CN113652081A - Antibacterial flame-retardant foamed plastic - Google Patents

Antibacterial flame-retardant foamed plastic Download PDF

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CN113652081A
CN113652081A CN202110966242.6A CN202110966242A CN113652081A CN 113652081 A CN113652081 A CN 113652081A CN 202110966242 A CN202110966242 A CN 202110966242A CN 113652081 A CN113652081 A CN 113652081A
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parts
composite antibacterial
foam plastic
antibacterial
flame
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CN113652081B (en
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魏旭东
丁向丽
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Hubei Shifeng New Material Co ltd
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Ningbo Jiaxin Chemical Industry Co ltd
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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    • C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
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Abstract

The invention discloses an antibacterial flame-retardant foamed plastic which is prepared by the following method: (1) uniformly mixing the polyol composition, the flame retardant and the composite antibacterial agent; adding polyisocyanate, stirring, injecting into a mould, foaming and molding to obtain molded foam plastic; (2) and (3) putting the formed foam plastic and the mold into an oven for drying, and stripping and taking out the formed foam plastic from the mold to obtain the foam plastic. The antibacterial flame-retardant foamed plastic disclosed by the invention has good mechanical properties, antibacterial properties and flame retardant properties.

Description

Antibacterial flame-retardant foamed plastic
Technical Field
The invention belongs to the technical field of plastics, and particularly relates to an antibacterial flame-retardant foamed plastic.
Background
The foamed plastic is a high molecular material formed by dispersing a large number of gas micropores in solid plastic, and the interconnected or non-interconnected micropores can obviously reduce the apparent density of the foamed plastic. The foamed plastic has the excellent performances of light weight, heat insulation, sound absorption, shock absorption, good dielectric insulation, low water absorption rate and the like, and is widely applied to household appliance packaging, fruit and vegetable packaging, building heat insulation materials, heat insulation boxes for express delivery and cold chain transportation and the like. However, the traditional foam plastic has poor antibacterial and mildewproof performance, brings inconvenience in the using process and causes poor experience of users. In addition, the foam plastic belongs to flammable materials, and if sparks are encountered, a fire disaster is easily caused, and potential safety hazards exist. Therefore, the antibacterial and mildewproof performance of the foam plastic is improved, and the flame retardant performance of the foam plastic is improved, so that the antibacterial and mildewproof performance of the foam plastic is of great significance.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides an antibacterial flame-retardant foam plastic.
A preparation method of antibacterial flame-retardant foam plastic comprises the following steps:
(1) according to the weight portion, 40 to 70 portions of polyol composition and 0.5 to 1.8 portions of composite antibacterial agent are evenly mixed under the conditions of 25 to 30 ℃ and 30 to 60 percent of relative humidity; then adding 50-80 parts of polyisocyanate, stirring at the rotating speed of 400-800rpm for 14-30s, injecting into a mold preheated to 60-90 ℃, and foaming and molding at 60-90 ℃ for 3-10min to obtain molded foam plastic;
(2) and putting the formed foam plastic and the mold into an oven with the temperature of 80-100 ℃ for drying for 2-4h, naturally cooling to room temperature, and taking out the foam plastic after stripping from the mold.
Preferably, the preparation method of the antibacterial flame-retardant foam plastic comprises the following steps:
(1) according to the weight portion, 40 to 70 portions of polyol composition, 1 to 5 portions of flame retardant and 0.5 to 1.8 portions of composite antibacterial agent are evenly mixed under the conditions of 25 to 30 ℃ and 30 to 60 percent of relative humidity; then adding 50-80 parts of polyisocyanate, stirring at the rotating speed of 400-800rpm for 14-30s, injecting into a mold preheated to 60-90 ℃, and foaming and molding at 60-90 ℃ for 3-10min to obtain molded foam plastic;
(2) and putting the formed foam plastic and the mold into an oven with the temperature of 80-100 ℃ for drying for 2-4h, naturally cooling to room temperature, and taking out the foam plastic after stripping from the mold.
The polyisocyanate is any one of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI), Lysine Diisocyanate (LDI) and polyphenyl polymethylene polyisocyanate (PAPI).
The polyol composition comprises the following components in parts by weight: 80-120 parts of polyol, 2-5 parts of plasticizer, 2-8 parts of catalyst, 6-14 parts of foaming agent and 3-6 parts of foam stabilizer.
The polyol is at least one of polyether polyol, polyester polyol and polymer polyol. Preferably, the polyol is a polyether polyol mixture with a hydroxyl value of 350-650mg KOH/g and a functionality of 2.8-3.6. Further, the polyol is a mixture of 60 to 90 parts by weight of polyether polyol 303 and 10 to 40 parts by weight of polyether polyol 204.
The plasticizer is any one of dibutyl phthalate and dioctyl phthalate.
The catalyst is an organic tin catalyst and/or a tertiary amine catalyst.
Preferably, the catalyst is a mixture of an organotin-based catalyst and a tertiary amine-based catalyst.
Further preferably, the catalyst is prepared by mixing an organic tin catalyst and a tertiary amine catalyst in a mass ratio of (1-2.4): 1.
The organic tin catalyst is one of dibutyltin dilaurate and stannous octoate.
The tertiary amine catalyst is one of triethanolamine, triethylene diamine and triethylamine.
Tertiary amine catalyst to isocyano (-NCO)/water (H)2O) reaction has high catalytic rate, and the organotin catalyst is p-NCO/H2The O reaction has low catalytic speed, but the p-NCO/-OH reaction has high catalytic speed, and the molecular weight of the product can be rapidly increased, gel is generated, and the viscosity is rapidly increased. The main foaming agent of the invention is a chemical foaming agent H2And O, when the tertiary amine catalyst is used alone, the generation of gas reduces the viscosity of the system, influences the chain growth rate, and further causes bubble breakage and structure collapse. The organic tin catalyst used alone is easy to cause insufficient body foaming and overlarge system viscosity. The reasonable combination of the two can simultaneously catalyze the foaming reaction and the chain growth reaction speed to ensure that the reaction is rapidly carried out, and the foaming agent and the foam stabilizer are combined togetherUnder the action, the two reach mutual balance to generate ideal foam. And the composite antibacterial agent can uniformly and stably exist in the foam plastic matrix, and the antibacterial and mildewproof functions are realized.
The foaming agent is a mixture of pentane hydrocarbon and water in a mass ratio of 1: (2.2-4.8).
The pentane hydrocarbon is one of n-pentane, cyclopentane and isopentane.
Isocyanate reacts with water to generate CO2The foaming gas generates heat, pentane hydrocarbon is easy to gasify at a low boiling point, and the pentane hydrocarbon absorbs reaction heat to generate the foaming gas. When water is used as a foaming agent alone, because reaction heat cannot be rapidly transferred and dissipated, heat overstock causes gas volume to expand too fast, side reaction is easy to generate, and the generated bubbles are large and uneven in pore size and mostly open pores. The proportion of pentane hydrocarbon and water is controlled by compounding, so that isocyanate and water are subjected to chemical reaction to generate CO2The foaming reaction heat is absorbed by a physical foaming agent pentane hydrocarbon, new foaming gas is generated, and the temperature is reduced at the same time, so that multipoint simultaneous foaming is realized, mutual overstocking is not easy to break, the gas expansion rate is in a controllable range, the generated foam is fine and dense, the proportion of open pores and closed pores is controlled to be appropriate under the condition that a cell opening agent is not used independently, and the mechanical strength of the foamed plastic is improved.
The foam stabilizer is a silicone oil foam stabilizer. Plays the roles of emulsifying foam materials, stabilizing foams and regulating cells.
The preparation method of the composite antibacterial agent comprises the following steps:
s1, adding 2-4 parts of nano tin dioxide into 76-88 parts of thin Ti layer with the concentration of 1-8mg/mL according to parts by weight3C2TXIn the water dispersion, ultrasonic dispersion treatment is carried out for 0.5-2h under the conditions of room temperature, 200-400W and 30-40kHz to obtain inorganic composite antibacterial liquid;
s2, adding 1-5 parts of chitosan into the inorganic composite antibacterial liquid, and stirring and reacting at the rotating speed of 100-300rpm for 10-15h at room temperature to obtain an organic-inorganic composite antibacterial liquid;
s3, carrying out vacuum filtration on the organic-inorganic composite antibacterial liquid to obtain a filter cake a, then adding water until the filter cake a is immersed, washing, carrying out suction filtration, washing for 1-3 times to obtain a filter cake b, then adding absolute ethyl alcohol until the filter cake b is immersed, carrying out alcohol washing, carrying out suction filtration, and washing for 1-3 times to obtain a solid substance I, and carrying out vacuum drying on the solid substance I at the temperature of 40-55 ℃ for 8-10 hours to obtain the composite antibacterial agent.
Nano tin dioxide, Ti3C2TXIs an inorganic antibacterial agent and is easy to agglomerate when used independently. The nano tin dioxide is uniformly distributed on the Ti by ultrasonic mixing3C2TXThe interlayer of the nano particles solves the problem that the nano particles are difficult to disperse uniformly, and is helpful to prevent the self-agglomeration of the nano particles. Ti3C2TXThe excellent conductivity is beneficial to the formation of more stable photo-generated electron-hole pairs by the nano tin dioxide, so that the catalytic antibacterial effect is synergistically improved. Ti3C2TXHas antioxidant function, so that no additional antioxidant is required to be added into the polyether polyol composition, and Ti3C2TXAfter being oxidized, can also generate inorganic antibacterial agent TiO2And the antibacterial effect is continuously exerted. The chitosan is a natural polymer bacteriostatic agent, has higher cationic charge density, is tightly combined with the effective components of the inorganic composite antibacterial liquid through electrostatic action, and the natural polymer antibacterial agent and the inorganic antibacterial agent act together, so that the prepared antibacterial flame-retardant foamed plastic has strong antibacterial mildew resistance, good durability, good biocompatibility, low toxicity and more environmental protection.
The composite antibacterial agent also plays a role of a nucleating agent in the preparation of the foam plastic, the nucleating agent particles distributed uniformly are beneficial to preparing high-quality foam with finer and more uniform foam cells, the composite antibacterial agent can play a role in enhancing the foam plastic, and the performance of the foam plastic is improved.
The composite antibacterial agent is easy to cause the rapid increase of the system viscosity, and meanwhile, hydroxyl in the structure and polyisocyanate undergo-NCO/-OH reaction under the action of an organotin catalyst to participate in the foaming reaction to promote the foaming reaction, and the composite antibacterial agent is uniformly and stably existed in the generated foam plastic as an important component of the matrix structure of the foam plastic, so that the composite antibacterial agent is not easy to separate out and has durable and stable antibacterial and mildew-proof properties.
Preferably, the preparation method of the composite antibacterial agent comprises the following steps:
s1, adding 2-4 parts of nano tin dioxide into 76-88 parts of thin Ti layer with the concentration of 1-8mg/mL according to parts by weight3C2TXIn the water dispersion, ultrasonic dispersion treatment is carried out for 0.5-2h under the conditions of room temperature, 200-400W and 30-40kHz to obtain inorganic composite antibacterial liquid;
s2, dropwise adding ammonia water into the inorganic composite antibacterial liquid to adjust the pH value to 8, then adding 0.5-1 part of dopamine, stirring at the rotation speed of 150-350rpm for 8-16min, and standing at room temperature for reaction for 24-36h to obtain dopamine co-modified inorganic composite antibacterial liquid;
s3, adding 1-5 parts of chitosan into the dopamine co-modified inorganic composite antibacterial liquid, and stirring and reacting at the rotating speed of 100-300rpm for 10-15 hours at room temperature to obtain an organic-inorganic composite antibacterial liquid;
s4, carrying out vacuum filtration on the organic-inorganic composite antibacterial liquid to obtain a filter cake a, then adding water until the filter cake a is immersed, washing, carrying out suction filtration, washing for 1-3 times to obtain a filter cake b, then adding absolute ethyl alcohol until the filter cake b is immersed, carrying out alcohol washing, carrying out suction filtration, and washing for 1-3 times to obtain a solid substance I, and carrying out vacuum drying on the solid substance I at the temperature of 40-55 ℃ for 8-10 hours to obtain the composite antibacterial agent.
Co-modification of thin Ti layer by dopamine3C2TXAnd nano tin dioxide, so that the nano tin dioxide can be in a thin layer of Ti3C2TXThe nano-sheets are firmly combined and are not easy to migrate, the self-polymerization of dispersed particles is effectively inhibited, and the stability of a dispersion system is ensured. Furthermore, a thin layer of Ti3C2TXThe specific surface area of the inorganic catalyst is improved by compounding with nano tin dioxide, and dopamine is in a thin layer Ti3C2TXThe surface of the nano tin dioxide is connected with more functional groups with stronger activity, such as hydroxyl, amino, carboxyl and the like, so that the thin Ti layer can be enhanced3C2TXAnd the compatibility and the electrostatic action of the nano tin dioxide compound and the natural organic polymer antibacterial agent chitosan, so that the nano tin dioxide compound and the natural organic polymer antibacterial agent chitosan are combined more closely.
After the dopamine modification, the composite antibacterial agent is more uniformly and stably distributed in a reaction system for generating the foam plastic by a one-step method, and the composite antibacterial agent is used as a nucleating agent to promote the prepared foam to be finer and more uniform, so that the performance of the foam plastic is further improved. And because the hydroxyl in the structure is richer, more hydroxyl participates in the foaming reaction, the foaming reaction is promoted to be carried out, and the hydroxyl stably and uniformly exists in the foam plastic structure, so that the antibacterial and mildew-proof properties are more durable and stable.
The preparation method of the flame retardant comprises the following steps:
adding 3-aminopropyltrimethoxysilane into water, stirring for 1-3h at the temperature of 90-100 ℃ and at the stirring speed of 100-150rpm, wherein the mass ratio of the 3-aminopropyltrimethoxysilane to the water is (1-2):3, so as to obtain a mixed solution A; then adding 1,3,5, 7-tetraethylcyclotetrasiloxane, tris (trimethylsiloxy) silane and potassium tert-butoxide, uniformly mixing, heating to 130 ℃ and 150 ℃, and continuously stirring for 3-6h, wherein the mass ratio of the 1,3,5, 7-tetraethylcyclotetrasiloxane, tris (trimethylsiloxy) silane, potassium tert-butoxide to the mixed solution A is (40-50): (0.3-0.6): 0.05-0.1): 5-15, so as to obtain a product B; mixing abietic acid and the product B according to the mass ratio of (1-3) to 5, and stirring for 3-5h at 95-100 ℃ and 50-100rpm to obtain a product C; adding the product C and N- [ (10-oxo-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-yl) methyl ] -6-phenyl-1, 3, 5-triazine-2, 4-diamine into trichloromethane, and heating for 10-15h at the temperature of 60-70 ℃, wherein the mass ratio of the product C, N- [ (10-oxo-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-yl) methyl ] -6-phenyl-1, 3, 5-triazine-2, 4-diamine to the trichloromethane is (3-6): 1-3): 15-25); and (4) performing rotary evaporation to remove the trichloromethane to obtain the product.
An antibacterial flame-retardant foamed plastic is prepared by adopting the method.
The invention has the beneficial effects that: the antibacterial flame-retardant foamed plastic disclosed by the invention has good mechanical properties, antibacterial performance and flame retardant performance, and is simple in preparation process, low in energy consumption and convenient to popularize and apply.
Detailed Description
The raw materials used in the examples were as follows:
polyether polyol 303 (glycerol polyoxypropylene ether), hydroxyl value: 550mgKOH/g, southwest City modest and chemical Co.
Polyether polyol 204 (propylene glycol and propylene oxide adduct), hydroxyl value: 280mgKOH/g, southeast City modest and chemical Co.
Silicone oil AK8805, viscosity (25 ℃): 1200mpa.s, mesde chemist gmbh, Jiangsu.
Nano tin dioxide, CAS number: 18282-10-5, type: YC-Sn20, purity: 99.9%, particle size: 20-30nm, Shanghai Yingyun New Material Co.
Thin layer of Ti3C2TXAqueous dispersion, CAS No.: 12363-89-2, concentration: 5mg/mL, plate diameter: 2-5 μm, thickness: 3-5nm, Xian Qiyue Biotech Co., Ltd.
Chitosan, CAS No.: 9012-76-4, viscosity: 200mpa.s, deacetylation degree not less than 90%, Qingdao cloud biotechnology limited.
Dopamine, CAS number: 51-61-6, cat #: ZL-01310021, West Aze Biotech, Inc.
Ammonia water, concentration: 25%, CAS number: 1336-21-6, Jinan Chuang chemical Co.
Toluene diisocyanate, CAS No.: 584-84-9; dibutyl phthalate, CAS No.: 84-74-2; triethanolamine, CAS No.: 102-71-6; cyclopentane, CAS number: 287-92-3; 3-aminopropyltrimethoxysilane, CAS No.: 13822-56-5; 1,3,5, 7-tetraethylcyclotetrasiloxane, CAS No.: 16066-10-7; tris (trimethylsiloxy) silane, CAS No.: 1873-89-8; potassium tert-butoxide, CAS No.: 865-47-4; abietic acid, CAS No.: 514-10-3; n- [ (10-oxo-9, 10-dihydro-9-oxa-10-phosphaphenanthren-10-yl) methyl ] -6-phenyl-1, 3, 5-triazine-2, 4-diamine, CAS No.: 66560-05-2.
Example 1
A preparation method of antibacterial flame-retardant foam plastic comprises the following steps:
(1) according to the weight portion, 60 portions of polyol composition and 1 portion of composite antibacterial agent are evenly mixed under the condition of 25 ℃ and 50% of relative humidity; adding 60 parts of polyisocyanate, stirring at the rotating speed of 600rpm for 25s, injecting into a mold preheated to 80 ℃, and carrying out foaming molding at 80 ℃ for 5min to obtain molded foam plastic;
(2) and putting the formed foam plastic and the mold into a 90 ℃ oven to be dried for 3h, naturally cooling to room temperature, and stripping and taking out the foam plastic from the mold to obtain the foam plastic.
The polyisocyanate is Toluene Diisocyanate (TDI).
The polyol composition comprises the following components in parts by weight: 100 parts of polyol, 4 parts of plasticizer, 5 parts of catalyst, 8 parts of foaming agent and 4 parts of foam stabilizer.
The polyol is a mixture of 64 parts by weight of polyether polyol 303 and 36 parts by weight of polyether polyol 204.
The plasticizer is dibutyl phthalate.
The catalyst is triethanolamine.
The foaming agent is prepared from cyclopentane and water in a mass ratio of 1: 3.4.
The foam stabilizer is silicone oil AK 8805.
The preparation method of the composite antibacterial agent comprises the following steps:
s1, adding 3 parts of nano tin dioxide into 80 parts of thin Ti layer with the concentration of 3mg/mL in parts by weight3C2TXPerforming ultrasonic dispersion treatment on the aqueous dispersion for 1h at room temperature and 300W and 30kHz to obtain an inorganic composite antibacterial liquid;
s2, adding 3 parts of chitosan into the inorganic composite antibacterial liquid, and stirring and reacting at the room temperature at the rotating speed of 200rpm for 12 hours to obtain an organic-inorganic composite antibacterial liquid;
s3, carrying out vacuum filtration on the organic-inorganic composite antibacterial liquid to obtain a filter cake a, then adding water until the filter cake a is immersed, washing, carrying out suction filtration, washing with water for 3 times to obtain a filter cake b, then adding absolute ethyl alcohol until the filter cake b is immersed, carrying out alcohol washing, carrying out suction filtration, and washing with alcohol for 3 times to obtain a solid substance I, and carrying out vacuum drying on the solid substance I at 45 ℃ for 10 hours to obtain the composite antibacterial agent.
Example 2
A preparation method of antibacterial flame-retardant foam plastic comprises the following steps:
(1) according to the weight portion, 60 portions of polyol composition and 1 portion of composite antibacterial agent are evenly mixed under the condition of 25 ℃ and 50% of relative humidity; adding 60 parts of polyisocyanate, stirring at the rotating speed of 600rpm for 25s, injecting into a mold preheated to 80 ℃, and carrying out foaming molding at 80 ℃ for 5min to obtain molded foam plastic;
(2) and putting the formed foam plastic and the mold into a 90 ℃ oven to be dried for 3h, naturally cooling to room temperature, and stripping and taking out the foam plastic from the mold to obtain the foam plastic.
The polyisocyanate is Toluene Diisocyanate (TDI).
The polyol composition comprises the following components in parts by weight: 100 parts of polyol, 4 parts of plasticizer, 5 parts of catalyst, 8 parts of foaming agent and 4 parts of foam stabilizer.
The polyol is a mixture of 64 parts by weight of polyether polyol 303 and 36 parts by weight of polyether polyol 204.
The plasticizer is dibutyl phthalate.
The catalyst is dibutyltin dilaurate.
The foaming agent is prepared from cyclopentane and water in a mass ratio of 1: 3.4.
The foam stabilizer is silicone oil AK 8805.
The preparation method of the composite antibacterial agent comprises the following steps:
s1, adding 3 parts of nano tin dioxide into 80 parts of thin Ti layer with the concentration of 3mg/mL in parts by weight3C2TXPerforming ultrasonic dispersion treatment on the aqueous dispersion for 1h at room temperature and 300W and 30kHz to obtain an inorganic composite antibacterial liquid;
s2, adding 3 parts of chitosan into the inorganic composite antibacterial liquid, and stirring and reacting at the room temperature at the rotating speed of 200rpm for 12 hours to obtain an organic-inorganic composite antibacterial liquid;
s3, carrying out vacuum filtration on the organic-inorganic composite antibacterial liquid to obtain a filter cake a, then adding water until the filter cake a is immersed, washing, carrying out suction filtration, washing with water for 3 times to obtain a filter cake b, then adding absolute ethyl alcohol until the filter cake b is immersed, carrying out alcohol washing, carrying out suction filtration, and washing with alcohol for 3 times to obtain a solid substance I, and carrying out vacuum drying on the solid substance I at 45 ℃ for 10 hours to obtain the composite antibacterial agent.
Example 3
A preparation method of antibacterial flame-retardant foam plastic comprises the following steps:
(1) according to the weight portion, 60 portions of polyol composition and 1 portion of composite antibacterial agent are evenly mixed under the condition of 25 ℃ and 50% of relative humidity; adding 60 parts of polyisocyanate, stirring at the rotating speed of 600rpm for 25s, injecting into a mold preheated to 80 ℃, and carrying out foaming molding at 80 ℃ for 5min to obtain molded foam plastic;
(2) and putting the formed foam plastic and the mold into a 90 ℃ oven to be dried for 3h, naturally cooling to room temperature, and stripping and taking out the foam plastic from the mold to obtain the foam plastic.
The polyisocyanate is Toluene Diisocyanate (TDI).
The polyol composition comprises the following components in parts by weight: 100 parts of polyol, 4 parts of plasticizer, 5 parts of catalyst, 8 parts of foaming agent and 4 parts of foam stabilizer.
The polyol is a mixture of 64 parts by weight of polyether polyol 303 and 36 parts by weight of polyether polyol 204.
The plasticizer is dibutyl phthalate.
The catalyst is prepared from dibutyltin dilaurate and triethanolamine in a mass ratio of 1.8: 1.
The foaming agent is prepared from cyclopentane and water in a mass ratio of 1: 3.4.
The foam stabilizer is silicone oil AK 8805.
The preparation method of the composite antibacterial agent comprises the following steps:
s1, adding 3 parts of nano tin dioxide into 80 parts of thin Ti layer with the concentration of 3mg/mL in parts by weight3C2TXPerforming ultrasonic dispersion treatment on the aqueous dispersion for 1h at room temperature and 300W and 30kHz to obtain an inorganic composite antibacterial liquid;
s2, adding 3 parts of chitosan into the inorganic composite antibacterial liquid, and stirring and reacting at the room temperature at the rotating speed of 200rpm for 12 hours to obtain an organic-inorganic composite antibacterial liquid;
s3, carrying out vacuum filtration on the organic-inorganic composite antibacterial liquid to obtain a filter cake a, then adding water until the filter cake a is immersed, washing, carrying out suction filtration, washing with water for 3 times to obtain a filter cake b, then adding absolute ethyl alcohol until the filter cake b is immersed, carrying out alcohol washing, carrying out suction filtration, and washing with alcohol for 3 times to obtain a solid substance I, and carrying out vacuum drying on the solid substance I at 45 ℃ for 10 hours to obtain the composite antibacterial agent.
Example 4
A preparation method of antibacterial flame-retardant foam plastic comprises the following steps:
(1) according to the weight portion, 60 portions of polyol composition and 1 portion of composite antibacterial agent are evenly mixed under the condition of 25 ℃ and 50% of relative humidity; adding 60 parts of polyisocyanate, stirring at the rotating speed of 600rpm for 25s, injecting into a mold preheated to 80 ℃, and carrying out foaming molding at 80 ℃ for 5min to obtain molded foam plastic;
(2) and putting the formed foam plastic and the mold into a 90 ℃ oven to be dried for 3h, naturally cooling to room temperature, and stripping and taking out the foam plastic from the mold to obtain the foam plastic.
The polyisocyanate is Toluene Diisocyanate (TDI).
The polyol composition comprises the following components in parts by weight: 100 parts of polyol, 4 parts of plasticizer, 5 parts of catalyst, 8 parts of foaming agent and 4 parts of foam stabilizer.
The polyol is a mixture of 64 parts by weight of polyether polyol 303 and 36 parts by weight of polyether polyol 204.
The plasticizer is dibutyl phthalate.
The catalyst is prepared from dibutyltin dilaurate and triethanolamine in a mass ratio of 1.8: 1.
The foaming agent is prepared from cyclopentane and water in a mass ratio of 1: 3.4.
The foam stabilizer is silicone oil AK 8805.
The preparation method of the composite antibacterial agent comprises the following steps:
s1, adding 3 parts of nano tin dioxide into 80 parts of thin Ti layer with the concentration of 3mg/mL in parts by weight3C2TXPerforming ultrasonic dispersion treatment on the aqueous dispersion for 1h at room temperature and 300W and 30kHz to obtain an inorganic composite antibacterial liquid;
s2, dropwise adding ammonia water into the inorganic composite antibacterial liquid to adjust the pH value to 8, then adding 0.8 part of dopamine, stirring at the rotating speed of 200rpm for 12min, and standing at room temperature for reaction for 28h to obtain dopamine co-modified inorganic composite antibacterial liquid;
s3, adding 3 parts of chitosan into the dopamine co-modified inorganic composite antibacterial liquid, and stirring and reacting at the room temperature at the rotating speed of 200rpm for 12 hours to obtain an organic-inorganic composite antibacterial liquid;
s4, carrying out vacuum filtration on the organic-inorganic composite antibacterial liquid to obtain a filter cake a, then adding water until the filter cake a is immersed, washing, carrying out suction filtration, washing with water for 3 times to obtain a filter cake b, then adding absolute ethyl alcohol until the filter cake b is immersed, carrying out alcohol washing, carrying out suction filtration, and washing with alcohol for 3 times to obtain a solid substance I, and carrying out vacuum drying on the solid substance I at 45 ℃ for 10 hours to obtain the composite antibacterial agent.
Comparative example 1
A preparation method of antibacterial flame-retardant foam plastic comprises the following steps:
(1) according to the parts by weight, 60 parts of polyol composition and 1 part of composite antibacterial agent are uniformly mixed at 25 ℃, then 60 parts of polyisocyanate are added, the mixture is stirred at the rotating speed of 600rpm for 25s, then the mixture is injected into a mold preheated to 50 ℃, and the mixture is foamed and molded at 50 ℃ for 5min to obtain molded foam plastic;
(2) and putting the formed foam plastic and the mold into a 90 ℃ oven to be dried for 3h, naturally cooling to room temperature, and stripping and taking out the foam plastic from the mold to obtain the foam plastic.
The polyisocyanate is Toluene Diisocyanate (TDI).
The polyol composition comprises the following components in parts by weight: 100 parts of polyol, 4 parts of plasticizer, 5 parts of catalyst, 8 parts of foaming agent and 4 parts of foam stabilizer.
The polyol is a mixture of 64 parts by weight of polyether polyol 303 and 36 parts by weight of polyether polyol 204.
The plasticizer is dibutyl phthalate.
The catalyst is triethanolamine.
The foaming agent is prepared from cyclopentane and water in a mass ratio of 1: 3.4.
The foam stabilizer is silicone oil AK 8805.
The preparation method of the composite antibacterial agent comprises the following steps:
s1, adding 3 parts of nano tin dioxide into 80 parts of water by weight, and performing ultrasonic dispersion treatment for 1 hour at room temperature under the conditions of 300W and 30kHz to obtain inorganic antibacterial liquid;
s2, adding 3 parts of chitosan into the inorganic antibacterial liquid, and stirring and reacting at the room temperature at the rotating speed of 200rpm for 12 hours to obtain an organic-inorganic composite antibacterial liquid;
s3, carrying out vacuum filtration on the organic-inorganic composite antibacterial liquid to obtain a filter cake a, then adding water until the filter cake a is immersed, washing, carrying out suction filtration, washing with water for 3 times to obtain a filter cake b, then adding absolute ethyl alcohol until the filter cake b is immersed, carrying out alcohol washing, carrying out suction filtration, and washing with alcohol for 3 times to obtain a solid substance I, and carrying out vacuum drying on the solid substance I at 45 ℃ for 10 hours to obtain the composite antibacterial agent.
Comparative example 2
A preparation method of antibacterial flame-retardant foam plastic comprises the following steps:
(1) according to the parts by weight, 60 parts of polyol composition and 1 part of composite antibacterial agent are uniformly mixed at 25 ℃, then 60 parts of polyisocyanate are added, the mixture is stirred at the rotating speed of 600rpm for 25s, then the mixture is injected into a mold preheated to 50 ℃, and the mixture is foamed and molded at 50 ℃ for 5min to obtain molded foam plastic;
(2) and putting the formed foam plastic and the mold into a 90 ℃ oven to be dried for 3h, naturally cooling to room temperature, and stripping and taking out the foam plastic from the mold to obtain the foam plastic.
The polyisocyanate is Toluene Diisocyanate (TDI).
The polyol composition comprises the following components in parts by weight: 100 parts of polyol, 4 parts of plasticizer, 5 parts of catalyst, 8 parts of foaming agent and 4 parts of foam stabilizer.
The polyol is a mixture of 64 parts by weight of polyether polyol 303 and 36 parts by weight of polyether polyol 204.
The plasticizer is dibutyl phthalate.
The catalyst is triethanolamine.
The foaming agent is prepared from cyclopentane and water in a mass ratio of 1: 3.4.
The foam stabilizer is silicone oil AK 8805.
The preparation method of the composite antibacterial agent comprises the following steps:
s1, according to parts by weight, 83 parts of thin-layer Ti with the concentration of 3mg/mL3C2TXIn the water dispersion, the reaction temperature is 300W and 30kHz at room temperaturePerforming sound dispersion treatment for 1h to obtain inorganic antibacterial liquid;
s2, adding 3 parts of chitosan into the inorganic antibacterial liquid, and stirring and reacting at the room temperature at the rotating speed of 200rpm for 12 hours to obtain an organic-inorganic composite antibacterial liquid;
s3, carrying out vacuum filtration on the organic-inorganic composite antibacterial liquid to obtain a filter cake a, then adding water until the filter cake a is immersed, washing, carrying out suction filtration, washing with water for 3 times to obtain a filter cake b, then adding absolute ethyl alcohol until the filter cake b is immersed, carrying out alcohol washing, carrying out suction filtration, and washing with alcohol for 3 times to obtain a solid substance I, and carrying out vacuum drying on the solid substance I at 45 ℃ for 10 hours to obtain the composite antibacterial agent.
Example 5
A preparation method of antibacterial flame-retardant foam plastic comprises the following steps:
(1) according to the weight portion, 60 portions of polyol composition, 3 portions of flame retardant and 1 portion of composite antibacterial agent are evenly mixed under the condition of 25 ℃ and 50% of relative humidity; adding 60 parts of polyisocyanate, stirring at the rotating speed of 600rpm for 25s, injecting into a mold preheated to 80 ℃, and carrying out foaming molding at 80 ℃ for 5min to obtain molded foam plastic;
(2) and putting the formed foam plastic and the mold into a 90 ℃ oven to be dried for 3h, naturally cooling to room temperature, and stripping and taking out the foam plastic from the mold to obtain the foam plastic.
The polyisocyanate is Toluene Diisocyanate (TDI).
The polyol composition comprises the following components in parts by weight: 100 parts of polyol, 4 parts of plasticizer, 5 parts of catalyst, 8 parts of foaming agent and 4 parts of foam stabilizer.
The polyol is a mixture of 64 parts by weight of polyether polyol 303 and 36 parts by weight of polyether polyol 204.
The plasticizer is dibutyl phthalate.
The catalyst is prepared from dibutyltin dilaurate and triethanolamine in a mass ratio of 1.8: 1.
The foaming agent is prepared from cyclopentane and water in a mass ratio of 1: 3.4.
The foam stabilizer is silicone oil AK 8805.
The preparation method of the composite antibacterial agent comprises the following steps:
s1, adding 3 parts of nano tin dioxide into 80 parts of thin Ti layer with the concentration of 3mg/mL in parts by weight3C2TXPerforming ultrasonic dispersion treatment on the aqueous dispersion for 1h at room temperature and 300W and 30kHz to obtain an inorganic composite antibacterial liquid;
s2, dropwise adding ammonia water into the inorganic composite antibacterial liquid to adjust the pH value to 8, then adding 0.8 part of dopamine, stirring at the rotating speed of 200rpm for 12min, and standing at room temperature for reaction for 28h to obtain dopamine co-modified inorganic composite antibacterial liquid;
s3, adding 3 parts of chitosan into the dopamine co-modified inorganic composite antibacterial liquid, and stirring and reacting at the room temperature at the rotating speed of 200rpm for 12 hours to obtain an organic-inorganic composite antibacterial liquid;
s4, carrying out vacuum filtration on the organic-inorganic composite antibacterial liquid to obtain a filter cake a, then adding water until the filter cake a is immersed, washing, carrying out suction filtration, washing with water for 3 times to obtain a filter cake b, then adding absolute ethyl alcohol until the filter cake b is immersed, carrying out alcohol washing, carrying out suction filtration, and washing with alcohol for 3 times to obtain a solid substance I, and carrying out vacuum drying on the solid substance I at 45 ℃ for 10 hours to obtain the composite antibacterial agent.
The preparation method of the flame retardant comprises the following steps:
adding 3-aminopropyltrimethoxysilane into water, and stirring for 3 hours at the stirring temperature of 95 ℃ and at the stirring speed of 120rpm, wherein the mass ratio of the 3-aminopropyltrimethoxysilane to the water is 2:3, so as to obtain a mixed solution A; adding 1,3,5, 7-tetraethylcyclotetrasiloxane, tris (trimethylsiloxy) silane and potassium tert-butoxide, uniformly mixing, heating to 135 ℃, and continuing stirring for 5 hours, wherein the mass ratio of the 1,3,5, 7-tetraethylcyclotetrasiloxane, tris (trimethylsiloxy) silane, potassium tert-butoxide to the mixed solution A is 45:0.5:0.06:10, so as to obtain a product B; mixing abietic acid and the product B according to the mass ratio of 3:5, and stirring for 3.5 hours at 98 ℃ and 80rpm to obtain a product C; adding the product C and N- [ (10-oxo-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-yl) methyl ] -6-phenyl-1, 3, 5-triazine-2, 4-diamine into trichloromethane, and heating for 12h at 65 ℃, wherein the mass ratio of the product C, N- [ (10-oxo-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-yl) methyl ] -6-phenyl-1, 3, 5-triazine-2, 4-diamine to the trichloromethane is 5:2: 20; and (4) performing rotary evaporation to remove the trichloromethane to obtain the product. The flame retardant performance of the antibacterial flame-retardant foam obtained in example 5 was determined with reference to GB/T2406.2-2009, and the oxygen index was 30.7%.
Comparative example 3
A preparation method of antibacterial flame-retardant foam plastic comprises the following steps:
(1) according to the weight portion, 60 portions of polyol composition, 3 portions of flame retardant and 1 portion of composite antibacterial agent are evenly mixed under the condition of 25 ℃ and 50% of relative humidity; adding 60 parts of polyisocyanate, stirring at the rotating speed of 600rpm for 25s, injecting into a mold preheated to 80 ℃, and carrying out foaming molding at 80 ℃ for 5min to obtain molded foam plastic;
(2) and putting the formed foam plastic and the mold into a 90 ℃ oven to be dried for 3h, naturally cooling to room temperature, and stripping and taking out the foam plastic from the mold to obtain the foam plastic.
The polyisocyanate is Toluene Diisocyanate (TDI).
The polyol composition comprises the following components in parts by weight: 100 parts of polyol, 4 parts of plasticizer, 5 parts of catalyst, 8 parts of foaming agent and 4 parts of foam stabilizer.
The polyol is a mixture of 64 parts by weight of polyether polyol 303 and 36 parts by weight of polyether polyol 204.
The plasticizer is dibutyl phthalate.
The catalyst is prepared from dibutyltin dilaurate and triethanolamine in a mass ratio of 1.8: 1.
The foaming agent is prepared from cyclopentane and water in a mass ratio of 1: 3.4.
The foam stabilizer is silicone oil AK 8805.
The preparation method of the composite antibacterial agent comprises the following steps:
s1, adding 3 parts of nano tin dioxide into 80 parts of thin Ti layer with the concentration of 3mg/mL in parts by weight3C2TXPerforming ultrasonic dispersion treatment on the aqueous dispersion for 1h at room temperature and 300W and 30kHz to obtain an inorganic composite antibacterial liquid;
s2, dropwise adding ammonia water into the inorganic composite antibacterial liquid to adjust the pH value to 8, then adding 0.8 part of dopamine, stirring at the rotating speed of 200rpm for 12min, and standing at room temperature for reaction for 28h to obtain dopamine co-modified inorganic composite antibacterial liquid;
s3, adding 3 parts of chitosan into the dopamine co-modified inorganic composite antibacterial liquid, and stirring and reacting at the room temperature at the rotating speed of 200rpm for 12 hours to obtain an organic-inorganic composite antibacterial liquid;
s4, carrying out vacuum filtration on the organic-inorganic composite antibacterial liquid to obtain a filter cake a, then adding water until the filter cake a is immersed, washing, carrying out suction filtration, washing with water for 3 times to obtain a filter cake b, then adding absolute ethyl alcohol until the filter cake b is immersed, carrying out alcohol washing, carrying out suction filtration, and washing with alcohol for 3 times to obtain a solid substance I, and carrying out vacuum drying on the solid substance I at 45 ℃ for 10 hours to obtain the composite antibacterial agent.
The preparation method of the flame retardant comprises the following steps:
adding 3-aminopropyltrimethoxysilane and N- [ (10-oxo-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-yl) methyl ] -6-phenyl-1, 3, 5-triazine-2, 4-diamine into trichloromethane, and heating for 12 hours at 65 ℃, wherein the mass ratio of the 3-aminopropyltrimethoxysilane to the N- [ (10-oxo-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-yl) methyl ] -6-phenyl-1, 3, 5-triazine-2, 4-diamine to the trichloromethane is 5:2: 20; and (4) performing rotary evaporation to remove the trichloromethane to obtain the product. The flame retardant performance of the antibacterial flame-retardant foam plastic obtained in comparative example 3 is determined by referring to GB/T2406.2-2009, and the oxygen index of the foam plastic is 27.5%.
Test example 1
The antibacterial flame-retardant foamed plastic prepared in each example is subjected to basic performance test, and the detection results are shown in table 1.
(1) And (3) testing the opening rate: test method referring to GB/T10799-.
(2) Size change rate test: the test method refers to GB/T8811-: the test was carried out at a relative humidity of 50% and a temperature of 23 ℃ for a total time of 48 hours, and the arithmetic mean of the dimensional change rates of the length, width and thickness was taken as the sample dimensional change rate, and 3 groups of the test samples were averaged for each test, and the conditions were adjusted at a relative humidity of 50% and a temperature of 23 ℃.
TABLE 1 basic Properties of antibacterial flame-retardant foams
Volume open area ratio/%) Rate of change in dimension/%)
Example 1 92 0.36
Example 2 28 0.41
Example 3 58 0.30
Example 4 65 0.22
Comparative example 1 90 0.52
Comparative example 2 88 0.54
Test example 2
The antibacterial flame-retardant foamed plastics prepared in each example are subjected to mechanical property tests, and the detection results are shown in table 2.
(1) And (3) testing the compression performance: the test method refers to GB/T8813-: 400mm 50mm, the conditions of 50% relative humidity, 23 ℃ conditions for conditioning and testing, using method A, test speed of 5mm/min, test compression strength, each test 5 groups of the average.
(2) And (3) testing tensile property: the test method refers to GB/T9641-1988 rigid foam plastic tensile property test method, and the sample size is as follows: the maximum tensile strength was measured by conditioning and testing at a relative humidity of 50% and a temperature of 23 ℃ at 400 mm. times.400 mm. times.50 mm, and 5 groups for each test were averaged.
(3) And (3) testing the bending property: the test method refers to GB/T8812.2-2007 Standard for determination of bending property of rigid foam, part 2, determination of bending strength and apparent bending elastic modulus, the state adjustment and test are carried out under the conditions of 50% of relative humidity and 23 ℃, and the size of a sample is as follows: 350mm × 100mm × 25mm, the test speed is 20mm/min, the bending strength is tested, and 5 groups of tests in each case are averaged.
TABLE 2 mechanical Properties of antibacterial flame-retardant foams
Figure BDA0003224085730000171
Figure BDA0003224085730000181
Test example 3
(1) And (3) detecting antibacterial performance: the test method refers to the standard of GB/T31402-2015 test method for surface antibacterial property of plastic plastics, and the test: a nutrient agar method,the test plastics have a size of 50mm × 50mm and a thickness of 4mm, the test strains are Escherichia coli ATCC 8739 and Staphylococcus aureus ATCC 6538, and the concentration of the selected strain is 5.0 × 105The cfu/mL diluted solution was used as the experimental bacterial solution, and the results are shown in Table 2.
(2) And (3) detecting the anti-mildew performance: the test method refers to the standard GB/T24128-: the nutrient agar method comprises testing plastic size of 40mm × 40mm and thickness of 4mm, and culturing Aspergillus niger ATCC 6275, Paecilomyces variotii CBS 628.66, Penicillium funiculosum ATCC 9644, Trichoderma longibrachiatum ATCC 13631 and Mucor globosum ATCC 6205 to obtain a culture product with concentration of 6.0 × 106And (3) mixing the five mould spore suspensions into a mixed bacterial liquid before use.
TABLE 3 antibacterial and mildewproof property test results of antibacterial and flame retardant foam
Figure BDA0003224085730000182
Example 1 the tertiary amine catalyst used alone has a faster foaming speed and a slower gelling speed than example 2 which uses the organotin catalyst alone, but the foam obtained has a high open cell content, but too fast foaming tends to result in non-uniform cell size and non-uniform distribution, resulting in a large dimensional change rate and having an influence on mechanical properties. Example 2 gel fast, foaming slow, the foamed plastic obtained is low in open cell rate, high in closed cell rate, easy to cause the foamed plastic to expand and deform by heating, and large in size change rate. Example 3 when the tertiary amine catalyst and the organotin catalyst were used in combination, the rate of formation of the foaming gas and the rate of formation of the polymer were easily adjusted and could be coordinated, resulting in more uniform foaming, production of ideal foams, and better dimensional stability and mechanical properties.
In comparison with the comparative examples, the examples use a thin Ti layer3C2TXAnd nano tin dioxide as inorganic antiseptic, and the nano tin dioxide is distributed homogeneously in Ti3C2TXSolves the problem that the nano particles are difficult to be uniformly dispersed, andhelping to prevent self-agglomeration of the nanoparticles. Then the composite antibacterial agent is compounded with organic antibacterial agent chitosan to obtain the composite antibacterial agent which can jointly play the antibacterial and mildewproof role. The prepared antibacterial flame-retardant foamed plastic has strong antibacterial and mildew-proof properties, good biocompatibility and environmental protection.
The composite antibacterial agent particles also play a role of nucleating agent in the preparation of the foam plastic, so that the nucleating agent particles distributed uniformly are beneficial to preparing high-quality foam with finer and more uniform foam cells, can play a role in enhancing the foam plastic and improve the performance of the foam plastic. And the viscosity of the system is easily and rapidly increased due to the composite antibacterial agent, and meanwhile, the structure contains hydroxyl, so that the composite antibacterial agent can participate in the foaming reaction under the action of an organic tin catalyst to promote the foaming reaction, and the composite antibacterial agent stably and uniformly exists in a foam plastic matrix structure, so that the antibacterial and mildew-proof performance is stronger, and the composite antibacterial agent is more durable and stable.
Example 4 Co-modification of thin Ti by dopamine3C2TXAnd the nano tin dioxide further ensures the stability of a dispersion system, and more active functional groups are connected to the surface of the inorganic antibacterial agent, so that the interaction between the organic antibacterial agent and the inorganic antibacterial agent is enhanced, the closer combination is realized, and the performances of the foam plastic are further improved.

Claims (10)

1. The preparation method of the antibacterial flame-retardant foam plastic is characterized by comprising the following steps:
(1) according to the weight portion, 40 to 70 portions of polyol composition, 1 to 5 portions of flame retardant and 0.5 to 1.8 portions of composite antibacterial agent are evenly mixed under the conditions of 25 to 30 ℃ and 30 to 60 percent of relative humidity; then adding 50-80 parts of polyisocyanate, stirring at the rotating speed of 400-800rpm for 14-30s, injecting into a mold preheated to 60-90 ℃, and foaming and molding at 60-90 ℃ for 3-10min to obtain molded foam plastic;
(2) and putting the formed foam plastic and the mold into an oven with the temperature of 80-100 ℃ for drying for 2-4h, naturally cooling to room temperature, and taking out the foam plastic after stripping from the mold.
2. The method for preparing the antibacterial flame-retardant foam plastic as claimed in claim 1, wherein the method for preparing the flame retardant comprises the following steps:
adding 3-aminopropyltrimethoxysilane into water, stirring for 1-3h at the temperature of 90-100 ℃ and at the stirring speed of 100-150rpm, wherein the mass ratio of the 3-aminopropyltrimethoxysilane to the water is (1-2):3, so as to obtain a mixed solution A; then adding 1,3,5, 7-tetraethylcyclotetrasiloxane, tris (trimethylsiloxy) silane and potassium tert-butoxide, uniformly mixing, heating to 130 ℃ and 150 ℃, and continuously stirring for 3-6h, wherein the mass ratio of the 1,3,5, 7-tetraethylcyclotetrasiloxane, tris (trimethylsiloxy) silane, potassium tert-butoxide to the mixed solution A is (40-50): (0.3-0.6): 0.05-0.1): 5-15, so as to obtain a product B; mixing abietic acid and the product B according to the mass ratio of (1-3) to 5, and stirring for 3-5h at 95-100 ℃ and 50-100rpm to obtain a product C; adding the product C and N- [ (10-oxo-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-yl) methyl ] -6-phenyl-1, 3, 5-triazine-2, 4-diamine into trichloromethane, and heating for 10-15h at the temperature of 60-70 ℃, wherein the mass ratio of the product C, N- [ (10-oxo-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-yl) methyl ] -6-phenyl-1, 3, 5-triazine-2, 4-diamine to the trichloromethane is (3-6): 1-3): 15-25); and (4) performing rotary evaporation to remove the trichloromethane to obtain the product.
3. The method of preparing the antibacterial flame-retardant foam of claim 1, wherein the polyol composition comprises, in parts by weight: 80-120 parts of polyol, 2-5 parts of plasticizer, 2-8 parts of catalyst, 6-14 parts of foaming agent and 3-6 parts of foam stabilizer.
4. The method of claim 3, wherein the polyol is at least one of polyether polyol, polyester polyol and polymer polyol.
5. The method for preparing the antibacterial flame-retardant foam according to claim 3, wherein the catalyst is a mixture of an organotin catalyst and a tertiary amine catalyst.
6. A process for preparing an antibacterial flame-retardant foam as claimed in claim 3, wherein the blowing agent is a mixture of water and pentane hydrocarbon.
7. The method of claim 3, wherein the foam stabilizer is a silicone oil foam stabilizer.
8. The method for preparing antibacterial flame-retardant foam according to claim 1, wherein the polyisocyanate is any one of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI), Lysine Diisocyanate (LDI), and polyphenyl polymethylene polyisocyanate (PAPI).
9. The method for preparing the antibacterial flame-retardant foamed plastic according to claim 1, wherein the method for preparing the composite antibacterial agent comprises the following steps:
s1, adding 2-4 parts of nano tin dioxide into 76-88 parts of thin Ti layer with the concentration of 1-8mg/mL according to parts by weight3C2TXIn the water dispersion, ultrasonic dispersion treatment is carried out for 0.5-2h under the conditions of room temperature, 200-400W and 30-40kHz to obtain inorganic composite antibacterial liquid;
s2, dropwise adding ammonia water into the inorganic composite antibacterial liquid to adjust the pH value to 8, then adding 0.5-1 part of dopamine, stirring at the rotation speed of 150-350rpm for 8-16min, and standing at room temperature for reaction for 24-36h to obtain dopamine co-modified inorganic composite antibacterial liquid;
s3, adding 1-5 parts of chitosan into the dopamine co-modified inorganic composite antibacterial liquid, and stirring and reacting at the rotating speed of 100-300rpm for 10-15 hours at room temperature to obtain an organic-inorganic composite antibacterial liquid;
s4, carrying out vacuum filtration on the organic-inorganic composite antibacterial liquid to obtain a filter cake a, then adding water until the filter cake a is immersed, washing, carrying out suction filtration, washing for 1-3 times to obtain a filter cake b, then adding absolute ethyl alcohol until the filter cake b is immersed, carrying out alcohol washing, carrying out suction filtration, and washing for 1-3 times to obtain a solid substance I, and carrying out vacuum drying on the solid substance I at the temperature of 40-55 ℃ for 8-10 hours to obtain the composite antibacterial agent.
10. An antibacterial flame-retardant foam plastic prepared by the method of any one of claims 1 to 9.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160222168A1 (en) * 2011-07-22 2016-08-04 Asahi Kasei Chemicals Corporation Composition and Polymer
CN107116857A (en) * 2017-04-01 2017-09-01 东华大学 Three-dimensional porous framework reinforcing fiber sponge high-efficiency sound-absorbing material and its preparation
CN108069725A (en) * 2016-11-09 2018-05-25 中国科学院金属研究所 A kind of hollow foam material and its preparation method and application
CN110875235A (en) * 2018-09-03 2020-03-10 信越化学工业株式会社 Method for producing thin wafers
WO2020252537A1 (en) * 2019-06-21 2020-12-24 The University Of Melbourne Antimicrobial peptide-selenium nanoparticles
CN112420997A (en) * 2019-08-20 2021-02-26 中国科学院化学研究所 Method for constructing thickness-controllable metal oxide coating layer in solution phase
CN112898766A (en) * 2021-01-27 2021-06-04 陈裕嫦 Hard antibacterial plastic material and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160222168A1 (en) * 2011-07-22 2016-08-04 Asahi Kasei Chemicals Corporation Composition and Polymer
CN108069725A (en) * 2016-11-09 2018-05-25 中国科学院金属研究所 A kind of hollow foam material and its preparation method and application
CN107116857A (en) * 2017-04-01 2017-09-01 东华大学 Three-dimensional porous framework reinforcing fiber sponge high-efficiency sound-absorbing material and its preparation
CN110875235A (en) * 2018-09-03 2020-03-10 信越化学工业株式会社 Method for producing thin wafers
WO2020252537A1 (en) * 2019-06-21 2020-12-24 The University Of Melbourne Antimicrobial peptide-selenium nanoparticles
CN112420997A (en) * 2019-08-20 2021-02-26 中国科学院化学研究所 Method for constructing thickness-controllable metal oxide coating layer in solution phase
CN112898766A (en) * 2021-01-27 2021-06-04 陈裕嫦 Hard antibacterial plastic material and preparation method thereof

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