WO2023097809A1 - An antibacterial fireproof coating based on a sulfanilamide-silver chemical compound and a preparation method thereof - Google Patents

An antibacterial fireproof coating based on a sulfanilamide-silver chemical compound and a preparation method thereof Download PDF

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WO2023097809A1
WO2023097809A1 PCT/CN2021/139899 CN2021139899W WO2023097809A1 WO 2023097809 A1 WO2023097809 A1 WO 2023097809A1 CN 2021139899 W CN2021139899 W CN 2021139899W WO 2023097809 A1 WO2023097809 A1 WO 2023097809A1
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parts
sulfonamide
silver compound
antibacterial
fireproof coating
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French (fr)
Chinese (zh)
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谢海
程家骥
唐帆
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江苏冠军科技集团股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/10—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D261/14—Nitrogen atoms
    • C07D261/16—Benzene-sulfonamido isoxazoles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/32—Radiation-absorbing paints
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0058—Biocides
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives

Definitions

  • the invention relates to the technical field of fireproof coatings, in particular to an antibacterial fireproof coating based on a sulfonamide-silver compound and a preparation method thereof.
  • Polyurethane is the most frequently researched product in the world. It usually has outstanding physical and chemical properties. However, the heat resistance and antibacterial properties of polyurethane materials are poor, and flame retardants and antibacterial agents need to be added to improve their properties. As an environment-friendly flame retardant, nitrogen-containing flame retardants have gradually attracted people's attention.
  • Sulfa drugs are the earliest effective chemotherapeutic drugs systematically applied to the prevention and treatment of human bacterial infections, because they can inhibit the proliferation and growth of bacteria, while sulfa ligands and their metal compounds are screened for antibacterial activity, and the antibacterial activity of metal compounds is higher than that of Its parent ligands, mixed with selected polyurethanes as additives, can improve the flame retardant and antimicrobial properties of coatings.
  • the present invention proposes an antibacterial fireproof coating based on sulfonamide-silver compounds and a preparation method thereof, by adding sulfonamide-silver to the polyurethane coating Compounds to obtain antibacterial fire-resistant coatings of sulfonamide-silver compounds, thereby effectively improving their flame-retardant and antibacterial properties.
  • a kind of preparation method based on the antibacterial type fireproof coating of sulfonamide-silver compound comprises the steps:
  • Step 1 Mix 30-40 parts of sunflower oil, 10-20 parts of glycerin, 40-50 parts of turpentine, 1-2 parts of catalyst, 2-4 parts of ultraviolet absorber, 1-2 parts of anti-skinning agent, 2-6 parts Mixing of sulfonamide-silver compound and 10-20 parts of flame retardant additive;
  • Step 2 then add 80-110 parts of toluene diisocyanate to react with various oils in step 1 to form polyurethane, and obtain an antibacterial fireproof coating of sulfonamide-silver compound.
  • step one the preparation method of described sulfonamide-silver compound comprises the following steps:
  • the catalyst in step 1, includes a mixture of dioctyltin oxide and stannous octoate, the mass ratio of which is 1:2.
  • the flame retardant additive is a mixture of pentaerythritol, boric acid and phosphoric acid ester, and its mass ratio is 10:1:1.
  • the heating method in step S3 is irradiated heating in a microwave chemical furnace, so as to avoid the violent fluctuation of the reaction curve caused by the uneven heat transfer mode of traditional heat conduction and convection heating, which can further improve the sulfonamide-silver compound. conversion rate.
  • An antibacterial fireproof coating based on a sulfonamide-silver compound comprising the following components in mass fractions: 30-40 parts of sunflower oil, 10-20 parts of glycerin, 40-50 parts of turpentine, 1-2 parts of catalyst, and 80 parts of toluene diisocyanate ⁇ 110 parts, 2 ⁇ 4 parts of ultraviolet absorber, 1 ⁇ 2 parts of anti-skinning agent, 2 ⁇ 6 parts of sulfonamide-silver compound, 10 ⁇ 20 parts of flame retardant additive.
  • Sunflower oil, glycerin, and turpentine react with toluene diisocyanate under the action of a catalyst to form a coating film-former.
  • the UV absorber can slow down the aging of the coating, and the anti-skinning agent can improve the coating effect of the coating.
  • the catalyst includes a mixture of dioctyltin oxide and stannous octoate, the mass ratio of which is 1:2, and participates in the reaction of toluene diisocyanate with sunflower oil, turpentine, and glycerin to generate polyurethane, and the strength of the obtained polyurethane material is higher.
  • the flame retardant additive is a mixture of pentaerythritol, boric acid and phosphoric acid ester, and its mass ratio is 10:1:1.
  • the flame retardant additive cooperates with the sulfonamide-silver compound to improve heat resistance and stability , enhance the flame retardant effect of fire retardant coatings.
  • the bond energy of C-Cl is low, and its decomposition temperature is basically the same as the thermal decomposition temperature of the material.
  • the sulfonamide-silver compound When the sulfonamide-silver compound is decomposed by heat, it absorbs part of the heat and lowers the temperature. At the same time, the density of hydrogen chloride gas generated by the decomposition is greater than that of air. It also has certain antibacterial properties, and can also squeeze away the air around the material, forming a gradient oxygen permeation barrier with N gas, weakening the Van der Waals force between the polymer chains, making the material in a viscous flow state when heated, and the material at this time It has fluidity, and it can take away part of the flame and heat when it flows under heat, so as to achieve the effect of flame retardancy, and then achieve the synergistic technical effect of the two in terms of flame retardancy and antibacterial performance;
  • the antibacterial fireproof coating of described sulfonamide-silver compound comprises sunflower oil 30 ⁇ 40 parts, glycerine 10 ⁇ 20 parts, turpentine 40 parts ⁇ 50 parts, catalyst 1 ⁇ 2 parts, toluene diisocyanate 80 ⁇ 110 parts, UV absorber 2 ⁇ 4 parts, anti-skinning agent 1 ⁇ 2 parts, sulfonamide-silver compound 2 ⁇ 6 parts and flame retardant additive 10 ⁇ 20 parts, thus forming the best formula ratio of antibacterial and flame retardancy, wherein sunflower oil, glycerin and turpentine react with toluene diisocyanate under the action of a catalyst to form a film-forming substance of the paint, and the UV absorber can slow down the aging of the paint , the anti-skinning agent can improve the coating effect of the coating; the flame retardant additive cooperates with the sulfonamide-silver
  • the heating mode in the reaction process is radiation heating in the microwave chemical furnace, avoids the inhomogeneous heating of traditional heat conduction and convection mode
  • the heat transfer mode causes the reaction curve to fluctuate violently, which can further increase the conversion rate of the sulfonamide-silver compound;
  • a kind of antibacterial fireproof coating based on sulfonamide-silver compound of the present invention and preparation method thereof, is housed in anhydrous CaCl Drying in the desiccator, can effectively avoid that drying temperature is excessively high and decomposes in advance, to further improve Conversion of sulfonamide-silver compounds.
  • a kind of preparation method of the antibacterial type fireproof coating based on sulfa-silver compound of the present embodiment comprises the steps:
  • Step 1 Mix 30-40 parts of sunflower oil, 10-20 parts of glycerin, 40-50 parts of turpentine, 1-2 parts of catalyst, 2-4 parts of ultraviolet absorber, 1-2 parts of anti-skinning agent, 2-6 parts Mixing of sulfonamide-silver compound and 10-20 parts of flame retardant additive;
  • Step 2 then adding 80 to 110 parts of toluene diisocyanate to obtain an antibacterial fireproof coating of sulfonamide-silver compound.
  • step one the preparation method of the sulfonamide-silver compound comprises the following steps:
  • the catalyst includes a mixture of dioctyltin oxide and stannous octoate, the mass ratio of which is 1:2, which participates in the reaction of toluene diisocyanate with sunflower oil, turpentine, and glycerin to form polyurethane, and the strength of the prepared polyurethane material is higher .
  • the flame retardant additive is a mixture of pentaerythritol, boric acid and phosphoric acid ester with a mass ratio of 10:1:1.
  • the heating method in step S3 is irradiated heating in a microwave chemical furnace, so as to avoid the violent fluctuation of the reaction curve caused by the uneven heat transfer mode of traditional heat conduction and convection heating, which can further improve the conversion of the sulfonamide-silver compound Rate
  • the catalyst includes a mixture of dioctyltin oxide and stannous octoate, the mass ratio of which is 1:2, and participates in the reaction of toluene diisocyanate with sunflower oil, turpentine, and glycerin to generate polyurethane, and the strength of the polyurethane material obtained is higher.
  • the flame retardant additive is a mixture of pentaerythritol, boric acid and phosphoric acid ester with a mass ratio of 10:1:1.
  • Component content First determine the reaction of sunflower oil, glycerin, turpentine and toluene diisocyanate. Excessive amounts of one of sunflower oil, glycerin, turpentine and toluene diisocyanate will lead to residual and reduce product strength. Too much catalyst will make the reaction If it is too fast, it is not conducive to the uniform mixing of the additives, and if it is too small, the reaction will be too slow and the additives will precipitate. The higher the addition amount of UV absorber, flame retardant additive and sulfonamide-silver compound, the better the anti-aging and antibacterial and flame-retardant effect of the coating, but it will reduce the mechanical properties of the coating material.
  • the silver ion in the sulfonamide-silver compound prepared in the present invention has excellent antibacterial performance, and the N-containing gas produced by thermal decomposition plays the role of isolating oxygen and making the carbon layer expand, and the flame-retardant additive cooperates with the sulfonamide-silver compound to improve the antibacterial properties.
  • the thermal stability is stronger, and the flame retardant effect of the fire retardant coating is enhanced.
  • Sunflower oil, glycerin, and turpentine react with toluene diisocyanate under the action of a catalyst to form a coating film-former.
  • the UV absorber can slow down the aging of the coating, and the anti-skinning agent can improve the coating effect of the coating.
  • the preparation method of the sulfonamide-silver compound comprises the following steps:
  • the catalyst includes a mixture of dioctyltin oxide and stannous octoate with a mass ratio of 1:2, which participates in the reaction of toluene diisocyanate with sunflower oil, turpentine, and glycerin to form polyurethane, and the resulting polyurethane material has higher strength.
  • the flame retardant additive is a mixture of pentaerythritol, boric acid and phosphoric acid ester with a mass ratio of 10:1:1.
  • the preparation method of the sulfonamide-silver compound comprises the following steps:
  • the reaction mixture is mixed with 30ml methanol, put into a microwave chemical furnace for irradiation, the reaction time is 4min, and the reaction power is 100W;
  • the catalyst includes a mixture of dioctyltin oxide and stannous octoate with a mass ratio of 1:2, which participates in the reaction of toluene diisocyanate with sunflower oil, turpentine, and glycerin to form polyurethane, and the resulting polyurethane material has higher strength.
  • the flame retardant additive is a mixture of pentaerythritol, boric acid and phosphoric acid ester with a mass ratio of 10:1:1.
  • the preparation method of the sulfonamide-silver compound comprises the following steps:
  • the reaction mixture is mixed with 50ml of methanol, put into a microwave chemical furnace for irradiation, the reaction time is 6min, and the reaction power is 100W;
  • the catalyst includes a mixture of dioctyltin oxide and stannous octoate with a mass ratio of 1:2, which participates in the reaction of toluene diisocyanate with sunflower oil, turpentine, and glycerin to form polyurethane, and the resulting polyurethane material has higher strength.
  • the flame retardant additive is a mixture of pentaerythritol, boric acid and phosphoric acid ester with a mass ratio of 10:1:1.
  • the fireproof coating of the comparative example comprises the following components in mass fractions: 40 parts of sunflower oil, 20 parts of glycerin, 50 parts of turpentine, 2 parts of catalyst, 110 parts of toluene diisocyanate, 2 parts of anti-skinning agent, and 20 parts of flame retardant additive.
  • the catalyst includes a mixture of dioctyltin oxide and stannous octoate with a mass ratio of 1:2, which participates in the reaction of toluene diisocyanate with sunflower oil, turpentine, and glycerin to form polyurethane, and the resulting polyurethane material has higher strength.
  • the flame retardant additive is a mixture of pentaerythritol, boric acid and phosphoric acid ester with a mass ratio of 1:1:1.
  • the preparation method of comparative example fireproof coating comprises the following steps:
  • the density of hydrogen chloride gas is higher than that of air, and it also has certain antibacterial properties. It can also squeeze away the air around the coating, and form a gradient oxygen permeation barrier with N gas, which is denser than air, and weaken the Van der Waals force between the polymer chains. It is in a viscous flow state when heated. At this time, the coating has fluidity, and when heated and flowed, it can take away part of the flame and heat, so as to realize the flame-retardant effect of the fire-resistant coating, and then achieve both in terms of flame-retardant and antibacterial properties.

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Abstract

The present invention relates to the technical field of fireproof flame-retardant coatings. An antibacterial fireproof coating based on a sulfanilamide-silver chemical compound and a preparation method thereof. The preparation method of the antibacterial fireproof coating based on the sulfanilamide-silver chemical compound comprises the following steps: Taking 30-40 parts sunflower oil, 10-20 parts glycerol, 40-50 parts turpentine, 1-2 parts catalyst, 2-4 parts ultraviolet absorbent, 1-2 parts anti-skinning agent, 2-6 parts sulfanilamide-silver chemical compound and 10-20 parts flame-retardant auxiliary mixture, then adding 80-110 parts toluene diisocyanate, obtaining an antibacterial fireproof coating of the sulfanilamide-silver chemical compound. The antibacterial performance of the coating is enhanced, the heat resistance of the coating is improved, and the flame retardance of the coating is improved.

Description

一种基于磺胺-银化合物的抗菌型防火涂料及其制备方法A kind of antibacterial type fireproof coating based on sulfonamide-silver compound and preparation method thereof 技术领域technical field
本发明涉及防火涂料技术领域，更具体地说是一种基于磺胺-银化合物的抗菌型防火涂料及其制备方法。The invention relates to the technical field of fireproof coatings, in particular to an antibacterial fireproof coating based on a sulfonamide-silver compound and a preparation method thereof.
背景技术Background technique
聚氨酯是世界上研究最频繁的产品，通常具有突出的物理和化学特性，然而聚氨酯材料的耐热性和抗菌性能较差，需加入阻燃剂和抗菌剂对其性能进行改善。含氮阻燃剂作为一种环境友好型阻燃剂逐渐受到人们的重视。Polyurethane is the most frequently researched product in the world. It usually has outstanding physical and chemical properties. However, the heat resistance and antibacterial properties of polyurethane materials are poor, and flame retardants and antibacterial agents need to be added to improve their properties. As an environment-friendly flame retardant, nitrogen-containing flame retardants have gradually attracted people's attention.
近年来，具有阻燃和抗菌作用的复合添加剂被应用于涂层材料。含有噻唑环的香豆素衍生物被用于作为聚氨酯涂料的环保型抗菌、阻燃和缓蚀添加剂。联氨配体和其金属配合物及其作为表面涂层配方中的抗菌、防污和阻燃添加剂的潜在应用也得到了报道，希夫碱化合物也被添加到醇酸漆配方来提高其阻燃性能。磺胺类药物是最早系统应用于预防和治疗人类细菌感染的有效化疗药物，因其可抑制细菌的增殖和生长，而磺胺类配体及其金属化合物进行抗菌活性筛选，金属化合物的抗菌活性高于其母体配体，将其与选定的聚氨酯混合作为添加剂，可提高涂料的阻燃和抗菌性能。In recent years, composite additives with flame retardant and antibacterial effects have been applied to coating materials. Coumarin derivatives containing thiazole rings are used as environmentally friendly antibacterial, flame-retardant and corrosion-inhibiting additives for polyurethane coatings. Hydrazine ligands and their metal complexes and their potential applications as antibacterial, antifouling, and flame retardant additives in surface coating formulations have also been reported, and Schiff base compounds have also been added to alkyd paint formulations to improve their antibacterial properties. flammability. Sulfa drugs are the earliest effective chemotherapeutic drugs systematically applied to the prevention and treatment of human bacterial infections, because they can inhibit the proliferation and growth of bacteria, while sulfa ligands and their metal compounds are screened for antibacterial activity, and the antibacterial activity of metal compounds is higher than that of Its parent ligands, mixed with selected polyurethanes as additives, can improve the flame retardant and antimicrobial properties of coatings.
发明内容Contents of the invention
1.发明要解决的技术问题1. The technical problem to be solved by the invention
针对现有技术中聚氨酯材料在耐热性、抗菌性方面存在的局限性，本发明提出一种基于磺胺-银化合物的抗菌型防火涂料及其制备方法，通过在聚氨酯涂层中加入磺胺-银化合物，以得到磺胺-银化合物的抗菌型防火涂料，从而有效提高其阻燃性能和抗菌性能。In view of the limitations of polyurethane materials in the prior art in terms of heat resistance and antibacterial properties, the present invention proposes an antibacterial fireproof coating based on sulfonamide-silver compounds and a preparation method thereof, by adding sulfonamide-silver to the polyurethane coating Compounds to obtain antibacterial fire-resistant coatings of sulfonamide-silver compounds, thereby effectively improving their flame-retardant and antibacterial properties.
2.技术方案2. Technical solution
为达到上述目的，本发明提供的技术方案为：In order to achieve the above object, the technical scheme provided by the invention is:
一种基于磺胺-银化合物的抗菌型防火涂料的制备方法，包括如下步骤：A kind of preparation method based on the antibacterial type fireproof coating of sulfonamide-silver compound, comprises the steps:
步骤一、将30～40份葵花油，10～20份甘油，40～50份松节油，1～2份催化剂，2～4份紫外吸收剂，1～2份防结皮剂、2～6份磺胺-银化合物以及10～20份阻燃助剂混合；Step 1. Mix 30-40 parts of sunflower oil, 10-20 parts of glycerin, 40-50 parts of turpentine, 1-2 parts of catalyst, 2-4 parts of ultraviolet absorber, 1-2 parts of anti-skinning agent, 2-6 parts Mixing of sulfonamide-silver compound and 10-20 parts of flame retardant additive;
步骤二、然后加入80～110份甲苯二异氰酸酯，与步骤一的各种油类发生反应生成聚氨酯，得到磺胺-银化合物的抗菌型防火涂料。Step 2, then add 80-110 parts of toluene diisocyanate to react with various oils in step 1 to form polyurethane, and obtain an antibacterial fireproof coating of sulfonamide-silver compound.
进一步的技术方案，步骤一中，所述磺胺-银化合物的制备方法包括以下步骤：Further technical scheme, in step one, the preparation method of described sulfonamide-silver compound comprises the following steps:
S1、将0.0015～0.004mol硝酸银和0.0006～0.0018mol吡啶-2,5-二羧酸溶解于100ml N,N- 二甲基甲酰胺中，磁力搅拌5min后将混合液移至反应釜中，置于150～180℃中36～48h，然后使用乙醇抽滤洗涤3次后置于100～130℃干燥24h，最终得到Ag-MOF；S1. Dissolve 0.0015～0.004mol of silver nitrate and 0.0006～0.0018mol of pyridine-2,5-dicarboxylic acid in 100ml of N,N-dimethylformamide, stir it magnetically for 5 minutes, and transfer the mixture to the reaction kettle. Place at 150-180°C for 36-48h, then use ethanol to filter and wash 3 times, then dry at 100-130°C for 24h to finally obtain Ag-MOF;
S2、将0.01～0.03mol对Ag-MOF与0.01～0.03mol偶氮化合物4-((3-甲酰基-4-羟基苯基)二氮苯)-N-(5-甲基异恶唑-3-酰基)苯磺酰胺充分混合；S2. Combine 0.01～0.03mol p-Ag-MOF with 0.01～0.03mol azo compound 4-((3-formyl-4-hydroxyphenyl)diazobenzene)-N-(5-methylisoxazole- 3-acyl)benzenesulfonamide is fully mixed;
S3、将反应混合物与30～50ml甲醇混合，加热，反应时间为3～6min，反应功率为80～100W；S3, mixing the reaction mixture with 30-50ml methanol, heating, the reaction time is 3-6min, and the reaction power is 80-100W;
S4、将混合物移至反应釜中，置于100～120℃中24～36h，然后使用乙醇抽滤洗涤3次后放入装有无水CaCl 2的干燥器内干燥，最终得到磺胺-银化合物。 S4. Move the mixture to a reaction kettle, place it at 100-120° C. for 24-36 hours, then use ethanol to filter and wash it for 3 times, then put it into a desiccator filled with anhydrous CaCl 2 and dry it to finally obtain the sulfonamide-silver compound .
进一步的技术方案，整个反应通式为：Further technical scheme, whole general reaction formula is:
Figure PCTCN2021139899-appb-000001
Figure PCTCN2021139899-appb-000001
，其中
Figure PCTCN2021139899-appb-000002
为预产物；
Figure PCTCN2021139899-appb-000003
为磺胺-银化合物。 ,in
Figure PCTCN2021139899-appb-000002
is a pre-product;
Figure PCTCN2021139899-appb-000003
For sulfonamide - silver compounds.
进一步的技术方案，步骤一中，所述催化剂包括氧化二辛基锡和辛酸亚锡的混合物，其质量比为1：2。In a further technical solution, in step 1, the catalyst includes a mixture of dioctyltin oxide and stannous octoate, the mass ratio of which is 1:2.
进一步的技术方案，步骤一中，所述阻燃助剂为季戊四醇、硼酸和磷酸酯的混合物，其质量比为10：1：1。In a further technical solution, in step 1, the flame retardant additive is a mixture of pentaerythritol, boric acid and phosphoric acid ester, and its mass ratio is 10:1:1.
进一步的技术方案，步骤S3中加热方式为放入微波化学炉中辐照加热，以避免传统的热传导和对流方式加热的不均匀的热量传递方式造成反应曲线剧烈波动，可进一步提高磺胺-银化合物的转化率。In a further technical solution, the heating method in step S3 is irradiated heating in a microwave chemical furnace, so as to avoid the violent fluctuation of the reaction curve caused by the uneven heat transfer mode of traditional heat conduction and convection heating, which can further improve the sulfonamide-silver compound. conversion rate.
一种基于磺胺-银化合物的抗菌型防火涂料，包括以下质量分数的组份：葵花油30～40份，甘油10～20份，松节油40～50份，催化剂1～2份，甲苯二异氰酸酯80～110份，紫外吸收剂2～4份，防结皮剂1～2份，磺胺-银化合物2～6份，阻燃助剂10～20份。葵花油、甘油、松节油在催化剂的作用下和甲苯二异氰酸酯反应生成涂料的成膜物，紫外吸收剂可以减缓涂料的老化，防结皮剂可以提高涂料的涂覆效果。An antibacterial fireproof coating based on a sulfonamide-silver compound, comprising the following components in mass fractions: 30-40 parts of sunflower oil, 10-20 parts of glycerin, 40-50 parts of turpentine, 1-2 parts of catalyst, and 80 parts of toluene diisocyanate ~110 parts, 2~4 parts of ultraviolet absorber, 1~2 parts of anti-skinning agent, 2~6 parts of sulfonamide-silver compound, 10~20 parts of flame retardant additive. Sunflower oil, glycerin, and turpentine react with toluene diisocyanate under the action of a catalyst to form a coating film-former. The UV absorber can slow down the aging of the coating, and the anti-skinning agent can improve the coating effect of the coating.
进一步的技术方案，所述催化剂包括氧化二辛基锡和辛酸亚锡的混合物，其质量比为1：2，参与甲苯二异氰酸酯与葵花油、松节油、甘油发生反应生成聚氨酯，制得的聚氨酯材料的强度更高。In a further technical solution, the catalyst includes a mixture of dioctyltin oxide and stannous octoate, the mass ratio of which is 1:2, and participates in the reaction of toluene diisocyanate with sunflower oil, turpentine, and glycerin to generate polyurethane, and the strength of the obtained polyurethane material is higher.
进一步的技术方案，所述阻燃助剂为季戊四醇、硼酸和磷酸酯的混合物，其质量比为10：1：1，阻燃助剂协同磺胺-银化合物相互配合，提高耐热稳定性更强，增强防火涂料的阻燃效果。In a further technical solution, the flame retardant additive is a mixture of pentaerythritol, boric acid and phosphoric acid ester, and its mass ratio is 10:1:1. The flame retardant additive cooperates with the sulfonamide-silver compound to improve heat resistance and stability , enhance the flame retardant effect of fire retardant coatings.
3.有益效果3. Beneficial effect
采用本发明提供的技术方案，与现有技术相比，具有如下有益效果：Compared with the prior art, the technical solution provided by the invention has the following beneficial effects:
(1)本发明的一种基于磺胺-银化合物的抗菌型防火涂料及其制备方法，通过在聚氨酯涂层中加入磺胺-银化合物，以得到磺胺-银化合物的抗菌型防火涂料，所述磺胺-银化合物中的银离子具有优异的抗菌性能，受热分解产生的含N气体，起到隔绝氧气使炭层膨胀的作用，从而有效提高其阻燃性能和抗菌性能；由于氯系阻燃系的C-Cl的键能低，它的分解温度基本与材料的热分解温度一致，磺胺-银化合物受热分解时，其间吸收一部分热量，降低了温度，同时，分解生成的氯化氢气体的密度大于空气，也有一定的抗菌性，还可以排挤走材料周围的空气，与N气形成梯度的氧渗屏障，减弱了高分子链之间的范德华力，使材料在受热时处于粘流态，此时的材料具有流动性，而在受热流动时可以带走一部分火焰和热量，从而实现阻燃的效果，进而达到两者在阻燃性能和抗菌性能上的协同式的技术效果；(1) a kind of antibacterial fireproof coating based on sulfonamide-silver compound of the present invention and preparation method thereof, by adding sulfonamide-silver compound in polyurethane coating, to obtain the antibacterial type fireproof coating of sulfonamide-silver compound, described sulfonamide -Silver ions in the silver compound have excellent antibacterial properties, and the N-containing gas produced by thermal decomposition plays the role of isolating oxygen and expanding the carbon layer, thereby effectively improving its flame retardancy and antibacterial performance; due to the chlorine-based flame-retardant system The bond energy of C-Cl is low, and its decomposition temperature is basically the same as the thermal decomposition temperature of the material. When the sulfonamide-silver compound is decomposed by heat, it absorbs part of the heat and lowers the temperature. At the same time, the density of hydrogen chloride gas generated by the decomposition is greater than that of air. It also has certain antibacterial properties, and can also squeeze away the air around the material, forming a gradient oxygen permeation barrier with N gas, weakening the Van der Waals force between the polymer chains, making the material in a viscous flow state when heated, and the material at this time It has fluidity, and it can take away part of the flame and heat when it flows under heat, so as to achieve the effect of flame retardancy, and then achieve the synergistic technical effect of the two in terms of flame retardancy and antibacterial performance;
(2)本发明的一种基于磺胺-银化合物的抗菌型防火涂料及其制备方法，所述磺胺-银化合物的抗菌型防火涂料包括葵花油30～40份，甘油10～20份，松节油40～50份，催化剂1～2份，甲苯二异氰酸酯80～110份，紫外吸收剂2～4份，防结皮剂1～2份，磺胺-银化合物2～6份以及阻燃助剂10～20份，从而组成了抗菌性和阻燃性最好的配方比例，其中葵花油、甘油、松节油在催化剂的作用下和甲苯二异氰酸酯反应生成涂料的成膜物，紫外吸收剂可以减缓涂料的老化，防结皮剂可以提高涂料的涂覆效果；阻燃助剂协同磺胺-银化合物，提高耐热稳定性更强，增强防火涂料的阻燃效果；(2) A kind of antibacterial fireproof coating based on sulfonamide-silver compound of the present invention and preparation method thereof, the antibacterial fireproof coating of described sulfonamide-silver compound comprises sunflower oil 30～40 parts, glycerine 10～20 parts, turpentine 40 parts ～50 parts, catalyst 1～2 parts, toluene diisocyanate 80～110 parts, UV absorber 2～4 parts, anti-skinning agent 1～2 parts, sulfonamide-silver compound 2～6 parts and flame retardant additive 10～ 20 parts, thus forming the best formula ratio of antibacterial and flame retardancy, wherein sunflower oil, glycerin and turpentine react with toluene diisocyanate under the action of a catalyst to form a film-forming substance of the paint, and the UV absorber can slow down the aging of the paint , the anti-skinning agent can improve the coating effect of the coating; the flame retardant additive cooperates with the sulfonamide-silver compound to improve the heat resistance and stability, and enhance the flame retardant effect of the fireproof coating;
(3)本发明的一种基于磺胺-银化合物的抗菌型防火涂料及其制备方法，反应过程中的加热方式为微波化学炉中辐照加热，避免传统的热传导和对流方式加热的不均匀的热量传递方式造成反应曲线剧烈波动，可进一步提高磺胺-银化合物的转化率；(3) a kind of antibacterial type fireproof coating based on sulfonamide-silver compound of the present invention and preparation method thereof, the heating mode in the reaction process is radiation heating in the microwave chemical furnace, avoids the inhomogeneous heating of traditional heat conduction and convection mode The heat transfer mode causes the reaction curve to fluctuate violently, which can further increase the conversion rate of the sulfonamide-silver compound;
(4)本发明的一种基于磺胺-银化合物的抗菌型防火涂料及其制备方法，在装有无水CaCl 2的干燥器中干燥，可有效避免干燥温度过高而提前分解，以进一步提高磺胺-银化合物的转化率。 (4) a kind of antibacterial fireproof coating based on sulfonamide-silver compound of the present invention and preparation method thereof, is housed in anhydrous CaCl Drying in the desiccator, can effectively avoid that drying temperature is excessively high and decomposes in advance, to further improve Conversion of sulfonamide-silver compounds.
具体实施方式Detailed ways
为进一步了解本发明的内容，以下对发明作详细描述。In order to further understand the content of the present invention, the invention is described in detail below.
实施例1Example 1
本实施例的一种基于磺胺-银化合物的抗菌型防火涂料的制备方法，包括如下步骤：A kind of preparation method of the antibacterial type fireproof coating based on sulfa-silver compound of the present embodiment, comprises the steps:
步骤一、将30～40份葵花油，10～20份甘油，40～50份松节油，1～2份催化剂，2～4份紫外吸收剂，1～2份防结皮剂，2～6份磺胺-银化合物以及10～20份阻燃助剂混合；Step 1. Mix 30-40 parts of sunflower oil, 10-20 parts of glycerin, 40-50 parts of turpentine, 1-2 parts of catalyst, 2-4 parts of ultraviolet absorber, 1-2 parts of anti-skinning agent, 2-6 parts Mixing of sulfonamide-silver compound and 10-20 parts of flame retardant additive;
步骤二、然后加入80～110份甲苯二异氰酸酯，得到磺胺-银化合物的抗菌型防火涂料。Step 2, then adding 80 to 110 parts of toluene diisocyanate to obtain an antibacterial fireproof coating of sulfonamide-silver compound.
本实施例中，步骤一中，所述磺胺-银化合物的制备方法包括以下步骤：In the present embodiment, in step one, the preparation method of the sulfonamide-silver compound comprises the following steps:
S1、将0.0015～0.004mol硝酸银和0.0006～0.0018mol吡啶-2,5-二羧酸溶解于100ml N,N-二甲基甲酰胺中，磁力搅拌5min后将混合液移至反应釜中，置于150～180℃中36～48h，然后使用乙醇抽滤洗涤3次后置于100～130℃干燥24h，最终得到Ag-MOF；S1. Dissolve 0.0015～0.004mol of silver nitrate and 0.0006～0.0018mol of pyridine-2,5-dicarboxylic acid in 100ml of N,N-dimethylformamide, stir the mixture for 5 minutes with magnetic force, and transfer the mixture to the reaction kettle. Place at 150-180°C for 36-48h, then use ethanol to filter and wash 3 times, then dry at 100-130°C for 24h to finally obtain Ag-MOF;
S2、将0.01～0.03mol对Ag-MOF与0.01～0.03mol偶氮化合物4-((3-甲酰基-4-羟基苯基)二氮苯)-N-(5-甲基异恶唑-3-酰基)苯磺酰胺充分混合；S2. Combine 0.01～0.03mol p-Ag-MOF with 0.01～0.03mol azo compound 4-((3-formyl-4-hydroxyphenyl)diazobenzene)-N-(5-methylisoxazole- 3-acyl)benzenesulfonamide is fully mixed;
S3、将反应混合物与30～50ml甲醇混合，加热，反应时间为3～6min，反应功率为80～100W；S3, mixing the reaction mixture with 30-50ml methanol, heating, the reaction time is 3-6min, and the reaction power is 80-100W;
S4、将混合物移至反应釜中，置于100～120℃中24～36h，然后使用乙醇抽滤洗涤3次后放入装有无水CaCl 2的干燥器内干燥，最终得到磺胺-银化合物，反应通式为： S4. Move the mixture to a reaction kettle, place it at 100-120° C. for 24-36 hours, then use ethanol to filter and wash it for 3 times, then put it into a desiccator filled with anhydrous CaCl 2 and dry it to finally obtain the sulfonamide-silver compound , the general reaction formula is:
Figure PCTCN2021139899-appb-000004
Figure PCTCN2021139899-appb-000004
进一步的，所述催化剂包括氧化二辛基锡和辛酸亚锡的混合物，其质量比为1：2，参与甲苯二异氰酸酯与葵花油、松节油、甘油发生反应生成聚氨酯，制得的聚氨酯材料的强度更高。Further, the catalyst includes a mixture of dioctyltin oxide and stannous octoate, the mass ratio of which is 1:2, which participates in the reaction of toluene diisocyanate with sunflower oil, turpentine, and glycerin to form polyurethane, and the strength of the prepared polyurethane material is higher .
进一步的，所述阻燃助剂为季戊四醇、硼酸和磷酸酯的混合物，其质量比为10：1：1。Further, the flame retardant additive is a mixture of pentaerythritol, boric acid and phosphoric acid ester with a mass ratio of 10:1:1.
进一步的，步骤S3中加热方式为放入微波化学炉中辐照加热，以避免传统的热传导和对流方式加热的不均匀的热量传递方式造成反应曲线剧烈波动，可进一步提高磺胺-银化合物的转化率Further, the heating method in step S3 is irradiated heating in a microwave chemical furnace, so as to avoid the violent fluctuation of the reaction curve caused by the uneven heat transfer mode of traditional heat conduction and convection heating, which can further improve the conversion of the sulfonamide-silver compound Rate
实施例2Example 2
本实施例的一种基于磺胺-银化合物的抗菌型防火涂料，基本结构同实施例1，不同和改进之处在于：包括以下质量分数的组份：葵花油30～40份，甘油10～20份，松节油40～50份，催化剂1～2份，甲苯二异氰酸酯80～110份，紫外吸收剂2～4份，防结皮剂1～2份，磺胺-银化合物2～6份和阻燃助剂10～20份。A kind of antibacterial fireproof coating based on sulfonamide-silver compound of the present embodiment, basic structure is the same as embodiment 1, difference and improvement are: comprise the component of following mass fraction: sunflower oil 30～40 parts, glycerin 10～20 40-50 parts of turpentine, 1-2 parts of catalyst, 80-110 parts of toluene diisocyanate, 2-4 parts of UV absorber, 1-2 parts of anti-skinning agent, 2-6 parts of sulfonamide-silver compound and flame retardant 10-20 parts of additives.
本实施例中，所述催化剂包括氧化二辛基锡和辛酸亚锡的混合物，其质量比为1：2，参与甲苯二异氰酸酯与葵花油、松节油、甘油发生反应生成聚氨酯，制得的聚氨酯材料的强度更高。In this example, the catalyst includes a mixture of dioctyltin oxide and stannous octoate, the mass ratio of which is 1:2, and participates in the reaction of toluene diisocyanate with sunflower oil, turpentine, and glycerin to generate polyurethane, and the strength of the polyurethane material obtained is higher.
进一步的，所述阻燃助剂为季戊四醇、硼酸和磷酸酯的混合物，其质量比为10：1：1。Further, the flame retardant additive is a mixture of pentaerythritol, boric acid and phosphoric acid ester with a mass ratio of 10:1:1.
组分含量首先确定葵花油、甘油、松节油和甲苯二异氰酸酯的反应，葵花油、甘油、松节油和甲苯二异氰酸酯某一种量过多会导致有有剩余并且降低产物强度，催化剂过多会使反应过快，不利于添加物混合均匀，过少会使反应过慢，添加物沉淀。紫外吸收剂、阻燃助剂和磺胺-银化合物的添加量越高减缓涂料的老化和抗菌阻燃效果越好，但是会降低涂层材料的力学性能。本发明中制备的磺胺-银化合物中的银离子具有优异的抗菌性能，受热分解产生的含N气体，起到隔绝氧气使炭层膨胀的作用，阻燃助剂协同磺胺-银化合物，提高耐热稳定性更强，增强防火涂料的阻燃效果。葵花油、甘油、松节油在催化剂的作用下和甲苯二异氰酸酯反应生成涂料的成膜物，紫外吸收剂可以减缓涂料的老化，防结皮剂可以提高涂料的涂覆效果。Component content First determine the reaction of sunflower oil, glycerin, turpentine and toluene diisocyanate. Excessive amounts of one of sunflower oil, glycerin, turpentine and toluene diisocyanate will lead to residual and reduce product strength. Too much catalyst will make the reaction If it is too fast, it is not conducive to the uniform mixing of the additives, and if it is too small, the reaction will be too slow and the additives will precipitate. The higher the addition amount of UV absorber, flame retardant additive and sulfonamide-silver compound, the better the anti-aging and antibacterial and flame-retardant effect of the coating, but it will reduce the mechanical properties of the coating material. The silver ion in the sulfonamide-silver compound prepared in the present invention has excellent antibacterial performance, and the N-containing gas produced by thermal decomposition plays the role of isolating oxygen and making the carbon layer expand, and the flame-retardant additive cooperates with the sulfonamide-silver compound to improve the antibacterial properties. The thermal stability is stronger, and the flame retardant effect of the fire retardant coating is enhanced. Sunflower oil, glycerin, and turpentine react with toluene diisocyanate under the action of a catalyst to form a coating film-former. The UV absorber can slow down the aging of the coating, and the anti-skinning agent can improve the coating effect of the coating.
实施例3Example 3
本实施例的一种基于磺胺-银化合物的抗菌型防火涂料，基本结构同实施例2，不同和改进之处在于：包括以下质量分数的组份：葵花油30份，甘油10份，松节油40份，催化剂1份，甲苯二异氰酸酯80份，紫外吸收剂2份，防结皮剂1份，磺胺-银化合物2份和阻燃助剂10份。将上述组份的葵花油，甘油，松节油，催化剂，紫外吸收剂，防结皮剂，磺胺-银化合物以及阻燃助剂混合，然后加入甲苯二异氰酸酯混合反应，得到磺胺-银化合物的抗菌型防火涂料。A kind of antibacterial type fireproof coating based on sulfonamide-silver compound of the present embodiment, basic structure is the same as embodiment 2, difference and improvement are: comprise the component of following mass fraction: 30 parts of sunflower oils, 10 parts of glycerin, turpentine 40 parts 1 part of catalyst, 80 parts of toluene diisocyanate, 2 parts of UV absorber, 1 part of anti-skinning agent, 2 parts of sulfonamide-silver compound and 10 parts of flame retardant additive. Mix the sunflower oil, glycerin, turpentine, catalyst, UV absorber, anti-skinning agent, sulfonamide-silver compound and flame retardant additive of the above components, and then add toluene diisocyanate for mixed reaction to obtain the antibacterial type of sulfonamide-silver compound fire retardant coating.
本实施例中，所述磺胺-银化合物的制备方法包括以下步骤：In the present embodiment, the preparation method of the sulfonamide-silver compound comprises the following steps:
a、将0.0015mol硝酸银和0.0006mol吡啶-2,5-二羧酸溶解于100ml N,N-二甲基甲酰胺，磁力搅拌5min后将混合液移至反应釜中，置于150℃中36h，然后使用乙醇抽滤洗涤3次后置于100℃干燥24h，最终得到Ag-MOF；a. Dissolve 0.0015mol of silver nitrate and 0.0006mol of pyridine-2,5-dicarboxylic acid in 100ml of N,N-dimethylformamide, stir the mixture for 5min, and transfer the mixture to the reaction kettle, and place it at 150°C 36h, then washed with ethanol for 3 times and dried at 100°C for 24h to finally obtain Ag-MOF;
b、将0.01mol对Ag-MOF与0.01mol偶氮化合物4-((3-甲酰基-4-羟基苯基)二氮苯)-N-(5-甲基异恶唑-3-酰基)苯磺酰胺充分混合；b. Mix 0.01mol p-Ag-MOF with 0.01mol azo compound 4-((3-formyl-4-hydroxyphenyl)diazobenzene)-N-(5-methylisoxazole-3-acyl) Benzenesulfonamide is fully mixed;
c、将反应混合物与30ml甲醇混合，放入微波化学炉中辐照，反应时间为3min，反应功率为80W；c. Mix the reaction mixture with 30ml of methanol, put it into a microwave chemical furnace for irradiation, the reaction time is 3min, and the reaction power is 80W;
d、将混合物移至反应釜中，置于100℃中24h，然后使用乙醇抽滤洗涤3次后在装有无水CaCl 2的干燥器内干燥，最终得到磺胺-银化合物。 d. Move the mixture to a reaction kettle, place it at 100° C. for 24 hours, then use ethanol to filter and wash it three times, and then dry it in a desiccator filled with anhydrous CaCl 2 to finally obtain the sulfonamide-silver compound.
所述催化剂包括氧化二辛基锡、辛酸亚锡的混合物，其质量比为1：2，参与甲苯二异氰酸酯与葵花油、松节油、甘油发生反应生成聚氨酯，制得的聚氨酯材料的强度更高。The catalyst includes a mixture of dioctyltin oxide and stannous octoate with a mass ratio of 1:2, which participates in the reaction of toluene diisocyanate with sunflower oil, turpentine, and glycerin to form polyurethane, and the resulting polyurethane material has higher strength.
所述阻燃助剂为季戊四醇、硼酸和磷酸酯的混合物，其质量比为10：1：1。The flame retardant additive is a mixture of pentaerythritol, boric acid and phosphoric acid ester with a mass ratio of 10:1:1.
实施例4Example 4
本实施例的一种基于磺胺-银化合物的抗菌型防火涂料，基本结构同实施例3，不同和改进之处在于：包括以下质量分数的组份：葵花油35份，甘油15份，松节油45份，催化剂1.2份，甲苯二异氰酸酯90份，紫外吸收剂3份，防结皮剂1.4份，磺胺-银化合物3份和阻燃助剂14份。将上述组份的葵花油，甘油，松节油，催化剂，紫外吸收剂，防结皮剂，磺胺-银化合物以及阻燃助剂混合，然后加入甲苯二异氰酸酯混合反应，得到磺胺-银化合物的抗菌型防火涂料。A kind of antibacterial type fireproof coating based on sulfonamide-silver compound of the present embodiment, basic structure is the same as embodiment 3, difference and improvement are: comprise the component of following mass fraction: 35 parts of sunflower oils, 15 parts of glycerin, turpentine 45 parts 1.2 parts of catalyst, 90 parts of toluene diisocyanate, 3 parts of ultraviolet absorber, 1.4 parts of anti-skinning agent, 3 parts of sulfonamide-silver compound and 14 parts of flame retardant additive. Mix the sunflower oil, glycerin, turpentine, catalyst, UV absorber, anti-skinning agent, sulfonamide-silver compound and flame retardant additive of the above components, and then add toluene diisocyanate for mixed reaction to obtain the antibacterial type of sulfonamide-silver compound fire retardant coating.
本实施例中，所述磺胺-银化合物的制备方法包括以下步骤：In the present embodiment, the preparation method of the sulfonamide-silver compound comprises the following steps:
a、将0.003mol硝酸银和0.001mol吡啶-2,5-二羧酸溶解于100ml N,N-二甲基甲酰胺，磁力搅拌5min后将混合液移至反应釜中，置于160℃中36h，然后使用乙醇抽滤洗涤3次后置于120℃干燥24h，最终得到Ag-MOF；a. Dissolve 0.003mol of silver nitrate and 0.001mol of pyridine-2,5-dicarboxylic acid in 100ml of N,N-dimethylformamide, stir the mixture for 5min and transfer the mixture to a reaction kettle, and place it at 160°C 36h, then washed with ethanol for 3 times and dried at 120°C for 24h to finally obtain Ag-MOF;
b、将0.02mol对Ag-MOF与0.02mol偶氮化合物4-((3-甲酰基-4-羟基苯基)二氮苯)-N-(5-甲基异恶唑-3-酰基)苯磺酰胺充分混合；b. Mix 0.02mol p-Ag-MOF with 0.02mol azo compound 4-((3-formyl-4-hydroxyphenyl)diazobenzene)-N-(5-methylisoxazole-3-acyl) Benzenesulfonamide is fully mixed;
c、将反应混合物与30ml甲醇混合，放入微波化学炉中辐照，反应时间为4min，反应功率为100W；c, the reaction mixture is mixed with 30ml methanol, put into a microwave chemical furnace for irradiation, the reaction time is 4min, and the reaction power is 100W;
d、将混合物移至反应釜中，置于120℃中36h，然后使用乙醇抽滤洗涤3次后在装有无水CaCl 2的干燥器内干燥，最终得到磺胺-银化合物； d. Move the mixture to a reaction kettle, place it at 120° C. for 36 hours, then use ethanol to filter and wash 3 times, and then dry it in a desiccator equipped with anhydrous CaCl 2 to finally obtain a sulfonamide-silver compound;
所述催化剂包括氧化二辛基锡、辛酸亚锡的混合物，其质量比为1：2，参与甲苯二异氰酸酯与葵花油、松节油、甘油发生反应生成聚氨酯，制得的聚氨酯材料的强度更高。The catalyst includes a mixture of dioctyltin oxide and stannous octoate with a mass ratio of 1:2, which participates in the reaction of toluene diisocyanate with sunflower oil, turpentine, and glycerin to form polyurethane, and the resulting polyurethane material has higher strength.
所述阻燃助剂为季戊四醇、硼酸和磷酸酯的混合物，其质量比为10：1：1。The flame retardant additive is a mixture of pentaerythritol, boric acid and phosphoric acid ester with a mass ratio of 10:1:1.
实施例5Example 5
本实施例的一种基于磺胺-银化合物的抗菌型防火涂料，基本结构同实施例4，不同和改进之处在于：包括以下质量分数的组份：葵花油40份，甘油20份，松节油50份，催化剂2 份，甲苯二异氰酸酯110份，紫外吸收剂4份，防结皮剂2份，磺胺-银化合物6份和阻燃助剂20份。将上述组份的葵花油，甘油，松节油，催化剂，紫外吸收剂，防结皮剂，磺胺-银化合物以及阻燃助剂混合，然后加入甲苯二异氰酸酯混合反应，得到磺胺-银化合物的抗菌型防火涂料。A kind of antibacterial fireproof coating based on sulfonamide-silver compound of the present embodiment, basic structure is the same as embodiment 4, difference and improvement are: comprise the component of following mass fraction: 40 parts of sunflower oils, 20 parts of glycerin, 50 parts of turpentine oils 2 parts of catalyst, 110 parts of toluene diisocyanate, 4 parts of ultraviolet absorber, 2 parts of anti-skinning agent, 6 parts of sulfonamide-silver compound and 20 parts of flame retardant additive. Mix the sunflower oil, glycerin, turpentine, catalyst, UV absorber, anti-skinning agent, sulfonamide-silver compound and flame retardant additive of the above components, and then add toluene diisocyanate for mixed reaction to obtain the antibacterial type of sulfonamide-silver compound fire retardant coating.
本实施例中，所述磺胺-银化合物的制备方法包括以下步骤：In the present embodiment, the preparation method of the sulfonamide-silver compound comprises the following steps:
a、将0.004mol硝酸银和0.0018mol吡啶-2,5-二羧酸溶解于100ml N,N-二甲基甲酰胺，磁力搅拌5min后将混合液移至反应釜中，置于180℃中48h，然后使用乙醇抽滤洗涤3次后置于130℃干燥24h，最终得到Ag-MOF；a. Dissolve 0.004mol of silver nitrate and 0.0018mol of pyridine-2,5-dicarboxylic acid in 100ml of N,N-dimethylformamide, stir the mixture for 5 minutes, and transfer the mixture to a reaction kettle, and place it at 180°C 48h, then use ethanol to filter and wash 3 times, and then dry at 130°C for 24h to finally obtain Ag-MOF;
b、将0.03mol对Ag-MOF与0.03mol偶氮化合物4-((3-甲酰基-4-羟基苯基)二氮苯)-N-(5-甲基异恶唑-3-酰基)苯磺酰胺充分混合；b. Mix 0.03mol p-Ag-MOF with 0.03mol azo compound 4-((3-formyl-4-hydroxyphenyl)diazobenzene)-N-(5-methylisoxazole-3-acyl) Benzenesulfonamide is fully mixed;
c、将反应混合物与50ml甲醇混合，放入微波化学炉中辐照，反应时间为6min，反应功率为100W；c, the reaction mixture is mixed with 50ml of methanol, put into a microwave chemical furnace for irradiation, the reaction time is 6min, and the reaction power is 100W;
d、将混合物移至反应釜中，置于120℃中36h，然后使用乙醇抽滤洗涤3次后在装有无水CaCl 2的干燥器内干燥，最终得到磺胺-银化合物； d. Move the mixture to a reaction kettle, place it at 120° C. for 36 hours, then use ethanol to filter and wash 3 times, and then dry it in a desiccator equipped with anhydrous CaCl 2 to finally obtain a sulfonamide-silver compound;
所述催化剂包括氧化二辛基锡、辛酸亚锡的混合物，其质量比为1：2，参与甲苯二异氰酸酯与葵花油、松节油、甘油发生反应生成聚氨酯，制得的聚氨酯材料的强度更高。The catalyst includes a mixture of dioctyltin oxide and stannous octoate with a mass ratio of 1:2, which participates in the reaction of toluene diisocyanate with sunflower oil, turpentine, and glycerin to form polyurethane, and the resulting polyurethane material has higher strength.
所述阻燃助剂为季戊四醇、硼酸和磷酸酯的混合物，其质量比为10：1：1。The flame retardant additive is a mixture of pentaerythritol, boric acid and phosphoric acid ester with a mass ratio of 10:1:1.
对比例：Comparative example:
对比例防火涂料，包括以下质量分数的组份：葵花油40份，甘油20份，松节油50份，催化剂2份，甲苯二异氰酸酯110份，防结皮剂2份，阻燃助剂20份。The fireproof coating of the comparative example comprises the following components in mass fractions: 40 parts of sunflower oil, 20 parts of glycerin, 50 parts of turpentine, 2 parts of catalyst, 110 parts of toluene diisocyanate, 2 parts of anti-skinning agent, and 20 parts of flame retardant additive.
所述催化剂包括氧化二辛基锡、辛酸亚锡的混合物，其质量比为1：2，参与甲苯二异氰酸酯与葵花油、松节油、甘油发生反应生成聚氨酯，制得的聚氨酯材料的强度更高。The catalyst includes a mixture of dioctyltin oxide and stannous octoate with a mass ratio of 1:2, which participates in the reaction of toluene diisocyanate with sunflower oil, turpentine, and glycerin to form polyurethane, and the resulting polyurethane material has higher strength.
所述阻燃助剂为季戊四醇、硼酸和磷酸酯的混合物，其质量比为1：1：1。The flame retardant additive is a mixture of pentaerythritol, boric acid and phosphoric acid ester with a mass ratio of 1:1:1.
对比例防火涂料的制备方法包括以下步骤：The preparation method of comparative example fireproof coating comprises the following steps:
将葵花油，甘油，松节油，催化剂，防结皮剂以及阻燃助剂混合，然后加入甲苯二异氰酸酯混合反应，得到对比例防火涂料。Mix sunflower oil, glycerin, turpentine, catalyst, anti-skinning agent and flame retardant additive, and then add toluene diisocyanate for mixing reaction to obtain a comparative fireproof coating.
以国家标准和行业标准对防火涂料的各项参数的要求作为对比，与实施例3～5制备的防火涂料的各项参数进行对比，检测结果如表1所示：The requirements of national standards and industry standards for the parameters of fire-resistant coatings are compared, compared with the parameters of the fire-resistant coatings prepared in Examples 3-5, and the test results are as shown in Table 1:
表1对比例和实验例3～5的防火涂料的各项参数检测结果The test results of each parameter of the fireproof coatings of Table 1 Comparative Examples and Experimental Examples 3 to 5
Figure PCTCN2021139899-appb-000005
Figure PCTCN2021139899-appb-000005
由表1可知，由于本发明中制备的磺胺-银化合物受热分解后产生的含N气体，起到隔绝氧气使炭层膨胀的作用，阻燃助剂协同磺胺-银化合物，能够提高耐热稳定性更强，增强防火涂料的阻燃效果。鉴于氯系阻燃剂的C-Cl的键能低，它的分解温度基本与涂料的热分解温度一致，磺胺-银化合物受热分解时，其间吸收一部分热量，降低了温度，同时，分解生成的氯化氢气体的密度大于空气，也有一定的抗菌性，还可以排挤走涂料周围的空气，与密度大于空气的N气形成梯度的氧渗屏障，减弱了高分子链之间的范德华力，使涂料在受热时处于粘流态，此时的涂料具有流动性，而在受热流动时可以带走一部分火焰和热量，从而实现防火涂料的阻燃的效果，进而达到两者在阻燃性能和抗菌性能上的协同式的技术效果；由本实施例3～5制备的涂料的抑菌活性(抗菌率)、最大热释放速率(依据ISO 5660-1:2002《热释放量—锥形量热仪测试方法》检测)以及LOI(LOI:GB T2406-93氧指数法-塑料燃烧性能试验方法)检测数据均优于对比例，也可以证明，加入本发明制备的基于磺胺-银化合物的防火涂料的抗菌性能和阻燃性能更优。其中抗菌率参照GB/T 21510-2008纳米无机涂料抗菌性能检测方法。As can be seen from Table 1, due to the N-containing gas produced after the thermal decomposition of the sulfonamide-silver compound prepared in the present invention, it plays the role of isolating oxygen and making the carbon layer expand, and the flame-retardant additive cooperates with the sulfonamide-silver compound to improve heat resistance and stability. Stronger, enhance the flame retardant effect of fire retardant coatings. In view of the low C-Cl bond energy of chlorine-based flame retardants, its decomposition temperature is basically the same as the thermal decomposition temperature of the coating. When the sulfonamide-silver compound is decomposed by heat, it absorbs part of the heat and reduces the temperature. At the same time, the decomposition generated The density of hydrogen chloride gas is higher than that of air, and it also has certain antibacterial properties. It can also squeeze away the air around the coating, and form a gradient oxygen permeation barrier with N gas, which is denser than air, and weaken the Van der Waals force between the polymer chains. It is in a viscous flow state when heated. At this time, the coating has fluidity, and when heated and flowed, it can take away part of the flame and heat, so as to realize the flame-retardant effect of the fire-resistant coating, and then achieve both in terms of flame-retardant and antibacterial properties. The synergistic technical effect of formula; By the bacteriostasis activity (antibacterial rate) of the coating prepared by present embodiment 3～5, maximum heat release rate (according to ISO 5660-1:2002 " heat release amount-cone calorimeter test method " detection) and LOI (LOI: GB T2406-93 oxygen index method-plastic combustion performance test method) detection data are all better than comparative example, also can prove, add the antibacterial performance and antibacterial property of the fireproof coating based on sulfonamide-silver compound prepared by the present invention The flame retardant performance is better. Among them, the antibacterial rate refers to GB/T 21510-2008 test method for antibacterial performance of nano-inorganic coatings.
以上示意性的对本发明及其实施方式进行了描述，该描述没有限制性，附图中所示的也只是本发明的实施方式之一，实际的结构并不局限于此。所以，如果本领域的普通技术人员受其启示，在不脱离本发明创造宗旨的情况下，不经创造性的设计出与该技术方案相似的结构方式及实施例，均应属于本发明的保护范围。The above schematically describes the present invention and its implementation, which is not restrictive, and what is shown in the drawings is only one of the implementations of the present invention, and the actual structure is not limited thereto. Therefore, if a person of ordinary skill in the art is inspired by it, without departing from the inventive concept of the present invention, without creatively designing a structural mode and embodiment similar to the technical solution, it shall all belong to the protection scope of the present invention .

Claims (9)

  1. 一种基于磺胺-银化合物的抗菌型防火涂料的制备方法，其特征在于：包括如下步骤：A kind of preparation method based on the antibacterial type fireproof coating of sulfonamide-silver compound, it is characterized in that: comprise the steps:
    步骤一、将30～40份葵花油，10～20份甘油，40～50份松节油，1～2份催化剂，2～4份紫外吸收剂，1～2份防结皮剂，2～6份磺胺-银化合物以及10～20份阻燃助剂混合；Step 1. Mix 30-40 parts of sunflower oil, 10-20 parts of glycerin, 40-50 parts of turpentine, 1-2 parts of catalyst, 2-4 parts of ultraviolet absorber, 1-2 parts of anti-skinning agent, 2-6 parts Mixing of sulfonamide-silver compound and 10-20 parts of flame retardant additive;
    步骤二、然后加入80～110份甲苯二异氰酸酯，得到磺胺-银化合物的抗菌型防火涂料。Step 2, then adding 80 to 110 parts of toluene diisocyanate to obtain an antibacterial fireproof coating of sulfonamide-silver compound.
  2. 根据权利要求1所述的一种基于磺胺-银化合物的抗菌型防火涂料的制备方法，其特征在于，步骤一中，所述磺胺-银化合物的制备方法包括以下步骤：A kind of preparation method based on the antibacterial type fireproof coating of sulfonamide-silver compound according to claim 1, it is characterized in that, in step 1, the preparation method of described sulfonamide-silver compound comprises the following steps:
    S1、将0.0015～0.004mol硝酸银和0.0006～0.0018mol吡啶-2,5-二羧酸溶解于100ml N,N-二甲基甲酰胺中，磁力搅拌5min后将混合液移至反应釜中，置于150～180℃中36～48h，然后使用乙醇抽滤洗涤3次后置于100～130℃干燥24h，最终得到Ag-MOF；S1. Dissolve 0.0015～0.004mol of silver nitrate and 0.0006～0.0018mol of pyridine-2,5-dicarboxylic acid in 100ml of N,N-dimethylformamide, stir the mixture for 5 minutes with magnetic force, and transfer the mixture to the reaction kettle. Place at 150-180°C for 36-48h, then use ethanol to filter and wash 3 times, then dry at 100-130°C for 24h to finally obtain Ag-MOF;
    S2、将0.01～0.03mol对Ag-MOF与0.01～0.03mol偶氮化合物4-((3-甲酰基-4-羟基苯基)二氮苯)-N-(5-甲基异恶唑-3-酰基)苯磺酰胺充分混合；S2. Combine 0.01～0.03mol p-Ag-MOF with 0.01～0.03mol azo compound 4-((3-formyl-4-hydroxyphenyl)diazobenzene)-N-(5-methylisoxazole- 3-acyl)benzenesulfonamide is fully mixed;
    S3、将反应混合物与30～50ml甲醇混合，加热，反应时间为3～6min，反应功率为80～100W；S3, mixing the reaction mixture with 30-50ml methanol, heating, the reaction time is 3-6min, and the reaction power is 80-100W;
    S4、将混合物移至反应釜中，置于100～120℃中24～36h，然后使用乙醇抽滤洗涤3次后放入装有无水CaCl 2的干燥器内干燥，最终得到磺胺-银化合物。 S4. Move the mixture to a reaction kettle, place it at 100-120° C. for 24-36 hours, then use ethanol to filter and wash for 3 times, then put it into a desiccator equipped with anhydrous CaCl 2 and dry it to finally obtain the sulfonamide-silver compound .
  3. 根据权利要求2所述的一种基于磺胺-银化合物的抗菌型防火涂料的制备方法，整个反应通式为：A kind of preparation method based on the antibacterial type fireproof coating of sulfonamide-silver compound according to claim 2, whole general reaction formula is:
    Figure PCTCN2021139899-appb-100001
    Figure PCTCN2021139899-appb-100001
    ，其中
    Figure PCTCN2021139899-appb-100002
    为预产物；
    Figure PCTCN2021139899-appb-100003
    为磺胺-银化合物。     ,in
    Figure PCTCN2021139899-appb-100002
    is a pre-product;
    Figure PCTCN2021139899-appb-100003
    For sulfonamide - silver compounds.
  4. 根据权利要求1所述的一种基于磺胺-银化合物的抗菌型防火涂料的制备方法，其特征在于：步骤一中，所述催化剂包括氧化二辛基锡和辛酸亚锡的混合物，其质量比为1：2。A kind of preparation method based on the antibacterial type fireproof coating of sulfonamide-silver compound according to claim 1, it is characterized in that: in step 1, described catalyst comprises the mixture of dioctyltin oxide and stannous octoate, and its mass ratio is 1 :2.
  5. 根据权利要求1所述的一种基于磺胺-银化合物的抗菌型防火涂料的制备方法，其特征在于：步骤一中，所述阻燃助剂为季戊四醇、硼酸和磷酸酯的混合物，其质量比为10：1：1。A kind of preparation method based on the antibacterial type fireproof coating of sulfonamide-silver compound according to claim 1, it is characterized in that: in step 1, described flame retardant additive is the mixture of pentaerythritol, boric acid and phosphoric acid ester, its mass ratio It is 10:1:1.
  6. 根据权利要求2所述的一种基于磺胺-银化合物的抗菌型防火涂料的制备方法，其特征在于：步骤S3中的加热方式为放入微波化学炉中辐照。A method for preparing an antibacterial fireproof coating based on a sulfonamide-silver compound according to claim 2, characterized in that: the heating method in step S3 is irradiating in a microwave chemical furnace.
  7. 一种基于磺胺-银化合物的抗菌型防火涂料，其特征在于：包括以下质量分数的组份：葵花油30～40份，甘油10～20份，松节油40～50份，催化剂1～2份，甲苯二异氰酸酯80～110份，紫外吸收剂2～4份，防结皮剂1～2份，磺胺-银化合物2～6份和阻燃助剂10～20份。An antibacterial fireproof coating based on a sulfonamide-silver compound, characterized in that it comprises the following components in mass fractions: 30-40 parts of sunflower oil, 10-20 parts of glycerin, 40-50 parts of turpentine, 1-2 parts of catalyst, 80-110 parts of toluene diisocyanate, 2-4 parts of ultraviolet absorber, 1-2 parts of anti-skinning agent, 2-6 parts of sulfonamide-silver compound and 10-20 parts of flame retardant additive.
  8. 根据权利要求7所述的一种基于磺胺-银化合物的抗菌型防火涂料，其特征在于：所述催化剂包括氧化二辛基锡和辛酸亚锡的混合物，其质量比为1：2。The antibacterial fireproof coating based on sulfonamide-silver compound according to claim 7, characterized in that: the catalyst comprises a mixture of dioctyltin oxide and stannous octoate, the mass ratio of which is 1:2.
  9. 根据权利要求7所述的一种基于磺胺-银化合物的抗菌型防火涂料，其特征在于：所述阻燃助剂为季戊四醇、硼酸和磷酸酯的混合物，其质量比为10：1：1。The antibacterial fireproof coating based on sulfonamide-silver compound according to claim 7, characterized in that: the flame retardant additive is a mixture of pentaerythritol, boric acid and phosphoric acid ester, and its mass ratio is 10:1:1.
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