, naturally cooling and discharging gas to obtain hydrogenated Cu-N-S doped TiO 2 MgO deposition of expanded graphite;
s3, modifying polydopamine: 11 parts by weight of hydrogenated Cu-N-S doped TiO prepared in step S2 2 Adding MgO deposition expanded graphite into 200 parts by weight of water, adding 8.6 parts by weight of dopamine hydrochloride and 0.7 part by weight of catalyst, heating to 45 ℃, stirring for reacting for 4 hours, centrifuging, washing and drying to obtain modified hydrogenated Cu-N-S doped TiO 2 MgO deposition of expanded graphite;
the catalyst is Tris-HCl solution with pH=8.7;
s4, fixing a synergistic flame retardant: 3 parts by weight of urea and 6 parts by weight of tributyl phosphate are dissolved in 200 parts by weight of ethanol, and 45 parts by weight of modified hydrogenated Cu-N-S doped TiO prepared in the step S3 is added 2 MgO deposition expanded graphite, heating to 37 ℃, stirring and reacting for 2 hours, centrifuging, washing and drying to obtain the antibacterial flame retardant;
s5, preparing an auxiliary agent: mixing 1.4 parts by weight of hydroquinone, 0.7 part by weight of polyethylene wax, 2.2 parts by weight of tributyl citrate, 4 parts by weight of talcum powder and 3 parts by weight of nano calcium carbonate for 15 minutes to prepare an auxiliary agent;
S6, preparation of antibacterial flame-retardant plastic: adding 80 parts by weight of polypropylene resin and 4 parts by weight of the auxiliary agent prepared in the step S5 into a mixer, mixing for 25min, and adding the mixture into a double-screw extruder together with 2.5 parts by weight of the antibacterial flame retardant prepared in the step S4, stirring and mixing, wherein the technological parameters are as follows: the antibacterial flame-retardant plastic is prepared by heating and melting the materials at 160 ℃ in the first region, 172 ℃ in the second region, 187 ℃ in the third region and 170 ℃ in the fourth region, extruding and granulating.
Example 6
The embodiment provides a food bottle, which is prepared by adopting the antibacterial flame-retardant plastic prepared in preparation example 3 to be subjected to melt extrusion and blow molding.
Test example 1
The antibacterial flame retardant plastics prepared in examples 1 to 5 and comparative examples 1 to 10 of the present invention were subjected to mechanical property test, and the results are shown in Table 1.
(1) Tensile strength and elongation at break: the tensile rate is 50.00mm/min, the sample is a 1A dumbbell type standard spline with the thickness of 4mm, and the experimental temperature is 22+/-3 ℃ according to the specification of GB/T1040.2-2022;
(2) bending, elastic touch: the bending rate is 2.0mm/min, the deformation is 4.8mm, the sample size is 80mm multiplied by 10mm multiplied by 4mm, and the experimental temperature is 22+/-3 ℃ according to the specification of GB/T9341-2008;
(3) notched Izod impact Strength: after milling a 2mm deep V-shaped notch on a standard sample, testing the impact strength of the cantilever according to the specification of GB/T1043-2008, wherein the sample size is 80mm multiplied by 10mm multiplied by 4mm, and the experimental temperature is 22+/-3 ℃.
TABLE 1
As shown in the table above, the antibacterial flame retardant plastic prepared in the examples 1-3 of the invention has better mechanical properties.
Test example 2
The antibacterial flame retardant plastics prepared in examples 1 to 5 and comparative examples 1 to 10 of the present invention were subjected to antibacterial and mildew-proof property test, and the results are shown in tables 2 and 3.
1. Antibacterial property
Test was performed according to test method 1 film-sticking method of standard GB 21551.2-2010, and bacteria for detection: coli (ATCC 25922), staphylococcus aureus (ATCC 6538) and candida albicans (ATCC 10231); 5 samples were tested in parallel for each example and comparative example, and the average was taken.
The results are shown in Table 2.
TABLE 2
Group of Coli antibacterial efficiency (%) Staphylococcus aureus antibacterial rate (%) Candida albicans (%)
Example 1 >99.9 >99.9 >99.9
Example 2 >99.9 >99.9 >99.9
Example 3 >99.9 >99.9 >99.9
Example 4 97.2 95.7 94.9
Example 5 96.9 96.0 95.0
Comparative example 1 99.8 98.9 98.1
Comparative example 2 90.1 89.5 88.6
Comparative example 3 92.4 91.9 91.0
Comparative example 4 88.7 86.9 86.0
Comparative example 5 91.7 90.5 89.8
Comparative example 6 94.2 93.6 92.7
Comparative example 7 98.7 98.0 97.9
Comparative example 8 98.9 98.1 97.6
Comparative example 9 98.2 97.5 97.0
Comparative example 10 95.7 94.2 93.1
2. Mildew resistance
The test was performed according to the test method of standard QB/T2591-2003, and the bacteria used for detection were: aspergillus niger (ATCC 20611), aspergillus terreus (ATCC 1012), aureobasidium pullulans (ATCC 201428), 5 per example and comparative example were tested in parallel and averaged.
The results are shown in Table 3.
TABLE 3 Table 3
Group of Aspergillus niger longum grade Aspergillus terreus longus grade Aureobasidium pullulans mould grade
Example 1 Level 0 Level 0 Level 0
Example 2 Level 0 Level 0 Level 0
Example 3 Level 0 Level 0 Level 0
Example 4 Level 1 Level 0 Level 0
Example 5 Level 0 Level 1 Level 0
Comparative example 1 Level 0 Level 0 Level 0
Comparative example 2 Level 1 Level 2 Level 1
Comparative example 3 Level 1 Level 1 Level 1
Comparative example 4 Level 2 Level 2 Level 2
Comparative example 5 Level 1 Level 1 Level 1
Comparative example 6 Level 0 Level 1 Level 1
Comparative example 7 Level 0 Level 0 Level 0
Comparative example 8 Level 0 Level 0 Level 0
Comparative example 9 Level 0 Level 0 Level 0
Comparative example 10 Level 1 Level 1 Level 1
As shown in the table above, the antibacterial flame-retardant plastic prepared by the invention has good antibacterial, bacteriostatic and mildew-proof effects.
Test example 3
The antibacterial flame retardant plastics prepared in examples 1 to 5 and comparative examples 1 to 10 of the present invention were subjected to flame retardant property test, and the results are shown in Table 4.
Limiting Oxygen Index (LOI): the sample sizes were 80mm by 10mm by 4mm according to GB/T2406.2-2009 test.
The vertical burn performance was measured according to GB/T2408-2021 with sample dimensions of 125mm by 12.5mm by 3.2mm.
TABLE 4 Table 4
Group of Vertical combustion grade (stage) LOI(％)
Example 1 V-0 35.7
Example 2 V-0 36.1
Example 3 V-0 36.5
Example 4 V-0 33.2
Example 5 V-0 32.9
Comparative example 1 V-1 30.2
Comparative example 2 V-0 34.7
Comparative example 3 V-0 34.5
Comparative example 4 V-0 33.9
Comparative example 5 V-0 34.9
Comparative example 6 V-0 31.4
Comparative example 7 V-1 29.3
Comparative example 8 V-2 27.8
Comparative example 9 V-2 25.6
Comparative example 10 V-1 29.8
As shown in the table above, the antibacterial flame retardant plastic prepared in the examples 1-3 of the invention has better flame retardant property.
Examples 4 and 5 compare with example 3, the composite silane coupling agent was KH570 or A151 alone. Comparative example 10 compared to example 3, step S5 was not performed. The mechanical property, the flame retardant property and the antibacterial and mildew-proof property are reduced. After the prepared antibacterial flame retardant is modified by a silane coupling agent with double bonds, the surface of the prepared modified antibacterial flame retardant is provided with double bonds, and the double bonds of a small amount of free radicals in polypropylene or polyethylene resin can be polymerized under a melting condition so as to be fixed on a matrix molecular chain, so that the dispersibility and compatibility of the modified antibacterial flame retardant are improved, on the other hand, si element in the modified antibacterial flame retardant can also play a role in synergistic flame retardance, a carbon-containing silicate layer is formed on the surface of a polymer, the escape of combustible gas and the generation of free radicals are delayed or prevented, and meanwhile, the carbon formation of the polymer is promoted, the degradation speed of the polymer is reduced, and the thermal decomposition of the polymer is not easy to occur at high temperature.
In comparative example 1, as compared with example 3, no magnesium sulfate was added in step S1. The flame retardant properties are reduced. The metal oxide MgO carried on the surface of the invention is used for desorbing the heat of the surface of the combustion product when being heated, simultaneously releasing water to dilute the oxygen on the surface of the combustion product, and the active magnesium oxide generated by decomposition is attached to the surface of the matrix, so that the combustion is further prevented, and the active magnesium oxide can be well cooperated with the expanded graphite for flame retardance.
In comparative examples 2 and 3, copper sulfate or thiourea was not added in step S1, as compared with example 3. Comparative example 4 in contrast to example 3, no thiourea and copper sulphate were added in step S1. The antibacterial and mildew-proof performance is reduced. Preparation of Cu-N-S doped TiO by sol-gel reaction of the invention 2 At the time, tiO is prepared by adding thiourea 2 In the process of doping N/S element, sulfur element enters TiO in the form of cation 2 In the lattice, electron occupying energy level is formed above the valence band, nitrogen is doped with NH 3 In the form of TiO 2 The valence band (O2 p) forms an unfilled intermediate energy level (N2 p) which, in combination, causes TiO to form 2 Is narrower and the spectral response range is wider. Under the addition of copper salt, the prepared N-S doped TiO 2 On the one hand, the forbidden band width can be further narrowed, the valence band moves upwards, the conduction band moves downwards to the vicinity of the fermi surface, the energy required by exciting electrons in the valence band to the conduction band is reduced, and the corresponding spectrum range is widened after Cu doping. On the other hand, cu ion is also an excellent broad-spectrum antibacterial material, has the advantage of low price and practicality compared with Ag, and has good antibacterial effect, and can directly act on the cell wall of bacteria, be combined with-SH and the like, act on proteins or enzymes of the bacteria; or accumulate on the surface of bacterial cell membrane under the action of electric field adsorption to destroy the permeability of bacterial cell membrane; or can be combined with bacterial cell DNA to inhibit RNA, DNA and cell protein synthesis, reduce bacterial activity, and inhibit bacterial proliferation.
Comparative example 5 compared to example 3, step S2 was not performed. The antibacterial and mildew-proof performance is reduced. The invention prepares Cu-N-S doped TiO 2 The MgO deposition expanded graphite is hydrogenated under the action of high-pressure hydrogen, and the TiO is enabled by the reduction of the hydrogen 2 The tetravalent titanium in the crystal is reduced to form low-valence titanium, so that the perfect crystal structure is partially destroyed and interrupted, crystal defects are formed, the movement condition of photo-generated electrons and holes is influenced, the distribution state is adjusted or TiO is changed 2 Therefore, the response range of the available absorbed light is further widened, so that the hydrogenated Cu-N-S doped TiO is prepared 2 Can well utilize visible light to exert the effect of formaldehyde pollutant degradation and photocatalysis antibiosis.
Comparative example 6 compared to example 3, step S3 was not performed. The flame retardant property, the antibacterial and mildew-proof properties and the mechanical properties are reduced. The invention prepares the hydrogenated Cu-N-S doped TiO 2 On one hand, the nitrogen element in the modified antibacterial flame retardant is improved by modifying the surface of MgO deposition expanded graphite by polydopamineOn the other hand, under the polyamino, carboxyl and hydroxyl structures of the polydopamine, the urea and phosphate ester synergistic flame retardant can be well fixed, and meanwhile, the synergistic flame retardant has certain antibacterial performance.
In comparative examples 7 and 8, urea or tributyl phosphate was not added in step S4, as compared with example 3. Comparative example 9 compared to example 3, step S4 was not performed. The flame retardant property and the mechanical property are reduced. The invention fixes urea and phosphate ester synergistic flame retardant, urea can be regarded as the air source when the expanded graphite burns, the compound which discharges inert gas when being heated, thus has cut off the contact of flammable substance of the basal body and oxygen, raise the fire resistance, the phosphate ester can raise the mechanical property of basal body material on the one hand, on the other hand, the compound use of expandable graphite, urea, phosphorus compound, magnesium oxide, the residue of the charcoal remains on the burning surface totally, form a complete barrier layer, the residue has absorbed the basal body resin melted in the combustion process, have thoroughly overcome the molten drop phenomenon produced in the resin combustion process, will not produce the fly ash phenomenon too, have very good smoke suppression effect, several produce the synergistic effect, the consumption is very little can reach the fire-retardant goal.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims (10)

1. A preparation method of an antibacterial flame-retardant plastic is characterized in that Cu-N-S doped TiO is prepared through sol-gel reaction 2 And (3) carrying out hydrogenation treatment on MgO deposition expanded graphite, then carrying out surface modification on polydopamine, fixing urea and phosphate, preparing a modified antibacterial flame retardant under the modification effect of a silane coupling agent, mixing with an auxiliary agent, polyethylene or polypropylene resin, and carrying out melt extrusion granulation to obtain the antibacterial flame retardant plastic.
2. The method of manufacturing according to claim 1, comprising the steps of:
s1.Cu-N-S doped TiO 2 Preparation of MgO-deposited expanded graphite: dissolving tetrabutyl titanate and magnesium salt in ethanol, adding glacial acetic acid and expanded graphite, and uniformly dispersing to obtain a suspension A; dissolving copper salt and thiourea in ethanol water solution to obtain solution B; dropwise adding the solution B into the suspension A, stirring and reacting to form sol, aging to form gel, drying, calcining to obtain Cu-N-S doped TiO 2 MgO deposition of expanded graphite;
s2, hydrogenation Cu-N-S doped TiO 2 Preparation of MgO-deposited expanded graphite: doping the Cu-N-S prepared in the step S1 with TiO 2 Adding MgO deposition expanded graphite into a high-pressure reaction kettle, introducing high-purity hydrogen, heating, stirring, reacting, naturally cooling and deflating to obtain hydrogenated Cu-N-S doped TiO 2 MgO deposition of expanded graphite;
s3, modifying polydopamine: adding hydrogenated Cu-N-S doped TiO prepared in the step S2 2 Adding MgO deposition expanded graphite into water, adding dopamine hydrochloride and a catalyst, heating and stirring for reaction, centrifuging, washing and drying to obtain modified hydrogenated Cu-N-S doped TiO 2 MgO deposition of expanded graphite;
s4, fixing a synergistic flame retardant: dissolving urea and phosphate in ethanol, and adding modified hydrogenated Cu-N-S doped TiO prepared in the step S3 2 MgO deposition expanded graphite, heating and stirring for reaction, centrifuging, washing and drying to obtain the antibacterial flame retardant;
s5, modification: dissolving a composite silane coupling agent in ethanol, adding the antibacterial flame retardant prepared in the step S4, heating, stirring, reacting, centrifuging, washing, and drying to obtain a modified antibacterial flame retardant;
s6, preparing an auxiliary agent: uniformly mixing an antioxidant, a lubricant, a plasticizer, talcum powder and nano calcium carbonate to prepare an auxiliary agent;
s7, preparation of antibacterial flame-retardant plastic: adding the auxiliary agent prepared in the step S6 into a mixer for uniform mixing, adding the auxiliary agent and the modified antibacterial flame retardant prepared in the step S5 into a double-screw extruder for stirring and mixing, heating and melting, extruding and granulating to obtain the antibacterial flame retardant plastic.
3. The preparation method according to claim 2, wherein in the step S1, the mass ratio of tetrabutyl titanate, magnesium salt, glacial acetic acid, expanded graphite, copper salt and thiourea is 10-12:7-10:5-7:22-27:1-2:3-5, the concentration of the aqueous ethanol solution is 30-50wt%, the stirring reaction time is 1-3 hours, the aging time is 7-10 hours, the calcining temperature is 450-500 ℃ and the time is 2-4 hours, the magnesium salt is at least one of magnesium chloride, magnesium sulfate and magnesium nitrate, and the copper salt is at least one of copper chloride, copper sulfate and copper nitrate.
4. The preparation method according to claim 2, wherein the purity of the high-purity hydrogen in the step S2 is more than 99.9%, 2-3MPa of high-purity hydrogen is introduced, the temperature of the heating and stirring reaction is 150-170 ℃, and the time is 12-15h.
5. The method according to claim 2, wherein the hydrogenated Cu-N-S doped TiO in step S3 2 The mass ratio of the MgO deposition expanded graphite to the dopamine hydrochloride to the catalyst is 10-12:7-10:0.5-1, the catalyst is Tris-HCl solution with pH value of 8.5-9, the temperature of the heating and stirring reaction is 40-50 ℃, and the time is 3-5h.
6. The preparation method according to claim 2, wherein in the step S4, the mass ratio of urea, phosphate ester and modified hydrogenated Cu-N-S doped TiO2/MgO deposited expanded graphite is 2-4:5-7:40-50, the phosphate ester is at least one selected from trimethyl phosphate, triethyl phosphate and tributyl phosphate, the temperature of the heating and stirring reaction is 35-40 ℃ and the time is 1-3h.
7. The preparation method according to claim 2, wherein the composite silane coupling agent in step S5 is at least two selected from KH570, a151, a171, a172, preferably a mixture of KH570 and a151, the mass ratio of the composite silane coupling agent to the antibacterial flame retardant is 10-12:3-5, the mass ratio of the composite silane coupling agent to the antibacterial flame retardant is 3-5:12-15, the temperature of the heating and stirring reaction is 45-50 ℃, and the time is 1-2h.
8. The preparation method according to claim 2, wherein in the step S6, the mass ratio of the antioxidant, the lubricant, the plasticizer, the talcum powder and the nano calcium carbonate is 1-2:0.5-1:2-3:3-5:2-4, the antioxidant is at least one of p-phenylenediamine, polyphenol and hydroquinone, the lubricant is polyethylene wax, and the plasticizer is at least one of triethyl citrate, acetyl triethyl citrate and tributyl citrate; in the step S7, the mass ratio of the polyethylene or polypropylene resin, the auxiliary agent and the modified antibacterial flame retardant is 70-90:3-5:2-3, the mixing time in the mixer is 20-30min, and the technological parameters of the double-screw extruder are as follows: first region 155-165 ℃, second region 170-175 ℃, third region 185-190 ℃, and fourth region 165-175 ℃.
9. An antibacterial flame retardant plastic prepared by the preparation method as claimed in any one of claims 1 to 8.
10. A food bottle is characterized in that the antibacterial flame-retardant plastic is prepared by melt extrusion and blow molding of the antibacterial flame-retardant plastic in claim 9.
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