WO2016109910A1 - Method for preparing polyurethane coating and adhesive with antibacterial and waterproof properties - Google Patents

Method for preparing polyurethane coating and adhesive with antibacterial and waterproof properties Download PDF

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WO2016109910A1
WO2016109910A1 PCT/CN2015/000419 CN2015000419W WO2016109910A1 WO 2016109910 A1 WO2016109910 A1 WO 2016109910A1 CN 2015000419 W CN2015000419 W CN 2015000419W WO 2016109910 A1 WO2016109910 A1 WO 2016109910A1
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water
nano
antibacterial
zirconium phosphate
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袁福德
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杨磊
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    • 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
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08K5/00—Use of organic ingredients
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
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    • C08K2003/0806—Silver
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    • C08K2003/0893—Zinc
    • C—CHEMISTRY; METALLURGY
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    • C08K3/00—Use of inorganic substances as compounding ingredients
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    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Definitions

  • a method for preparing an antibacterial and water repellent polyurethane coating and an adhesive characterized in that:

Abstract

A method for preparing a polyurethane coating and adhesive with antibacterial and waterproof properties comprises preparing a layered nanometer zirconium phosphate antibacterial body containing Ag ions and Zn ions, adding titanium trichloride and triethylaluminum as catalysts into polytetramethylene ether glycol and isophorone diisocyanate for performing a catalytic reaction so as to obtain polyurethane, and using the layered nanometer zirconium phosphate as an antibacterial agent and trimethylsilyl cyanide as a waterproof agent to modify the polyurethane, thereby obtaining the polyurethane coating and adhesive with antibacterial and waterproof properties, and involving the characteristic of environmental protection.

Description

抗菌性与防水性聚氨酯涂料与胶黏剂的制备方法Antibacterial and waterproof polyurethane coating and adhesive preparation method 技术领域Technical field
本发明涉及的聚氨酯的制备方法，特别涉及抗菌性与防水性聚氨酯涂料与胶黏剂的制备方法。The invention relates to a method for preparing a polyurethane, in particular to a method for preparing an antibacterial and waterproof polyurethane coating and an adhesive.
背景技术Background technique
防水材料主要应用领域包括房屋建筑的屋面、地下、外墙和室内；城市道路桥梁和地下空间等市政工程；高速公路和高速铁路的桥梁、隧道；地下铁道等交通工程；引水渠、水库、坝体、水利发电站及水处理等水利工程，适用于屋面和厕浴间、地下室、蓄水池、墙面的防水，防渗、防潮。按照应用材料来分可用于造纸、纺织、皮革等领域。The main application areas of waterproof materials include roofing, underground, exterior wall and interior of building construction; municipal engineering such as urban road bridges and underground spaces; bridges and tunnels of expressways and high-speed railways; traffic engineering such as underground railways; diversion canals, reservoirs and dams Water conservancy projects such as water power stations and water treatments are suitable for waterproofing, anti-seepage and moisture-proof of roofs and toilets, basements, reservoirs and walls. According to the application materials, it can be used in the fields of paper making, textile, leather and so on.
聚氨酯进行合成常采用二月桂酸二丁基锡做催化剂，但由于重金属锡在随着聚氨酯的降解而对环境造成危害，筛选高效无毒的催化剂是聚氨酯合成中的一大难题。Polyurethane dilaurate is often used as a catalyst for the synthesis of polyurethane. However, since heavy metal tin is harmful to the environment with the degradation of polyurethane, screening for highly efficient and non-toxic catalysts is a major problem in polyurethane synthesis.
水性聚氨酯(又称水基聚氨酯)是一种在聚氨酯的分子链中含有亲水性基团的聚氨酯树脂，与水具有很强的亲和性，采用特定的工艺能使之在水中分散并形成稳定的体系。水性聚氨酯主要应用于皮革涂饰、纺织印染、造纸业、建筑涂料、胶粘剂、铸钢涂料等方面，这些领域目前对抗菌性提出了新的要求。Waterborne polyurethane (also known as water-based polyurethane) is a polyurethane resin containing a hydrophilic group in the molecular chain of polyurethane. It has a strong affinity with water and can be dispersed and formed in water by a specific process. A stable system. Waterborne polyurethane is mainly used in leather finishing, textile printing and dyeing, papermaking, architectural coatings, adhesives, cast steel coatings, etc. These areas currently impose new requirements on antimicrobial properties.
含银离子、含锌离子的纳米层状磷酸锆抗菌体是以层状磷酸锆为载体，银锌等多种金属离子为抗菌离子以及多种助剂制成的无机类抗菌剂。它具有安全性高和更好的耐热性好，化学稳定性好，可添加到各类树脂中，起到抗菌作用，可对各类细菌进行高效广谱的杀灭和去除。在涤纶、丙纶、锦纶中有一定的应用，对大肠杆菌、金黄色葡萄球菌、白色念珠菌等抑菌率为99.9％以上。The nano-layered zirconium phosphate antibacterial body containing silver ions and zinc ions is an inorganic antibacterial agent made of layered zirconium phosphate as a carrier, and various metal ions such as silver and zinc are antibacterial ions and various auxiliary agents. It has high safety and better heat resistance, good chemical stability, can be added to various types of resins, plays an antibacterial role, and can effectively kill and remove various types of bacteria. It has certain applications in polyester, polypropylene and nylon. The bacteriostatic rate against Escherichia coli, Staphylococcus aureus and Candida albicans is 99.9% or more.
发明内容Summary of the invention
选择催化剂三氯化钛和三乙基铝替代传统的聚氨酯催化剂，加入到聚四氢呋喃醚二醇与异佛尔酮二异氰酸酯中进行催化，选择纳米层状磷酸锆抗菌体和防水剂对聚氨酯进行改性，聚氨酯涂料与胶粘剂的抗菌性与防水性。Selecting catalysts such as titanium trichloride and triethylaluminum to replace the traditional polyurethane catalyst, adding to polytetrahydrofuran ether glycol and isophorone diisocyanate for catalysis, selecting nano-layered zirconium phosphate antibacterial and water repellent to modify polyurethane Properties, antibacterial and waterproof properties of polyurethane coatings and adhesives.
本发明采用了以下技术方案。The present invention adopts the following technical solutions.
1.抗菌性与防水性聚氨酯涂料与胶黏剂的制备方法，其特征在于：1. A method for preparing an antibacterial and water repellent polyurethane coating and an adhesive, characterized in that:
(1)、纳米层状磷酸锆载体的制备(1) Preparation of nano-layered zirconium phosphate carrier
往三口瓶中加入11.2g氯氧化锆水溶液和草酸6.5g，搅拌15min中后加入磷酸氢二钠4.3g，搅拌升温到85℃，搅拌保温70min，加入用5g水溶解的0.78g聚乙二醇200，85℃搅拌60min，过滤沉淀物，水洗上述沉淀物，将洗净的沉淀物放入70℃下恒温48h，脱水，得到纳米层状磷酸锆载体A，其圆片最长直径小于100nm，厚度小于40nm；将上述的3.4g纳米层状磷酸锆载体A，分散在用32g水溶解的60g硝酸锌溶液，升温到95℃，搅拌保温1h，过滤分离出含锌的中间载体B，滤液回收；向2.7g含锌的中间载体B中加入蒸馏水45g、硝酸银0.65g和硝酸铬0.7g，在75℃下搅拌1h，过滤分离出含银离子、含锌离子的纳米层状磷酸锆抗菌体C，其中抗菌体C的含水率为26％；11.2g of zirconium oxychloride aqueous solution and 6.5g of oxalic acid were added to the three-necked bottle. After stirring for 15 minutes, 4.3 g of disodium hydrogen phosphate was added, and the mixture was stirred and heated to 85 ° C, stirred and kept for 70 min, and 0.78 g of polyethylene glycol dissolved in 5 g of water was added. After stirring at 200 °C for 85 min, the precipitate was filtered, and the precipitate was washed with water, and the precipitate was placed at 70 ° C for 48 h, and dehydrated to obtain a nano-layered zirconium phosphate carrier A having a longest diameter of less than 100 nm. The thickness is less than 40 nm; the above 3.4 g of the nano-layered zirconium phosphate carrier A is dispersed in 60 g of a zinc nitrate solution dissolved in 32 g of water, heated to 95 ° C, stirred and kept for 1 h, and the zinc-containing intermediate carrier B is separated by filtration, and the filtrate is recovered. To 2.7 g of zinc-containing intermediate carrier B, 45 g of distilled water, 0.65 g of silver nitrate and 0.7 g of chromium nitrate were added, and stirred at 75 ° C for 1 h, and a nano-layered zirconium phosphate antibacterial containing silver ions and zinc ions was separated by filtration. C, wherein the water content of the antibacterial body C is 26%;
(2)、在装有搅拌浆、温度计、冷凝管的500ml的三口烧瓶中，将聚四氢呋喃醚二醇102g与异佛尔酮二异氰酸酯33.6g混合，在三氯化钛0.18g和三乙基铝0.08g存在的条件下，于85℃下反应2.5h，得到135.5g聚氨酯预聚体A；(2) In a 500 ml three-necked flask equipped with a stirring slurry, a thermometer, and a condenser, 102 g of polytetrahydrofuran ether glycol and 33.6 g of isophorone diisocyanate were mixed, and 0.18 g of trichloride and triethylamine. Aluminum in the presence of 0.08g, reacted at 85 ° C for 2.5h, to obtain 135.5g polyurethane prepolymer A;
(3)、向聚氨酯预聚体A中加入二羟甲基丙酸4.76g和乙酸异丙酯15g，于75℃条件下反应1.5h，加入 三乙胺5.99g进行中和反应30min，加水20g进行乳化，形成179g的聚氨酯B备用；(3) Add 4.76 g of dimethylolpropionic acid and 15 g of isopropyl acetate to the polyurethane prepolymer A, and react at 75 ° C for 1.5 h, and add 3.99 g of triethylamine was neutralized for 30 min, and 20 g of water was added for emulsification to form 179 g of polyurethane B for use;
(4)、将十二烷基苯磺酸钠12g溶于60g水中，加入上述(1)所得的1.1g纳米层状磷酸锆抗菌体C、乙烯基三乙氧基硅烷2g、三乙醇胺1g和1g三甲基硅化腈，在剪切速度700r/min下乳化，乳化时间30min，得纳米材料乳液C备用；(4) Dissolving 12 g of sodium dodecylbenzenesulfonate in 60 g of water, and adding 1.1 g of the nano-layered zirconium phosphate antibacterial C obtained in the above (1), 2 g of vinyltriethoxysilane, 1 g of triethanolamine, and 1g of trimethylsilicated nitrile, emulsified at a shear rate of 700r/min, and an emulsification time of 30min, to obtain a nanomaterial emulsion C for use;
(5)、往聚氨酯B中加入9g纳米材料乳液C，在pH为7的条件下，剪切搅拌速度800rpm，搅拌时间30min，得到抗菌性与防水性聚氨酯涂料与胶黏剂187g。(5) To the polyurethane B, 9 g of the nano material emulsion C was added, and under the condition of pH 7, the shear stirring speed was 800 rpm, and the stirring time was 30 min, and 187 g of an antibacterial and water-repellent polyurethane coating and an adhesive were obtained.
2.抗菌性与防水性聚氨酯涂料与胶黏剂的制备方法，其特征在于：2. A method for preparing an antibacterial and water repellent polyurethane coating and an adhesive, characterized in that:
(1)、纳米层状磷酸锆载体的制备(1) Preparation of nano-layered zirconium phosphate carrier
往三口瓶中加入11.2g氯氧化锆水溶液和草酸6.5g，搅拌15min中后加入磷酸氢二钠4.3g，搅拌升温到85℃，搅拌保温70min，加入用5g水溶解的0.78g聚乙二醇200，搅拌保温60min，过滤沉淀物，水洗上述沉淀物，将洗净的沉淀物放入70℃下恒温48h，脱水，得到纳米层状磷酸锆载体A，其圆片最长直径小于100nm，厚度小于40nm；将上述的3.4g纳米层状磷酸锆载体A，分散在用32g水溶解的60g硝酸锌溶液，升温到95℃，搅拌保温1h，过滤分离出含锌的中间载体B，滤液回收；向2.7g含锌的中间载体B中加入蒸馏水45g、硝酸银0.65g和硝酸铁0.43g，在75℃下搅拌保温1h，过滤分离出含银离子、含锌离子的纳米层状磷酸锆抗菌体C，其中抗菌体C的含水率为26％；11.2g of zirconium oxychloride aqueous solution and 6.5g of oxalic acid were added to the three-necked bottle. After stirring for 15 minutes, 4.3 g of disodium hydrogen phosphate was added, and the mixture was stirred and heated to 85 ° C, stirred and kept for 70 min, and 0.78 g of polyethylene glycol dissolved in 5 g of water was added. 200, stirring and holding for 60min, filtering the precipitate, washing the above precipitate, washing the precipitate into 70 ° C constant temperature for 48h, dehydration, to obtain nano-layered zirconium phosphate carrier A, the longest diameter of the wafer is less than 100nm, thickness The above-mentioned 3.4 g of the nano-layered zirconium phosphate carrier A is dispersed in 60 g of zinc nitrate solution dissolved in 32 g of water, heated to 95 ° C, stirred and kept for 1 h, and the zinc-containing intermediate carrier B is separated by filtration, and the filtrate is recovered; To 2.7 g of zinc-containing intermediate carrier B, 45 g of distilled water, 0.65 g of silver nitrate and 0.43 g of ferric nitrate were added, and the mixture was stirred and kept at 75 ° C for 1 h, and the nano-layered zirconium phosphate antibacterial body containing silver ions and zinc ions was separated by filtration. C, wherein the water content of the antibacterial body C is 26%;
(2)、在装有搅拌浆、温度计、冷凝管的500ml的三口烧瓶中，将聚四氢呋喃醚二醇100g与异佛尔酮二异氰酸酯109.9g混合，在三氯化钛0.58g和三乙基铝0.18g存在的条件下，于95℃下反应3.5h，得到208.1g聚氨酯预聚体A；(2) In a 500 ml three-necked flask equipped with a stirring slurry, a thermometer, and a condenser, 100 g of polytetrahydrofuran ether glycol and 109.9 g of isophorone diisocyanate were mixed with 0.58 g of titanium trichloride and triethylamine. In the presence of 0.18 g of aluminum, the reaction was carried out at 95 ° C for 3.5 h to obtain 208.1 g of polyurethane prepolymer A;
(3)、向聚氨酯预聚体A中加入二羟甲基丁酸21.1g和四氢呋喃52.2g，于85℃条件下反应4.5h，加入三乙胺13.1g进行中和反应50min，加水20g进行乳化，形成305g的聚氨酯乳液B备用；(3) Add 21.1 g of dimethylol butyric acid and 52.2 g of tetrahydrofuran to the polyurethane prepolymer A, react at 85 ° C for 4.5 h, add 13.1 g of triethylamine for neutralization for 50 min, and add 20 g of water for emulsification. Forming 305 g of polyurethane emulsion B for use;
(4)、将聚丙烯酸钠12g溶于55g水中，加入上述(1)所得的1.2g纳米层状磷酸锆抗菌体C、乙烯基三甲氧基硅烷4g和1g三甲基硅化腈，在剪切1200r/min下乳化，乳化70min，得纳米材料乳液C备用；(4) Dissolving 12 g of sodium polyacrylate in 55 g of water, adding 1.2 g of the nano-layered zirconium phosphate antibacterial C obtained in the above (1), vinyl trimethoxysilane 4 g, and 1 g of trimethylsilylated nitrile, in the shearing Emulsified at 1200r/min, emulsified for 70min, and obtained nano material emulsion C for use;
(5)、往B中加入的30.6g纳米材料乳液C，在pH为7的条件下，剪切搅拌速度为1100rpm，剪切搅拌时间60min，得抗菌性与防水性聚氨酯涂料与胶黏剂331g。(5) 30.6g nanomaterial emulsion C added to B, under the condition of pH 7, shearing stirring speed is 1100rpm, shearing stirring time is 60min, and antibacterial and waterproof polyurethane coating and adhesive 331g are obtained. .
3.抗菌性与防水性聚氨酯涂料与胶黏剂的制备方法，其特征在于：3. A method for preparing an antibacterial and water repellent polyurethane coating and an adhesive, characterized in that:
(1)、纳米层状磷酸锆载体的制备(1) Preparation of nano-layered zirconium phosphate carrier
往三口瓶中加入11.2g氯氧化锆水溶液和草酸6.5g，搅拌15min中后加入磷酸氢二钠4.3g，搅拌升温到85℃，搅拌70min，加入用5g水溶解的0.78g聚乙二醇200，搅拌保温60min，过滤沉淀物，水洗上述沉淀物后得到干净的纳米层状磷酸锆载体A，放入70℃下恒温48h，脱水，得到纳米层状磷酸锆载体A，圆片最长直径小于100nm，厚度小于40nm；将3.4g纳米层状磷酸锆载体A，分散在用32g水溶解的60g硝酸锌溶液中，升温到95℃中，搅拌保温1h，过滤分离出含锌的中间载体B，滤液回收；向2.7g含锌的中间载体B中加入蒸馏水45g、硝酸银0.65g和硝酸镁0.21g，在75℃下搅拌保温1h，过滤分离出2.1g含银离子、含锌离子的纳米层状磷酸锆抗菌体C，其中抗菌体C的含水率为26％；11.2g of zirconium oxychloride aqueous solution and 6.5g of oxalic acid were added to the three-necked bottle. After stirring for 15 minutes, 4.3 g of disodium hydrogen phosphate was added, and the mixture was stirred and heated to 85 ° C, stirred for 70 min, and 0.78 g of polyethylene glycol 200 dissolved in 5 g of water was added. After stirring for 60 min, the precipitate was filtered, and the precipitate was washed with water to obtain a clean nano-layered zirconium phosphate carrier A, which was placed at 70 ° C for 48 h, and dehydrated to obtain a nano-layered zirconium phosphate carrier A. The longest diameter of the wafer was smaller than 100 nm, thickness less than 40 nm; 3.4 g of nano-layered zirconium phosphate carrier A, dispersed in 60 g of zinc nitrate solution dissolved in 32 g of water, heated to 95 ° C, stirred for 1 h, filtered to separate the zinc-containing intermediate carrier B, The filtrate was recovered. To 2.7 g of the zinc-containing intermediate carrier B, 45 g of distilled water, 0.65 g of silver nitrate and 0.21 g of magnesium nitrate were added, and the mixture was stirred and kept at 75 ° C for 1 h, and 2.1 g of a silver layer containing silver ions and containing zinc ions was separated by filtration. Zirconium phosphate antibacterial C, wherein the water content of the antibacterial C is 26%;
(2)、在装有搅拌浆、温度计、冷凝管的500ml的四口烧瓶中，将聚四氢呋喃醚二醇100g与异佛尔酮二异氰酸酯69.6g混合，在三氯化钛0.48g和三乙基铝0.2g存在的条件下，于78℃下反应2.5h，得到165.2g聚氨酯预聚体A； (2) In a 500 ml four-necked flask equipped with a stirring slurry, a thermometer, and a condenser, 100 g of polytetrahydrofuran ether glycol and 69.6 g of isophorone diisocyanate were mixed, and 0.48 g of titanium trichloride and triethyl bromide. In the presence of 0.2 g of base aluminum, reacted at 78 ° C for 2.5 h to obtain 165.2 g of polyurethane prepolymer A;
(3)、向聚氨酯预聚体A中加入二羟甲基丁酸10.5g和二甲基亚砜29.3g，于75℃条件下反应1.5h，加入三乙胺9.78g进行中和反应60min，加水20g进行乳化，形成231g聚氨酯B备用；(3) Adding 10.5 g of dimethylolbutanoic acid and 29.3 g of dimethyl sulfoxide to the polyurethane prepolymer A, reacting at 75 ° C for 1.5 h, adding 9.78 g of triethylamine for neutralization for 60 min. 20 g of water was added for emulsification to form 231 g of polyurethane B for use;
(4)、将聚乙烯醇10g溶于46g水中，加入上述(1)所得的2.4g纳米层状磷酸锆抗菌体C、γ-甲基丙烯酰氧基丙基三甲氧基硅烷3g、酒石酸1.9g、对羧基苯磺酰胺0.56g和1g三甲基硅化腈，在700r/min下剪切乳化，乳化30min，得纳米材料乳液C备用；(4) Dissolving 10 g of polyvinyl alcohol in 46 g of water, and adding 2.4 g of the nano-layered zirconium phosphate antibacterial C obtained in the above (1), γ-methacryloxypropyltrimethoxysilane 3 g, and tartaric acid 1.9. g, p-carboxybenzenesulfonamide 0.56g and 1g trimethylsilylated nitrile, shear emulsified at 700r/min, emulsified for 30min, to obtain nano material emulsion C spare;
(5)、往聚氨酯B中加入17.6g纳米材料乳液C，在pH为8的条件下，剪切搅拌速度900rpm，搅拌时间35min，得到抗菌性与防水性聚氨酯涂料与胶黏剂241g。(5) 17.6 g of nano material emulsion C was added to the polyurethane B, and under a condition of pH 8, a shear stirring speed of 900 rpm and a stirring time of 35 minutes were obtained to obtain an antibacterial and water-repellent polyurethane coating and an adhesive 241 g.
4.抗菌性与防水性聚氨酯涂料与胶黏剂的制备方法，其特征在于：4. A method for preparing an antibacterial and water repellent polyurethane coating and an adhesive, characterized in that:
(1)、纳米层状磷酸锆载体的制备(1) Preparation of nano-layered zirconium phosphate carrier
往三口瓶中加入11.2g氯氧化锆水溶液和草酸6.5g，搅拌15min中后加入磷酸氢二钠4.3g，搅拌升温到85℃，搅拌70min，加入用5g水溶解的0.78g聚乙二醇200，搅拌保温60min，过滤沉淀物，水洗上述沉淀物后得到干净的纳米层状磷酸锆载体A，放入70℃下恒温48h，脱水，得到纳米层状磷酸锆载体A，圆片最长直径小于100nm，厚度小于40nm；将3.4g纳米层状磷酸锆载体A，分散在用32g水溶解的60g硝酸锌溶液中，升温到95℃中，搅拌保温1h，过滤分离出含锌的中间载体B，滤液回收；向2.7g含锌的中间载体B中加入蒸馏水45g、硝酸银0.65g和硝酸铅0.12g，在75℃下搅拌保温1h，过滤分离出2.1g含银离子、含锌离子的纳米层状磷酸锆抗菌体C，其中抗菌体C的含水率为26％；11.2g of zirconium oxychloride aqueous solution and 6.5g of oxalic acid were added to the three-necked bottle. After stirring for 15 minutes, 4.3 g of disodium hydrogen phosphate was added, and the mixture was stirred and heated to 85 ° C, stirred for 70 min, and 0.78 g of polyethylene glycol 200 dissolved in 5 g of water was added. After stirring for 60 min, the precipitate was filtered, and the precipitate was washed with water to obtain a clean nano-layered zirconium phosphate carrier A, which was placed at 70 ° C for 48 h, and dehydrated to obtain a nano-layered zirconium phosphate carrier A. The longest diameter of the wafer was smaller than 100 nm, thickness less than 40 nm; 3.4 g of nano-layered zirconium phosphate carrier A, dispersed in 60 g of zinc nitrate solution dissolved in 32 g of water, heated to 95 ° C, stirred for 1 h, filtered to separate the zinc-containing intermediate carrier B, The filtrate was recovered. To 2.7 g of zinc-containing intermediate carrier B, 45 g of distilled water, 0.65 g of silver nitrate and 0.12 g of lead nitrate were added, and the mixture was stirred and kept at 75 ° C for 1 h, and 2.1 g of a silver layer containing silver ions and containing zinc ions was separated by filtration. Zirconium phosphate antibacterial C, wherein the water content of the antibacterial C is 26%;
(2)、在装有搅拌浆、温度计、冷凝管的500m的四口烧瓶中，将聚四氢呋喃醚二醇100g与异佛尔酮二异氰酸酯33.3g混合，在三氯化钛0.38g和三乙基铝0.28g存在的条件下，于75℃下反应3.5h，得到132g聚氨酯预聚体A；(2) In a 500-m four-necked flask equipped with a stirring slurry, a thermometer, and a condenser, 100 g of polytetrahydrofuran ether glycol and 33.3 g of isophorone diisocyanate were mixed, and 0.38 g of titanium trichloride and triethyl bromide. The reaction of the base aluminum in the presence of 0.28g at 75 ° C for 3.5h, to obtain 132g polyurethane prepolymer A;
(3)、向聚氨酯预聚体A中加入二羟甲基丙酸4.75g和丙酮溶剂16g，于85℃条件下反应1.5h，加入三乙胺5.97g进行中和反应30min，加水20g进行乳化，形成177g的聚氨酯B备用；(3) Adding 4.75 g of dimethylolpropionic acid and 16 g of acetone solvent to the polyurethane prepolymer A, reacting at 85 ° C for 1.5 h, adding 5.97 g of triethylamine for neutralization for 30 min, and adding 20 g of water for emulsification. Forming 177g of polyurethane B for use;
(4)、将多聚磷酸钠10g溶于水50g中，加入上述(1)的0.9g纳米层状磷酸锆抗菌体C、γ-氨丙基三乙氧基硅烷3g和1.3g三甲基硅化腈，在300r/min下剪切乳化，乳化20min，得纳米材料乳液C备用；(4) Dissolving 10 g of sodium polyphosphate in 50 g of water, adding 0.9 g of the nano layered zirconium phosphate antibacterial agent C of the above (1), 3 g of γ-aminopropyltriethoxysilane, and 1.3 g of trimethyl group. Silicified nitrile, shear emulsified at 300r/min, emulsified for 20min, to obtain nano material emulsion C for use;
(5)、往聚氨酯B中加入9g纳米材料乳液C，在pH为7的条件下，剪切搅拌速度600rpm，搅拌时间50min，得到抗菌性与防水性聚氨酯涂料与胶黏剂186g。(5) To the polyurethane B, 9 g of the nano material emulsion C was added, and under the condition of pH 7, the shear stirring speed was 600 rpm, and the stirring time was 50 min, and 186 g of an antibacterial and water-repellent polyurethane coating and an adhesive were obtained.
5.抗菌性与防水性聚氨酯涂料与胶黏剂的制备方法，其特征在于：5. A method for preparing an antibacterial and water repellent polyurethane coating and an adhesive, characterized in that:
(1)、纳米层状磷酸锆载体的制备(1) Preparation of nano-layered zirconium phosphate carrier
往三口瓶中加入11.2g氯氧化锆水溶液和草酸6.5g，搅拌15min中后加入磷酸氢二钠4.3g，搅拌升温到85℃，搅拌70min，加入用5g水溶解的0.78g聚乙二醇200，搅拌保温60min，过滤沉淀物，水洗上述沉淀物后得到干净的纳米层状磷酸锆载体A，放入70℃下恒温48h，脱水，得到纳米层状磷酸锆载体A，圆片最长直径小于100nm，厚度小于40nm；将3.4g纳米层状磷酸锆载体A，分散在用32g水溶解的60g硝酸锌溶液中，升温到95℃中，搅拌保温1h，过滤分离出含锌的中间载体B，滤液回收；向2.7g含锌的中间载体B中加入蒸馏水45g、硝酸银0.65g和硝酸铜0.12g，在75℃下搅拌保温1h，过滤分离出2.1g含银离子、含锌离子的纳米层状磷酸锆抗菌体C，其中抗菌体C的含水率为26％；11.2g of zirconium oxychloride aqueous solution and 6.5g of oxalic acid were added to the three-necked bottle. After stirring for 15 minutes, 4.3 g of disodium hydrogen phosphate was added, and the mixture was stirred and heated to 85 ° C, stirred for 70 min, and 0.78 g of polyethylene glycol 200 dissolved in 5 g of water was added. After stirring for 60 min, the precipitate was filtered, and the precipitate was washed with water to obtain a clean nano-layered zirconium phosphate carrier A, which was placed at 70 ° C for 48 h, and dehydrated to obtain a nano-layered zirconium phosphate carrier A. The longest diameter of the wafer was smaller than 100 nm, thickness less than 40 nm; 3.4 g of nano-layered zirconium phosphate carrier A, dispersed in 60 g of zinc nitrate solution dissolved in 32 g of water, heated to 95 ° C, stirred for 1 h, filtered to separate the zinc-containing intermediate carrier B, The filtrate was recovered. To 2.7 g of the zinc-containing intermediate carrier B, 45 g of distilled water, 0.65 g of silver nitrate and 0.12 g of copper nitrate were added, and the mixture was stirred and kept at 75 ° C for 1 h, and 2.1 g of a silver layer containing silver ions and containing zinc ions was separated by filtration. Zirconium phosphate antibacterial C, wherein the water content of the antibacterial C is 26%;
(2)、在装有搅拌浆、温度计、冷凝管的500ml的四口烧瓶中，将聚四氢呋喃醚二醇100g与异佛尔酮二异氰酸酯99.9g混合，在三氯化钛0.42g和三乙基铝0.08g存在的条件下，于95℃下反应1.5h，得到200.1g 聚氨酯预聚体A；(2) In a 500 ml four-necked flask equipped with a stirring slurry, a thermometer, and a condenser, 100 g of polytetrahydrofuran ether glycol and 99.9 g of isophorone diisocyanate were mixed, and 0.42 g of titanium trichloride and tribromide. The reaction was carried out at 95 ° C for 1.5 h in the presence of 0.08 g of base aluminum to obtain 200.1 g. Polyurethane prepolymer A;
(3)、向聚氨酯预聚体A中加入二羟甲基丁酸21.1g和丙酮溶剂50.2g，于85℃条件下反应1.5h，加入三乙胺12.1g进行中和反应50min，加水25g进行乳化，形成304g的聚氨酯乳液B备用；(3) Adding 21.1 g of dimethylol butyric acid and 50.2 g of acetone solvent to the polyurethane prepolymer A, reacting at 85 ° C for 1.5 h, adding 12.1 g of triethylamine for neutralization for 50 min, and adding 25 g of water. Emulsified to form 304g of polyurethane emulsion B for use;
(4)、将十二烷基苯磺酸钠10g溶于50g水中，加入2.1g纳米层状磷酸锆抗菌体C、γ-缩水甘油醚氧丙基三甲氧基硅烷5g和1g三甲基硅化腈，在1100r/min下剪切乳化，乳化40min，得纳米材料乳液备用；(4) Dissolving 10 g of sodium dodecylbenzenesulfonate in 50 g of water, adding 2.1 g of nano-layered zirconium phosphate antibacterial C, γ-glycidoxypropyltrimethoxysilane 5 g and 1 g of trimethylsilation Nitrile, shear emulsified at 1100r/min, emulsified for 40min, to obtain nanomaterial emulsion for use;
(5)、往聚氨酯乳液B中加入30.4g上述纳米材料乳液C，在pH为7的条件下，剪切搅拌速度为1200rpm，剪切搅拌时间40min，得到抗菌性与防水性聚氨酯涂料与胶黏剂329g。(5), adding 30.4 g of the above nanomaterial emulsion C to the polyurethane emulsion B, under the condition of pH 7, the shear stirring speed is 1200 rpm, the shear stirring time is 40 min, and the antibacterial and waterproof polyurethane coating and the adhesive are obtained. Agent 329g.
本发明具有以下特点：The invention has the following characteristics:
(1)选择良好的纳米层状磷酸锆抗菌体作为抗菌剂，具有环保高效的效果；(1) Selecting a good nano-layered zirconium phosphate antibacterial agent as an antibacterial agent, which has an environmentally-friendly and efficient effect;
(2)三氯化钛和三乙基铝替代传统的二月桂酸二丁基锡做催化剂，具有环保的特点；(2) Titanium trichloride and triethyl aluminum replace the traditional dibutyltin dilaurate as a catalyst, which has environmental protection characteristics;
(3)选择硝酸铜、硝酸铅、硝酸铅、硝酸镁和硝酸铬作为抗菌剂的协效剂，使抗菌剂具有良好的抗菌效果；(3) Selecting copper nitrate, lead nitrate, lead nitrate, magnesium nitrate and chromium nitrate as synergists for the antibacterial agent, so that the antibacterial agent has a good antibacterial effect;
(4)三甲基硅化腈做防水材料，具有良好的防水性。(4) Trimethylsilylated nitrile is used as a waterproof material and has good water resistance.
实例一Example one
1.抗菌性与防水性聚氨酯涂料与胶黏剂的制备方法，其特征在于：1. A method for preparing an antibacterial and water repellent polyurethane coating and an adhesive, characterized in that:
(1)、纳米层状磷酸锆载体的制备(1) Preparation of nano-layered zirconium phosphate carrier
往三口瓶中加入11.2g氯氧化锆水溶液和草酸6.5g，搅拌15min中后加入磷酸氢二钠4.3g，搅拌升温到85℃，搅拌保温70min，加入用5g水溶解的0.78g聚乙二醇200，85℃搅拌60min，过滤沉淀物，水洗上述沉淀物，将洗净的沉淀物放入70℃下恒温48h，脱水，得到纳米层状磷酸锆载体A，其圆片最长直径小于100nm，厚度小于40nm；将上述的3.4g纳米层状磷酸锆载体A，分散在用32g水溶解的60g硝酸锌溶液，升温到95℃，搅拌保温1h，过滤分离出含锌的中间载体B，滤液回收；向2.7g含锌的中间载体B中加入蒸馏水45g、硝酸银0.65g和硝酸铬0.7g，在75℃下搅拌1h，过滤分离出含银离子、含锌离子的纳米层状磷酸锆抗菌体C，其中抗菌体C的含水率为26％；11.2g of zirconium oxychloride aqueous solution and 6.5g of oxalic acid were added to the three-necked bottle. After stirring for 15 minutes, 4.3 g of disodium hydrogen phosphate was added, and the mixture was stirred and heated to 85 ° C, stirred and kept for 70 min, and 0.78 g of polyethylene glycol dissolved in 5 g of water was added. After stirring at 200 °C for 85 min, the precipitate was filtered, and the precipitate was washed with water, and the precipitate was placed at 70 ° C for 48 h, and dehydrated to obtain a nano-layered zirconium phosphate carrier A having a longest diameter of less than 100 nm. The thickness is less than 40 nm; the above 3.4 g of the nano-layered zirconium phosphate carrier A is dispersed in 60 g of a zinc nitrate solution dissolved in 32 g of water, heated to 95 ° C, stirred and kept for 1 h, and the zinc-containing intermediate carrier B is separated by filtration, and the filtrate is recovered. To 2.7 g of zinc-containing intermediate carrier B, 45 g of distilled water, 0.65 g of silver nitrate and 0.7 g of chromium nitrate were added, and stirred at 75 ° C for 1 h, and a nano-layered zirconium phosphate antibacterial containing silver ions and zinc ions was separated by filtration. C, wherein the water content of the antibacterial body C is 26%;
(2)、在装有搅拌浆、温度计、冷凝管的500ml的三口烧瓶中，将聚四氢呋喃醚二醇102g与异佛尔酮二异氰酸酯33.6g混合，在三氯化钛0.18g和三乙基铝0.08g存在的条件下，于85℃下反应2.5h，得到135.5g聚氨酯预聚体A；(2) In a 500 ml three-necked flask equipped with a stirring slurry, a thermometer, and a condenser, 102 g of polytetrahydrofuran ether glycol and 33.6 g of isophorone diisocyanate were mixed, and 0.18 g of trichloride and triethylamine. Aluminum in the presence of 0.08g, reacted at 85 ° C for 2.5h, to obtain 135.5g polyurethane prepolymer A;
(3)、向聚氨酯预聚体A中加入二羟甲基丙酸4.76g和乙酸异丙酯15g，于75℃条件下反应1.5h，加入三乙胺5.99g进行中和反应30min，加水20g进行乳化，形成179g的聚氨酯B备用；(3) Add 4.76 g of dimethylolpropionic acid and 15 g of isopropyl acetate to the polyurethane prepolymer A, react at 75 ° C for 1.5 h, add 5.99 g of triethylamine for neutralization for 30 min, add water 20 g. Emulsified to form 179 g of polyurethane B for use;
(4)、将十二烷基苯磺酸钠12g溶于60g水中，加入上述(1)所得的1.1g纳米层状磷酸锆抗菌体C、乙烯基三乙氧基硅烷2g、三乙醇胺1g和1g三甲基硅化腈，在剪切速度700r/min下乳化，乳化时间30min，得纳米材料乳液C备用；(4) Dissolving 12 g of sodium dodecylbenzenesulfonate in 60 g of water, and adding 1.1 g of the nano-layered zirconium phosphate antibacterial C obtained in the above (1), 2 g of vinyltriethoxysilane, 1 g of triethanolamine, and 1g of trimethylsilicated nitrile, emulsified at a shear rate of 700r/min, and an emulsification time of 30min, to obtain a nanomaterial emulsion C for use;
(5)、往聚氨酯B中加入9g纳米材料乳液C，在pH为7的条件下，剪切搅拌速度800rpm，搅拌时间30min，得到抗菌性与防水性聚氨酯涂料与胶黏剂187g。(5) To the polyurethane B, 9 g of the nano material emulsion C was added, and under the condition of pH 7, the shear stirring speed was 800 rpm, and the stirring time was 30 min, and 187 g of an antibacterial and water-repellent polyurethane coating and an adhesive were obtained.
实例二Example two
(1)、纳米层状磷酸锆载体的制备 (1) Preparation of nano-layered zirconium phosphate carrier
往三口瓶中加入11.2g氯氧化锆水溶液和草酸6.5g，搅拌15min中后加入磷酸氢二钠4.3g，搅拌升温到85℃，搅拌保温70min，加入用5g水溶解的0.78g聚乙二醇200，搅拌保温60min，过滤沉淀物，水洗上述沉淀物，将洗净的沉淀物放入70℃下恒温48h，脱水，得到纳米层状磷酸锆载体A，其圆片最长直径小于100nm，厚度小于40nm；将上述的3.4g纳米层状磷酸锆载体A，分散在用32g水溶解的60g硝酸锌溶液，升温到95℃，搅拌保温1h，过滤分离出含锌的中间载体B，滤液回收；向2.7g含锌的中间载体B中加入蒸馏水45g、硝酸银0.65g和硝酸铁0.43g，在75℃下搅拌保温1h，过滤分离出含银离子、含锌离子的纳米层状磷酸锆抗菌体C，其中抗菌体C的含水率为26％；11.2g of zirconium oxychloride aqueous solution and 6.5g of oxalic acid were added to the three-necked bottle. After stirring for 15 minutes, 4.3 g of disodium hydrogen phosphate was added, and the mixture was stirred and heated to 85 ° C, stirred and kept for 70 min, and 0.78 g of polyethylene glycol dissolved in 5 g of water was added. 200, stirring and holding for 60min, filtering the precipitate, washing the above precipitate, washing the precipitate into 70 ° C constant temperature for 48h, dehydration, to obtain nano-layered zirconium phosphate carrier A, the longest diameter of the wafer is less than 100nm, thickness The above-mentioned 3.4 g of the nano-layered zirconium phosphate carrier A is dispersed in 60 g of zinc nitrate solution dissolved in 32 g of water, heated to 95 ° C, stirred and kept for 1 h, and the zinc-containing intermediate carrier B is separated by filtration, and the filtrate is recovered; To 2.7 g of zinc-containing intermediate carrier B, 45 g of distilled water, 0.65 g of silver nitrate and 0.43 g of ferric nitrate were added, and the mixture was stirred and kept at 75 ° C for 1 h, and the nano-layered zirconium phosphate antibacterial body containing silver ions and zinc ions was separated by filtration. C, wherein the water content of the antibacterial body C is 26%;
(2)、在装有搅拌浆、温度计、冷凝管的500ml的三口烧瓶中，将聚四氢呋喃醚二醇100g与异佛尔酮二异氰酸酯109.9g混合，在三氯化钛0.58g和三乙基铝0.18g存在的条件下，于95℃下反应3.5h，得到208.1g聚氨酯预聚体A；(2) In a 500 ml three-necked flask equipped with a stirring slurry, a thermometer, and a condenser, 100 g of polytetrahydrofuran ether glycol and 109.9 g of isophorone diisocyanate were mixed with 0.58 g of titanium trichloride and triethylamine. In the presence of 0.18 g of aluminum, the reaction was carried out at 95 ° C for 3.5 h to obtain 208.1 g of polyurethane prepolymer A;
(3)、向聚氨酯预聚体A中加入二羟甲基丁酸21.1g和四氢呋喃52.2g，于85℃条件下反应4.5h，加入三乙胺13.1g进行中和反应50min，加水20g进行乳化，形成305g的聚氨酯乳液B备用；(3) Add 21.1 g of dimethylol butyric acid and 52.2 g of tetrahydrofuran to the polyurethane prepolymer A, react at 85 ° C for 4.5 h, add 13.1 g of triethylamine for neutralization for 50 min, and add 20 g of water for emulsification. Forming 305 g of polyurethane emulsion B for use;
(4)、将聚丙烯酸钠12g溶于55g水中，加入上述(1)所得的1.2g纳米层状磷酸锆抗菌体C、乙烯基三甲氧基硅烷4g和1g三甲基硅化腈，在剪切1200r/min下乳化，乳化70min，得纳米材料乳液C备用；(4) Dissolving 12 g of sodium polyacrylate in 55 g of water, adding 1.2 g of the nano-layered zirconium phosphate antibacterial C obtained in the above (1), vinyl trimethoxysilane 4 g, and 1 g of trimethylsilylated nitrile, in the shearing Emulsified at 1200r/min, emulsified for 70min, and obtained nano material emulsion C for use;
(5)、往B中加入的30.6g纳米材料乳液C，在pH为7的条件下，剪切搅拌速度为1100rpm，剪切搅拌时间60min，得抗菌性与防水性聚氨酯涂料与胶黏剂331g。(5) 30.6g nanomaterial emulsion C added to B, under the condition of pH 7, shearing stirring speed is 1100rpm, shearing stirring time is 60min, and antibacterial and waterproof polyurethane coating and adhesive 331g are obtained. .
实例三Example three
(1)、纳米层状磷酸锆载体的制备(1) Preparation of nano-layered zirconium phosphate carrier
往三口瓶中加入11.2g氯氧化锆水溶液和草酸6.5g，搅拌15min中后加入磷酸氢二钠4.3g，搅拌升温到85℃，搅拌70min，加入用5g水溶解的0.78g聚乙二醇200，搅拌保温60min，过滤沉淀物，水洗上述沉淀物后得到干净的纳米层状磷酸锆载体A，放入70℃下恒温48h，脱水，得到纳米层状磷酸锆载体A，圆片最长直径小于100nm，厚度小于40nm；将3.4g纳米层状磷酸锆载体A，分散在用32g水溶解的60g硝酸锌溶液中，升温到95℃中，搅拌保温1h，过滤分离出含锌的中间载体B，滤液回收；向2.7g含锌的中间载体B中加入蒸馏水45g、硝酸银0.65g和硝酸镁0.21g，在75℃下搅拌保温1h，过滤分离出2.1g含银离子、含锌离子的纳米层状磷酸锆抗菌体C，其中抗菌体C的含水率为26％；11.2g of zirconium oxychloride aqueous solution and 6.5g of oxalic acid were added to the three-necked bottle. After stirring for 15 minutes, 4.3 g of disodium hydrogen phosphate was added, and the mixture was stirred and heated to 85 ° C, stirred for 70 min, and 0.78 g of polyethylene glycol 200 dissolved in 5 g of water was added. After stirring for 60 min, the precipitate was filtered, and the precipitate was washed with water to obtain a clean nano-layered zirconium phosphate carrier A, which was placed at 70 ° C for 48 h, and dehydrated to obtain a nano-layered zirconium phosphate carrier A. The longest diameter of the wafer was smaller than 100 nm, thickness less than 40 nm; 3.4 g of nano-layered zirconium phosphate carrier A, dispersed in 60 g of zinc nitrate solution dissolved in 32 g of water, heated to 95 ° C, stirred for 1 h, filtered to separate the zinc-containing intermediate carrier B, The filtrate was recovered. To 2.7 g of the zinc-containing intermediate carrier B, 45 g of distilled water, 0.65 g of silver nitrate and 0.21 g of magnesium nitrate were added, and the mixture was stirred and kept at 75 ° C for 1 h, and 2.1 g of a silver layer containing silver ions and containing zinc ions was separated by filtration. Zirconium phosphate antibacterial C, wherein the water content of the antibacterial C is 26%;
(2)、在装有搅拌浆、温度计、冷凝管的500ml的四口烧瓶中，将聚四氢呋喃醚二醇100g与异佛尔酮二异氰酸酯69.6g混合，在三氯化钛0.48g和三乙基铝0.2g存在的条件下，于78℃下反应2.5h，得到165.2g聚氨酯预聚体A；(2) In a 500 ml four-necked flask equipped with a stirring slurry, a thermometer, and a condenser, 100 g of polytetrahydrofuran ether glycol and 69.6 g of isophorone diisocyanate were mixed, and 0.48 g of titanium trichloride and triethyl bromide. In the presence of 0.2 g of base aluminum, reacted at 78 ° C for 2.5 h to obtain 165.2 g of polyurethane prepolymer A;
(3)、向聚氨酯预聚体A中加入二羟甲基丁酸10.5g和二甲基亚砜29.3g，于75℃条件下反应1.5h，加入三乙胺9.78g进行中和反应60min，加水20g进行乳化，形成231g聚氨酯B备用；(3) Adding 10.5 g of dimethylolbutanoic acid and 29.3 g of dimethyl sulfoxide to the polyurethane prepolymer A, reacting at 75 ° C for 1.5 h, adding 9.78 g of triethylamine for neutralization for 60 min. 20 g of water was added for emulsification to form 231 g of polyurethane B for use;
(4)、将聚乙烯醇10g溶于46g水中，加入上述(1)所得的2.4g纳米层状磷酸锆抗菌体C、γ-甲基丙烯酰氧基丙基三甲氧基硅烷3g、酒石酸1.9g、对羧基苯磺酰胺0.56g和1g三甲基硅化腈，在700r/min下剪切乳化，乳化30min，得纳米材料乳液C备用；(4) Dissolving 10 g of polyvinyl alcohol in 46 g of water, and adding 2.4 g of the nano-layered zirconium phosphate antibacterial C obtained in the above (1), γ-methacryloxypropyltrimethoxysilane 3 g, and tartaric acid 1.9. g, p-carboxybenzenesulfonamide 0.56g and 1g trimethylsilylated nitrile, shear emulsified at 700r/min, emulsified for 30min, to obtain nano material emulsion C spare;
(5)、往聚氨酯B中加入17.6g纳米材料乳液C，在pH为8的条件下，剪切搅拌速度900rpm，搅拌时间35min，得到抗菌性与防水性聚氨酯涂料与胶黏剂241g。(5) 17.6 g of nano material emulsion C was added to the polyurethane B, and under a condition of pH 8, a shear stirring speed of 900 rpm and a stirring time of 35 minutes were obtained to obtain an antibacterial and water-repellent polyurethane coating and an adhesive 241 g.
实例四 Example four
(1)、纳米层状磷酸锆载体的制备(1) Preparation of nano-layered zirconium phosphate carrier
往三口瓶中加入11.2g氯氧化锆水溶液和草酸6.5g，搅拌15min中后加入磷酸氢二钠4.3g，搅拌升温到85℃，搅拌70min，加入用5g水溶解的0.78g聚乙二醇200，搅拌保温60min，过滤沉淀物，水洗上述沉淀物后得到干净的纳米层状磷酸锆载体A，放入70℃下恒温48h，脱水，得到纳米层状磷酸锆载体A，圆片最长直径小于100nm，厚度小于40nm；将3.4g纳米层状磷酸锆载体A，分散在用32g水溶解的60g硝酸锌溶液中，升温到95℃中，搅拌保温1h，过滤分离出含锌的中间载体B，滤液回收；向2.7g含锌的中间载体B中加入蒸馏水45g、硝酸银0.65g和硝酸铅0.12g，在75℃下搅拌保温1h，过滤分离出2.1g含银离子、含锌离子的纳米层状磷酸锆抗菌体C，其中抗菌体C的含水率为26％；11.2g of zirconium oxychloride aqueous solution and 6.5g of oxalic acid were added to the three-necked bottle. After stirring for 15 minutes, 4.3 g of disodium hydrogen phosphate was added, and the mixture was stirred and heated to 85 ° C, stirred for 70 min, and 0.78 g of polyethylene glycol 200 dissolved in 5 g of water was added. After stirring for 60 min, the precipitate was filtered, and the precipitate was washed with water to obtain a clean nano-layered zirconium phosphate carrier A, which was placed at 70 ° C for 48 h, and dehydrated to obtain a nano-layered zirconium phosphate carrier A. The longest diameter of the wafer was smaller than 100 nm, thickness less than 40 nm; 3.4 g of nano-layered zirconium phosphate carrier A, dispersed in 60 g of zinc nitrate solution dissolved in 32 g of water, heated to 95 ° C, stirred for 1 h, filtered to separate the zinc-containing intermediate carrier B, The filtrate was recovered. To 2.7 g of zinc-containing intermediate carrier B, 45 g of distilled water, 0.65 g of silver nitrate and 0.12 g of lead nitrate were added, and the mixture was stirred and kept at 75 ° C for 1 h, and 2.1 g of a silver layer containing silver ions and containing zinc ions was separated by filtration. Zirconium phosphate antibacterial C, wherein the water content of the antibacterial C is 26%;
(2)、在装有搅拌浆、温度计、冷凝管的500m的四口烧瓶中，将聚四氢呋喃醚二醇100g与异佛尔酮二异氰酸酯33.3g混合，在三氯化钛0.38g和三乙基铝0.28g存在的条件下，于75℃下反应3.5h，得到132g聚氨酯预聚体A；(2) In a 500-m four-necked flask equipped with a stirring slurry, a thermometer, and a condenser, 100 g of polytetrahydrofuran ether glycol and 33.3 g of isophorone diisocyanate were mixed, and 0.38 g of titanium trichloride and triethyl bromide. The reaction of the base aluminum in the presence of 0.28g at 75 ° C for 3.5h, to obtain 132g polyurethane prepolymer A;
(3)、向聚氨酯预聚体A中加入二羟甲基丙酸4.75g和丙酮溶剂16g，于85℃条件下反应1.5h，加入三乙胺5.97g进行中和反应30min，加水20g进行乳化，形成177g的聚氨酯B备用；(3) Adding 4.75 g of dimethylolpropionic acid and 16 g of acetone solvent to the polyurethane prepolymer A, reacting at 85 ° C for 1.5 h, adding 5.97 g of triethylamine for neutralization for 30 min, and adding 20 g of water for emulsification. Forming 177g of polyurethane B for use;
(4)、将多聚磷酸钠10g溶于水50g中，加入上述(1)的0.9g纳米层状磷酸锆抗菌体C、γ-氨丙基三乙氧基硅烷3g和1.3g三甲基硅化腈，在300r/min下剪切乳化，乳化20min，得纳米材料乳液C备用；(4) Dissolving 10 g of sodium polyphosphate in 50 g of water, adding 0.9 g of the nano layered zirconium phosphate antibacterial agent C of the above (1), 3 g of γ-aminopropyltriethoxysilane, and 1.3 g of trimethyl group. Silicified nitrile, shear emulsified at 300r/min, emulsified for 20min, to obtain nano material emulsion C for use;
(5)、往聚氨酯B中加入9g纳米材料乳液C和氢化胡桃醌0.16g，在pH为7的条件下，剪切搅拌速度600rpm，搅拌时间50min，得到抗菌性与防水性聚氨酯涂料与胶黏剂186g。(5) Add 9g nanomaterial emulsion C and hydrogenated walnut to 0.16g to polyurethane B. Under the condition of pH 7, the shearing speed is 600rpm and the stirring time is 50min to obtain antibacterial and waterproof polyurethane coating and adhesive. Agent 186g.
实例五Example five
(1)、纳米层状磷酸锆载体的制备(1) Preparation of nano-layered zirconium phosphate carrier
往三口瓶中加入11.2g氯氧化锆水溶液和草酸6.5g，搅拌15min中后加入磷酸氢二钠4.3g，搅拌升温到85℃，搅拌70min，加入用5g水溶解的0.78g聚乙二醇200，搅拌保温60min，过滤沉淀物，水洗上述沉淀物后得到干净的纳米层状磷酸锆载体A，放入70℃下恒温48h，脱水，得到纳米层状磷酸锆载体A，圆片最长直径小于100nm，厚度小于40nm；将3.4g纳米层状磷酸锆载体A，分散在用32g水溶解的60g硝酸锌溶液中，升温到95℃中，搅拌保温1h，过滤分离出含锌的中间载体B，滤液回收；向2.7g含锌的中间载体B中加入蒸馏水45g、硝酸银0.65g、硝酸铜0.12g和三氯化锑0.12g，在75℃下搅拌保温1h，过滤分离出2.1g含银离子、含锌离子的纳米层状磷酸锆抗菌体C，其中抗菌体C的含水率为26％；11.2g of zirconium oxychloride aqueous solution and 6.5g of oxalic acid were added to the three-necked bottle. After stirring for 15 minutes, 4.3 g of disodium hydrogen phosphate was added, and the mixture was stirred and heated to 85 ° C, stirred for 70 min, and 0.78 g of polyethylene glycol 200 dissolved in 5 g of water was added. After stirring for 60 min, the precipitate was filtered, and the precipitate was washed with water to obtain a clean nano-layered zirconium phosphate carrier A, which was placed at 70 ° C for 48 h, and dehydrated to obtain a nano-layered zirconium phosphate carrier A. The longest diameter of the wafer was smaller than 100 nm, thickness less than 40 nm; 3.4 g of nano-layered zirconium phosphate carrier A, dispersed in 60 g of zinc nitrate solution dissolved in 32 g of water, heated to 95 ° C, stirred for 1 h, filtered to separate the zinc-containing intermediate carrier B, The filtrate was recovered. To 2.7 g of zinc-containing intermediate carrier B, 45 g of distilled water, 0.65 g of silver nitrate, 0.12 g of copper nitrate and 0.12 g of antimony trichloride were added, and the mixture was stirred at 75 ° C for 1 h, and 2.1 g of silver ions were separated by filtration. a nano-layered zirconium phosphate antibacterial C containing zinc ions, wherein the water content of the antibacterial C is 26%;
(2)、在装有搅拌浆、温度计、冷凝管的500ml的四口烧瓶中，将聚四氢呋喃醚二醇100g与异佛尔酮二异氰酸酯99.9g混合，在三氯化钛0.42g和三乙基铝0.08g存在的条件下，于95℃下反应1.5h，得到200.1g聚氨酯预聚体A；(2) In a 500 ml four-necked flask equipped with a stirring slurry, a thermometer, and a condenser, 100 g of polytetrahydrofuran ether glycol and 99.9 g of isophorone diisocyanate were mixed, and 0.42 g of titanium trichloride and tribromide. The reaction of the base aluminum in the presence of 0.08g, at 95 ° C for 1.5h, to obtain 200.1g polyurethane prepolymer A;
(3)、向聚氨酯预聚体A中加入二羟甲基丁酸21.1g和丙酮溶剂50.2g，于85℃条件下反应1.5h，加入三乙胺12.1g进行中和反应50min，加水25g进行乳化，形成304g的聚氨酯乳液B备用；(3) Adding 21.1 g of dimethylol butyric acid and 50.2 g of acetone solvent to the polyurethane prepolymer A, reacting at 85 ° C for 1.5 h, adding 12.1 g of triethylamine for neutralization for 50 min, and adding 25 g of water. Emulsified to form 304g of polyurethane emulsion B for use;
(4)、将十二烷基苯磺酸钠10g溶于50g水中，加入2.1g纳米层状磷酸锆抗菌体C、γ-缩水甘油醚氧丙基三甲氧基硅烷5g和1g三甲基硅化腈，在1100r/min下剪切乳化，乳化40min，得纳米材料乳液备用；(4) Dissolving 10 g of sodium dodecylbenzenesulfonate in 50 g of water, adding 2.1 g of nano-layered zirconium phosphate antibacterial C, γ-glycidoxypropyltrimethoxysilane 5 g and 1 g of trimethylsilation Nitrile, shear emulsified at 1100r/min, emulsified for 40min, to obtain nanomaterial emulsion for use;
(5)、往聚氨酯乳液B中加入30.4g上述纳米材料乳液C和脱乙酰甲壳素0.13g，在pH为7的条件下，剪切搅拌速度为1200rpm，剪切搅拌时间40min，得到抗菌性与防水性聚氨酯涂料与胶黏剂329g。(5) Add 30.4 g of the above nanomaterial emulsion C and 0.13 g of chitosan to the polyurethane emulsion B. Under the condition of pH 7, the shear stirring speed is 1200 rpm, the shear stirring time is 40 min, and the antibacterial property is obtained. Waterproof polyurethane coating and adhesive 329g.
下面通过相关实验数据进一步说明本发明的有益效果： The beneficial effects of the present invention are further illustrated by relevant experimental data below:
防水性采用取适量乳液均匀涂覆于玻璃板上，一定温度下干燥成膜后将玻璃板放入去离子水中浸泡，观察涂膜变蓝、发白、起泡、发皱、脱落的情况。The water repellency is uniformly applied to the glass plate by taking an appropriate amount of the emulsion, and after drying at a certain temperature, the glass plate is placed in deionized water to be immersed, and the coating film is observed to be blue, whitish, blistering, wrinkled, and peeled off.
表一抗菌性与防水性聚氨酯涂料与胶黏剂所成膜性能Table 1 Film-forming properties of antibacterial and waterproof polyurethane coatings and adhesives
实验组test group 实例一Example one 实例二Example two 实例三Example three 实例四Example four 实例五Example five
膜外观(耐水性48h)Film appearance (water resistance 48h) 透明Transparent 透明Transparent 透明Transparent 透明Transparent 透明Transparent
硬度hardness BB BB BB BB BB
附着力/级Adhesion / level 33 22 33 33 33
柔韧性/mmFlexibility / mm 22 22 22 22 33
从表一可以发现，从膜外观、硬度、附着力、柔韧性方面性能较好。It can be found from Table 1 that the performance is good in terms of film appearance, hardness, adhesion, and flexibility.
表二抗菌性与防水性聚氨酯涂料与胶黏剂所得膜的力学性能Table 2 Mechanical properties of the film obtained from antibacterial and waterproof polyurethane coatings and adhesives
实验组test group 实例一Example one 实例二Example two 实例三Example three 实例四Example four 实例五Example five
断裂伸长率/％Elongation at break /% 145145 158158 129129 168168 179179
抗张强度/MPaTensile strength / MPa 6.86.8 6.76.7 6.86.8 5.85.8 6.86.8
抗磨耗/级Anti-wear/grade 3.53.5 44 44 44 44
表二中指标的检测方法参考(蒋维祺.皮革成品理化检验[M].中国轻工业出版社，1999)，本发明涂料所得膜断裂伸长率、抗张强度、抗磨均表现较好。The reference method for the detection of the indicators in Table 2 (Jiang Weizhen. Physical and chemical testing of leather products [M]. China Light Industry Press, 1999), the film obtained by the coating of the invention has good elongation at break, tensile strength and antiwear.
表三抗菌性涂料对供试菌种的抗菌率(当天)(％)Table 3 Antibacterial rate of antibacterial coatings on the tested strains (the same day) (%)
Figure PCTCN2015000419-appb-000001
Figure PCTCN2015000419-appb-000001
从表三可以发现，实例一到五所制备的抗菌性涂料对大肠杆菌、金黄色葡萄球菌、黄曲霉均有很好的抗菌效果。It can be found from Table 3 that the antibacterial coatings prepared in Examples 1 to 5 have good antibacterial effects against Escherichia coli, Staphylococcus aureus and Aspergillus flavus.
表四抗菌性涂料抗菌90天的抗菌效果(％)Table 4 antibacterial effect of antibacterial coating antibacterial for 90 days (%)
Figure PCTCN2015000419-appb-000002
Figure PCTCN2015000419-appb-000002
表五抗菌性涂料抗菌360天的抗菌效果(％) Table 5 antibacterial effect of antibacterial coating antibacterial 360 days (%)
  市场涂料SB100Market coating SB100 实例一Example one 实例二Example two 实例三Example three 实例四Example four 实例五Example five
大肠杆菌E.coli 66 5858 6161 5454 5656 6666
金黄色葡萄球菌Staphylococcus aureus 66 5151 5252 5757 5656 5959
黄曲霉Aspergillus 55 5656 5858 5454 5353 6262
从表四和表五可以发现，实例一到五所制备的抗菌性涂料抗菌效果缓慢释放，放置90天到360天对大肠杆菌、金黄色葡萄球菌、黄曲霉仍能显示良好的抗菌效果。 It can be found from Tables 4 and 5 that the antibacterial effects of the antibacterial coatings prepared in Examples 1 to 5 are slowly released, and the antibacterial effect can still be exhibited against Escherichia coli, Staphylococcus aureus and Aspergillus flavus by leaving for 90 days to 360 days.

Claims (5)

  1. 抗菌性与防水性聚氨酯涂料与胶黏剂的制备方法，其特征在于：A method for preparing an antibacterial and water repellent polyurethane coating and an adhesive, characterized in that:
    (1)、纳米层状磷酸锆载体的制备(1) Preparation of nano-layered zirconium phosphate carrier
    往三口瓶中加入11.2g氯氧化锆水溶液和草酸6.5g，搅拌15min中后加入磷酸氢二钠4.3g，搅拌升温到85℃，搅拌保温70min，加入用5g水溶解的0.78g聚乙二醇200，85℃搅拌60min，过滤沉淀物，水洗上述沉淀物，将洗净的沉淀物放入70℃下恒温48h，脱水，得到纳米层状磷酸锆载体A，其圆片最长直径小于100nm，厚度小于40nm；将上述的3.4g纳米层状磷酸锆载体A，分散在用32g水溶解的60g硝酸锌溶液，升温到95℃，搅拌保温1h，过滤分离出含锌的中间载体B，滤液回收；向2.7g含锌的中间载体B中加入蒸馏水45g、硝酸银0.65g和硝酸铬0.7g，在75℃下搅拌1h，过滤分离出含银离子、含锌离子的纳米层状磷酸锆抗菌体C，其中抗菌体C的含水率为26％；11.2g of zirconium oxychloride aqueous solution and 6.5g of oxalic acid were added to the three-necked bottle. After stirring for 15 minutes, 4.3 g of disodium hydrogen phosphate was added, and the mixture was stirred and heated to 85 ° C, stirred and kept for 70 min, and 0.78 g of polyethylene glycol dissolved in 5 g of water was added. After stirring at 200 °C for 85 min, the precipitate was filtered, and the precipitate was washed with water, and the precipitate was placed at 70 ° C for 48 h, and dehydrated to obtain a nano-layered zirconium phosphate carrier A having a longest diameter of less than 100 nm. The thickness is less than 40 nm; the above 3.4 g of the nano-layered zirconium phosphate carrier A is dispersed in 60 g of a zinc nitrate solution dissolved in 32 g of water, heated to 95 ° C, stirred and kept for 1 h, and the zinc-containing intermediate carrier B is separated by filtration, and the filtrate is recovered. To 2.7 g of zinc-containing intermediate carrier B, 45 g of distilled water, 0.65 g of silver nitrate and 0.7 g of chromium nitrate were added, and stirred at 75 ° C for 1 h, and a nano-layered zirconium phosphate antibacterial containing silver ions and zinc ions was separated by filtration. C, wherein the water content of the antibacterial body C is 26%;
    (2)、在装有搅拌浆、温度计、冷凝管的500ml的三口烧瓶中，将聚四氢呋喃醚二醇102g与异佛尔酮二异氰酸酯33.6g混合，在三氯化钛0.18g和三乙基铝0.08g存在的条件下，于85℃下反应2.5h，得到135.5g聚氨酯预聚体A；(2) In a 500 ml three-necked flask equipped with a stirring slurry, a thermometer, and a condenser, 102 g of polytetrahydrofuran ether glycol and 33.6 g of isophorone diisocyanate were mixed, and 0.18 g of trichloride and triethylamine. Aluminum in the presence of 0.08g, reacted at 85 ° C for 2.5h, to obtain 135.5g polyurethane prepolymer A;
    (3)、向聚氨酯预聚体A中加入二羟甲基丙酸4.76g和乙酸异丙酯15g，于75℃条件下反应1.5h，加入三乙胺5.99g进行中和反应30min，加水20g进行乳化，形成179g的聚氨酯B备用；(3) Add 4.76 g of dimethylolpropionic acid and 15 g of isopropyl acetate to the polyurethane prepolymer A, react at 75 ° C for 1.5 h, add 5.99 g of triethylamine for neutralization for 30 min, add water 20 g. Emulsified to form 179 g of polyurethane B for use;
    (4)、将十二烷基苯磺酸钠12g溶于60g水中，加入上述(1)所得的1.1g纳米层状磷酸锆抗菌体C、乙烯基三乙氧基硅烷2g、三乙醇胺1g和1g三甲基硅化腈，在剪切速度700r/min下乳化，乳化时间30min，得纳米材料乳液C备用；(4) Dissolving 12 g of sodium dodecylbenzenesulfonate in 60 g of water, and adding 1.1 g of the nano-layered zirconium phosphate antibacterial C obtained in the above (1), 2 g of vinyltriethoxysilane, 1 g of triethanolamine, and 1g of trimethylsilicated nitrile, emulsified at a shear rate of 700r/min, and an emulsification time of 30min, to obtain a nanomaterial emulsion C for use;
    (5)、往聚氨酯B中加入9g纳米材料乳液C，在pH为7的条件下，剪切搅拌速度800rpm，搅拌时间30min，得到抗菌性与防水性聚氨酯涂料与胶黏剂187g。(5) To the polyurethane B, 9 g of the nano material emulsion C was added, and under the condition of pH 7, the shear stirring speed was 800 rpm, and the stirring time was 30 min, and 187 g of an antibacterial and water-repellent polyurethane coating and an adhesive were obtained.
  2. 抗菌性与防水性聚氨酯涂料与胶黏剂的制备方法，其特征在于：A method for preparing an antibacterial and water repellent polyurethane coating and an adhesive, characterized in that:
    (1)、纳米层状磷酸锆载体的制备(1) Preparation of nano-layered zirconium phosphate carrier
    往三口瓶中加入11.2g氯氧化锆水溶液和草酸6.5g，搅拌15min中后加入磷酸氢二钠4.3g，搅拌升温到85℃，搅拌保温70min，加入用5g水溶解的0.78g聚乙二醇200，搅拌保温60min，过滤沉淀物，水洗上述沉淀物，将洗净的沉淀物放入70℃下恒温48h，脱水，得到纳米层状磷酸锆载体A，其圆片最长直径小于100nm，厚度小于40nm；将上述的3.4g纳米层状磷酸锆载体A，分散在用32g水溶解的60g硝酸锌溶液，升温到95℃，搅拌保温1h，过滤分离出含锌的中间载体B，滤液回收；向2.7g含锌的中间载体B中加入蒸馏水45g、硝酸银0.65g和硝酸铁0.43g，在75℃1搅拌保温1h，过滤分离出含银离子、含锌离子的纳米层状磷酸锆抗菌体C，其中抗菌体C的含水率为26％；11.2g of zirconium oxychloride aqueous solution and 6.5g of oxalic acid were added to the three-necked bottle. After stirring for 15 minutes, 4.3 g of disodium hydrogen phosphate was added, and the mixture was stirred and heated to 85 ° C, stirred and kept for 70 min, and 0.78 g of polyethylene glycol dissolved in 5 g of water was added. 200, stirring and holding for 60min, filtering the precipitate, washing the above precipitate, washing the precipitate into 70 ° C constant temperature for 48h, dehydration, to obtain nano-layered zirconium phosphate carrier A, the longest diameter of the wafer is less than 100nm, thickness The above-mentioned 3.4 g of the nano-layered zirconium phosphate carrier A is dispersed in 60 g of zinc nitrate solution dissolved in 32 g of water, heated to 95 ° C, stirred and kept for 1 h, and the zinc-containing intermediate carrier B is separated by filtration, and the filtrate is recovered; To 2.7 g of zinc-containing intermediate carrier B, 45 g of distilled water, 0.65 g of silver nitrate and 0.43 g of ferric nitrate were added, and the mixture was stirred and kept at 75 ° C for 1 h, and the nano-layered zirconium phosphate antibacterial body containing silver ions and zinc ions was separated by filtration. C, wherein the water content of the antibacterial body C is 26%;
    (2)、在装有搅拌浆、温度计、冷凝管的500ml的三口烧瓶中，将聚四氢呋喃醚二醇100g与异佛尔酮二异氰酸酯109.9g混合，在三氯化钛0.58g和三乙基铝0.18g存在的条件下，于95℃下反应3.5h，得到208.1g聚氨酯预聚体A； (2) In a 500 ml three-necked flask equipped with a stirring slurry, a thermometer, and a condenser, 100 g of polytetrahydrofuran ether glycol and 109.9 g of isophorone diisocyanate were mixed with 0.58 g of titanium trichloride and triethylamine. In the presence of 0.18 g of aluminum, the reaction was carried out at 95 ° C for 3.5 h to obtain 208.1 g of polyurethane prepolymer A;
    (3)、向聚氨酯预聚体A中加入二羟甲基丁酸21.1g和四氢呋喃52.2g，于85℃条件下反应4.5h，加入三乙胺13.1g进行中和反应50min，加水20g进行乳化，形成305g的聚氨酯乳液B备用；(3) Add 21.1 g of dimethylol butyric acid and 52.2 g of tetrahydrofuran to the polyurethane prepolymer A, react at 85 ° C for 4.5 h, add 13.1 g of triethylamine for neutralization for 50 min, and add 20 g of water for emulsification. Forming 305 g of polyurethane emulsion B for use;
    (4)、将聚丙烯酸钠12g溶于55g水中，加入上述(1)所得的1.2g纳米层状磷酸锆抗菌体C、乙烯基三甲氧基硅烷4g和1g三甲基硅化腈，在剪切1200r/min下乳化，乳化70min，得纳米材料乳液C备用；(4) Dissolving 12 g of sodium polyacrylate in 55 g of water, adding 1.2 g of the nano-layered zirconium phosphate antibacterial C obtained in the above (1), vinyl trimethoxysilane 4 g, and 1 g of trimethylsilylated nitrile, in the shearing Emulsified at 1200r/min, emulsified for 70min, and obtained nano material emulsion C for use;
    (5)、往B中加入的30.6g纳米材料乳液C，在pH为7的条件下，剪切搅拌速度为1100rpm，剪切搅拌时间60min，得抗菌性与防水性聚氨酯涂料与胶黏剂331g。(5) 30.6g nanomaterial emulsion C added to B, under the condition of pH 7, shearing stirring speed is 1100rpm, shearing stirring time is 60min, and antibacterial and waterproof polyurethane coating and adhesive 331g are obtained. .
  3. 抗菌性与防水性聚氨酯涂料与胶黏剂的制备方法，其特征在于：A method for preparing an antibacterial and water repellent polyurethane coating and an adhesive, characterized in that:
    (1)、纳米层状磷酸锆载体的制备(1) Preparation of nano-layered zirconium phosphate carrier
    往三口瓶中加入11.2g氯氧化锆水溶液和草酸6.5g，搅拌15min中后加入磷酸氢二钠4.3g，搅拌升温到85℃，搅拌70min，加入用5g水溶解的0.78g聚乙二醇200，搅拌保温60min，过滤沉淀物，水洗上述沉淀物后得到干净的纳米层状磷酸锆载体A，放入70℃下恒温48h，脱水，得到纳米层状磷酸锆载体A，圆片最长直径小于100nm，厚度小于40nm；将3.4g纳米层状磷酸锆载体A，分散在用32g水溶解的60g硝酸锌溶液中，升温到95℃中，搅拌保温1h，过滤分离出含锌的中间载体B，滤液回收；向2.7g含锌的中间载体B中加入蒸馏水45g、硝酸银0.65g和硝酸镁0.21g，在75℃下搅拌保温1h，过滤分离出2.1g含银离子、含锌离子的纳米层状磷酸锆抗菌体C，其中抗菌体C的含水率为26％；11.2g of zirconium oxychloride aqueous solution and 6.5g of oxalic acid were added to the three-necked bottle. After stirring for 15 minutes, 4.3 g of disodium hydrogen phosphate was added, and the mixture was stirred and heated to 85 ° C, stirred for 70 min, and 0.78 g of polyethylene glycol 200 dissolved in 5 g of water was added. After stirring for 60 min, the precipitate was filtered, and the precipitate was washed with water to obtain a clean nano-layered zirconium phosphate carrier A, which was placed at 70 ° C for 48 h, and dehydrated to obtain a nano-layered zirconium phosphate carrier A. The longest diameter of the wafer was smaller than 100 nm, thickness less than 40 nm; 3.4 g of nano-layered zirconium phosphate carrier A, dispersed in 60 g of zinc nitrate solution dissolved in 32 g of water, heated to 95 ° C, stirred for 1 h, filtered to separate the zinc-containing intermediate carrier B, The filtrate was recovered. To 2.7 g of the zinc-containing intermediate carrier B, 45 g of distilled water, 0.65 g of silver nitrate and 0.21 g of magnesium nitrate were added, and the mixture was stirred and kept at 75 ° C for 1 h, and 2.1 g of a silver layer containing silver ions and containing zinc ions was separated by filtration. Zirconium phosphate antibacterial C, wherein the water content of the antibacterial C is 26%;
    (2)、在装有搅拌浆、温度计、冷凝管的500ml的四口烧瓶中，将聚四氢呋喃醚二醇100g与异佛尔酮二异氰酸酯69.6g混合，在三氯化钛0.48g和三乙基铝0.2g存在的条件下，于78℃下反应2.5h，得到165.2g聚氨酯预聚体A；(2) In a 500 ml four-necked flask equipped with a stirring slurry, a thermometer, and a condenser, 100 g of polytetrahydrofuran ether glycol and 69.6 g of isophorone diisocyanate were mixed, and 0.48 g of titanium trichloride and triethyl bromide. In the presence of 0.2 g of base aluminum, reacted at 78 ° C for 2.5 h to obtain 165.2 g of polyurethane prepolymer A;
    (3)、向聚氨酯预聚体A中加入二羟甲基丁酸10.5g和二甲基亚砜29.3g，于75℃条件下反应1.5h，加入三乙胺9.78g进行中和反应60min，加水20g进行乳化，形成231g聚氨酯B备用；(3) Adding 10.5 g of dimethylolbutanoic acid and 29.3 g of dimethyl sulfoxide to the polyurethane prepolymer A, reacting at 75 ° C for 1.5 h, adding 9.78 g of triethylamine for neutralization for 60 min. 20 g of water was added for emulsification to form 231 g of polyurethane B for use;
    (4)、将聚乙烯醇10g溶于46g水中，加入上述(1)所得的2.4g纳米层状磷酸锆抗菌体C、γ-甲基丙烯酰氧基丙基三甲氧基硅烷3g、酒石酸1.9g、对羧基苯磺酰胺0.56g和1g三甲基硅化腈，在700r/min下剪切乳化，乳化30min，得纳米材料乳液C备用；(4) Dissolving 10 g of polyvinyl alcohol in 46 g of water, and adding 2.4 g of the nano-layered zirconium phosphate antibacterial C obtained in the above (1), γ-methacryloxypropyltrimethoxysilane 3 g, and tartaric acid 1.9. g, p-carboxybenzenesulfonamide 0.56g and 1g trimethylsilylated nitrile, shear emulsified at 700r/min, emulsified for 30min, to obtain nano material emulsion C spare;
    (5)、往聚氨酯B中加入17.6g纳米材料乳液C，在pH为8的条件下，剪切搅拌速度900rpm，搅拌时间35min，得到抗菌性与防水性聚氨酯涂料与胶黏剂241g。(5) 17.6 g of nano material emulsion C was added to the polyurethane B, and under a condition of pH 8, a shear stirring speed of 900 rpm and a stirring time of 35 minutes were obtained to obtain an antibacterial and water-repellent polyurethane coating and an adhesive 241 g.
  4. 抗菌性与防水性聚氨酯涂料与胶黏剂的制备方法，其特征在于：A method for preparing an antibacterial and water repellent polyurethane coating and an adhesive, characterized in that:
    (1)、纳米层状磷酸锆载体的制备(1) Preparation of nano-layered zirconium phosphate carrier
    往三口瓶中加入11.2g氯氧化锆水溶液和草酸6.5g，搅拌15min中后加入磷酸氢二钠4.3g，搅拌升温到85℃，搅拌70min，加入用5g水溶解的0.78g聚乙二醇200，搅拌保温60min，过滤沉淀物，水洗上述沉淀物后得到干净的纳米层状磷酸锆载体A，放入70℃下恒温48h， 脱水，得到纳米层状磷酸锆载体A，圆片最长直径小于100nm，厚度小于40nm；将3.4g纳米层状磷酸锆载体A，分散在用32g水溶解的60g硝酸锌溶液中，升温到95℃中，搅拌保温1h，过滤分离出含锌的中间载体B，滤液回收；向2.7g含锌的中间载体B中加入蒸馏水45g、硝酸银0.65g和硝酸铅0.12g，在75℃下搅拌保温1h，过滤分离出2.1g含银离子、含锌离子的纳米层状磷酸锆抗菌体C，其中抗菌体C的含水率为26％；11.2g of zirconium oxychloride aqueous solution and 6.5g of oxalic acid were added to the three-necked bottle. After stirring for 15 minutes, 4.3 g of disodium hydrogen phosphate was added, and the mixture was stirred and heated to 85 ° C, stirred for 70 min, and 0.78 g of polyethylene glycol 200 dissolved in 5 g of water was added. The mixture was stirred and kept for 60 minutes, and the precipitate was filtered. After washing the above precipitate, a clean nano-layered zirconium phosphate carrier A was obtained, and the temperature was kept at 70 ° C for 48 hours. Dehydration, to obtain a nano-layered zirconium phosphate carrier A, the wafer has a longest diameter of less than 100 nm and a thickness of less than 40 nm; 3.4 g of the nano-layered zirconium phosphate carrier A is dispersed in a solution of 60 g of zinc nitrate dissolved in 32 g of water, and the temperature is raised to 95. In °C, stir and heat for 1h, the intermediate carrier B containing zinc was separated by filtration, and the filtrate was recovered. To 2.7g of zinc-containing intermediate carrier B, 45g of distilled water, 0.65g of silver nitrate and 0.12g of lead nitrate were added, and the mixture was stirred at 75 °C. 1h, filtered to separate 2.1g of silver-containing, zinc ion-containing nano-layered zirconium phosphate antibacterial C, wherein the water content of the antibacterial C is 26%;
    (2)、在装有搅拌浆、温度计、冷凝管的500m的四口烧瓶中，将聚四氢呋喃醚二醇100g与异佛尔酮二异氰酸酯33.3g混合，在三氯化钛0.38g和三乙基铝0.28g存在的条件下，于75℃下反应3.5h，得到132g聚氨酯预聚体A；(2) In a 500-m four-necked flask equipped with a stirring slurry, a thermometer, and a condenser, 100 g of polytetrahydrofuran ether glycol and 33.3 g of isophorone diisocyanate were mixed, and 0.38 g of titanium trichloride and triethyl bromide. The reaction of the base aluminum in the presence of 0.28g at 75 ° C for 3.5h, to obtain 132g polyurethane prepolymer A;
    (3)、向聚氨酯预聚体A中加入二羟甲基丙酸4.75g和丙酮溶剂16g，于85℃条件下反应1.5h，加入三乙胺5.97g进行中和反应30min，加水20g进行乳化，形成177g的聚氨酯B备用；(3) Adding 4.75 g of dimethylolpropionic acid and 16 g of acetone solvent to the polyurethane prepolymer A, reacting at 85 ° C for 1.5 h, adding 5.97 g of triethylamine for neutralization for 30 min, and adding 20 g of water for emulsification. Forming 177g of polyurethane B for use;
    (4)、将多聚磷酸钠10g溶于水50g中，加入上述(1)的0.9g纳米层状磷酸锆抗菌体C、γ-氨丙基三乙氧基硅烷3g和1.3g三甲基硅化腈，在300r/min下剪切乳化，乳化20min，得纳米材料乳液C备用；(4) Dissolving 10 g of sodium polyphosphate in 50 g of water, adding 0.9 g of the nano layered zirconium phosphate antibacterial agent C of the above (1), 3 g of γ-aminopropyltriethoxysilane, and 1.3 g of trimethyl group. Silicified nitrile, shear emulsified at 300r/min, emulsified for 20min, to obtain nano material emulsion C for use;
    (5)、往聚氨酯B中加入9g纳米材料乳液C，在pH为7的条件下，剪切搅拌速度600rpm，搅拌时间50min，得到抗菌性与防水性聚氨酯涂料与胶黏剂186g。(5) To the polyurethane B, 9 g of the nano material emulsion C was added, and under the condition of pH 7, the shear stirring speed was 600 rpm, and the stirring time was 50 min, and 186 g of an antibacterial and water-repellent polyurethane coating and an adhesive were obtained.
  5. 抗菌性与防水性聚氨酯涂料与胶黏剂的制备方法，其特征在于：A method for preparing an antibacterial and water repellent polyurethane coating and an adhesive, characterized in that:
    (1)、纳米层状磷酸锆载体的制备(1) Preparation of nano-layered zirconium phosphate carrier
    往三口瓶中加入11.2g氯氧化锆水溶液和草酸6.5g，搅拌15min中后加入磷酸氢二钠4.3g，搅拌升温到85℃，搅拌70min，加入用5g水溶解的0.78g聚乙二醇200，搅拌保温60min，过滤沉淀物，水洗上述沉淀物后得到干净的纳米层状磷酸锆载体A，放入70℃下恒温48h，脱水，得到纳米层状磷酸锆载体A，圆片最长直径小于100nm，厚度小于40nm；将3.4g纳米层状磷酸锆载体A，分散在用32g水溶解的60g硝酸锌溶液中，升温到95℃中，搅拌保温1h，过滤分离出含锌的中间载体B，滤液回收；向2.7g含锌的中间载体B中加入蒸馏水45g、硝酸银0.65g和硝酸铜0.12g，在75℃下搅拌保温1h，过滤分离出2.1g含银离子、含锌离子的纳米层状磷酸锆抗菌体C，其中抗菌体C的含水率为26％；11.2g of zirconium oxychloride aqueous solution and 6.5g of oxalic acid were added to the three-necked bottle. After stirring for 15 minutes, 4.3 g of disodium hydrogen phosphate was added, and the mixture was stirred and heated to 85 ° C, stirred for 70 min, and 0.78 g of polyethylene glycol 200 dissolved in 5 g of water was added. After stirring for 60 min, the precipitate was filtered, and the precipitate was washed with water to obtain a clean nano-layered zirconium phosphate carrier A, which was placed at 70 ° C for 48 h, and dehydrated to obtain a nano-layered zirconium phosphate carrier A. The longest diameter of the wafer was smaller than 100 nm, thickness less than 40 nm; 3.4 g of nano-layered zirconium phosphate carrier A, dispersed in 60 g of zinc nitrate solution dissolved in 32 g of water, heated to 95 ° C, stirred for 1 h, filtered to separate the zinc-containing intermediate carrier B, The filtrate was recovered. To 2.7 g of the zinc-containing intermediate carrier B, 45 g of distilled water, 0.65 g of silver nitrate and 0.12 g of copper nitrate were added, and the mixture was stirred and kept at 75 ° C for 1 h, and 2.1 g of a silver layer containing silver ions and containing zinc ions was separated by filtration. Zirconium phosphate antibacterial C, wherein the water content of the antibacterial C is 26%;
    (2)、在装有搅拌浆、温度计、冷凝管的500ml的四口烧瓶中，将聚四氢呋喃醚二醇100g与异佛尔酮二异氰酸酯99.9g混合，在三氯化钛0.42g和三乙基铝0.08g存在的条件下，于95℃下反应1.5h，得到200.1g聚氨酯预聚体A；(2) In a 500 ml four-necked flask equipped with a stirring slurry, a thermometer, and a condenser, 100 g of polytetrahydrofuran ether glycol and 99.9 g of isophorone diisocyanate were mixed, and 0.42 g of titanium trichloride and tribromide. The reaction of the base aluminum in the presence of 0.08g, at 95 ° C for 1.5h, to obtain 200.1g polyurethane prepolymer A;
    (3)、向聚氨酯预聚体A中加入二羟甲基丁酸21.1g和丙酮溶剂50.2g，于85℃条件下反应1.5h，加入三乙胺12.1g进行中和反应50min，加水25g进行乳化，形成304g的聚氨酯乳液B备用；(3) Adding 21.1 g of dimethylol butyric acid and 50.2 g of acetone solvent to the polyurethane prepolymer A, reacting at 85 ° C for 1.5 h, adding 12.1 g of triethylamine for neutralization for 50 min, and adding 25 g of water. Emulsified to form 304g of polyurethane emulsion B for use;
    (4)、将十二烷基苯磺酸钠10g溶于50g水中，加入2.1g纳米层状磷酸锆抗菌体C、γ-缩水甘油醚氧丙基三甲氧基硅烷5g和1g三甲基硅化腈，在1100r/min下剪切乳化，乳化 40min，得纳米材料乳液备用；(4) Dissolving 10 g of sodium dodecylbenzenesulfonate in 50 g of water, adding 2.1 g of nano-layered zirconium phosphate antibacterial C, γ-glycidoxypropyltrimethoxysilane 5 g and 1 g of trimethylsilation Nitrile, shear emulsified at 1100r/min, emulsified 40min, get the nano material emulsion for use;
    (5)、往聚氨酯乳液B中加入30.4g上述纳米材料乳液C，在pH为7的条件下，剪切搅拌速度为1200rpm，剪切搅拌时间40min，得到抗菌性与防水性聚氨酯涂料与胶黏剂329g。 (5), adding 30.4 g of the above nanomaterial emulsion C to the polyurethane emulsion B, under the condition of pH 7, the shear stirring speed is 1200 rpm, the shear stirring time is 40 min, and the antibacterial and waterproof polyurethane coating and the adhesive are obtained. Agent 329g.
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