CN108077308A - 一种核壳结构的抗菌纳米二氧化钛-二氧化硅水分散体 - Google Patents
一种核壳结构的抗菌纳米二氧化钛-二氧化硅水分散体 Download PDFInfo
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- CN108077308A CN108077308A CN201711307238.9A CN201711307238A CN108077308A CN 108077308 A CN108077308 A CN 108077308A CN 201711307238 A CN201711307238 A CN 201711307238A CN 108077308 A CN108077308 A CN 108077308A
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- nucleocapsid
- aqueous dispersion
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Classifications
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- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
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- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
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- Health & Medical Sciences (AREA)
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- Plant Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Nanotechnology (AREA)
- Environmental Sciences (AREA)
- Zoology (AREA)
- Pest Control & Pesticides (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Toxicology (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Composite Materials (AREA)
- Paints Or Removers (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Silicon Compounds (AREA)
Abstract
本发明涉及一种核壳结构的抗菌纳米TiO2/SiO2水分散体，核芯为纳米SiO2粒子，核壳为纳米TiO2粒子层；由有机硅单体在氨催化下缩聚成纳米SiO2，钛酸四丁酯与SiO2表面上的羟基反应生成核壳结构的TiO2包裹SiO2纳米微球。本发明还提供一种核壳结构的抗菌纳米TiO2/SiO2水分散体的制备方法。本发明制得的抗菌纳米TiO2/SiO2水分散体，在可见光或紫外线照射下，具有很强的氧化还原能力，能将甲醛、甲苯、二甲苯、氨、氡、TVOC、细菌、微生物等有害物分解，且具有持久性。因此本发明的核壳结构的抗菌纳米TiO2/SiO2水分散体可在涂料、油墨、表面处理以及陶瓷抛光上具有广阔的应用前景。
Description
技术领域
本发明涉及一种改性纳米二氧化硅，尤其涉及到一种核壳结构的抗菌纳米TiO2/SiO2水分散体，属于纳米材料技术领域。
技术背景
纳米二氧化硅是极其重要的高科技超微细无机新材料之一，因其粒径很小，比表面积大，表面吸附力强，表面能大，化学纯度高、分散性能好、热阻、电阻等方面具有特异的性能，以其优越的稳定性、补强性、增稠性和触变性，在众多学科及领域内独具特性，有着不可取代的作用。纳米二氧化硅广泛用于各行业作为添加剂、催化剂载体，石油化工，脱色剂，消光剂，橡胶补强剂，塑料充填剂，油墨增稠剂，金属软性磨光剂，绝缘绝热填充剂，高级日用化妆品填料及喷涂材料、医药、环保等各种领域。作为有机/无机复合材料的一种，具有核壳结构的聚合物/二氧化硅纳米复合微球已经被广泛地应用于生物医学、催化、电子器件以及胶体界面研究领域。
纳米二氧化硅包括粉体二氧化硅和胶体二氧化硅。由于纳米二氧化硅的粒径小、比表面大、比表面能高、表面带有羟基，所以能否发挥其在复合材料中的作用关键在于它的分散和与聚合物的复合。当二氧化硅表面未经改性与聚合物共混、共聚或接枝时，纳米二氧化硅容易团聚，与聚合物产生相分离或发生相反转。所以，对其进行改性是解决纳米二氧化硅团聚、制备无机-有机纳米复合材料的重要步骤。
二氧化硅表面改性的方法很多，依据成键机理不同可分为与二氧化硅表面形成共价键和与其表面形成氢键。如用硅烷偶联剂等对其进行表面改性是形成共价键，而用油酸对纳米改性则是通过氢键作用使油酸包覆在表面。依据二氧化硅类型可分为对粉体纳米二氧化硅和对胶体纳米二氧化硅进行表面改性两类，依据改性剂不同可分为用硅烷偶联剂改性和用其他改性剂改性等。
中国专利CN103739794A公开了一种超支化聚合物改性纳米二氧化硅杂化材料的制备方法，是将含巯基的硅烷偶联剂接枝到纳米二氧化硅表面，利用其表面巯基与多官能度丙烯酸酯进行点击反应形成末端为丙烯酸酯的改性纳米二氧化硅，再进一步与多官能度巯基化合物进行点击反应形成末端为巯基的改性二氧化硅，在多官能度丙烯酸酯与多官能度巯基化合物之间重复多次，在二氧化硅表面形成超支化聚合物。该发明方法制备的超支化聚合物改性纳米二氧化硅杂化材料具有末端巯基和超支化结构，应用于紫外光固化涂料中，可以改善涂料的耐热、硬度、耐磨等机械性能，尤其是解决纳米二氧化硅在紫外光固化涂料中的分散和迁移问题及紫外光固化涂料的氧阻聚问题。
中国专利CN104119631A公开了一种制备具有不同临界响应温度的温敏改性纳米二氧化硅复合物，方法是碱性物质加入SiO2前驱体和溶剂的混合溶液中反应后加入硅烷偶联剂，回流温度下反应，抽滤、洗涤、干燥得到SiO2-NH2粉末；将SiO2-NH2粉末分散到甲苯中，加入引发剂和缚酸剂反应，抽滤、洗涤、干燥得SiO2-Br粉末，将SiO2-Br粉末分散到二氯甲烷中，超声分散，加入催化剂和配体，通入氮气，搅拌下加入单体、去离子水，滴入还原剂聚合反应，抽滤、洗涤、干燥；将得到的样品用乙醇进行索式提取，干燥得温敏改性纳米SiO2复合物。该发明具有反应条件温和，制备具有不同临界响应温度的产品的优点。
在抗菌领域，银离子抗菌剂由于抗菌效率高、抗菌效果持久应用广泛；季铵盐型抗菌剂价格便宜、抗菌效率接近银离子抗菌剂，但作为抗菌添加剂易游离，因而抗菌持久性差，纳米二氧化钛是一种光触媒材料，具有杀菌作用。关于纳米二氧化钛接枝包覆纳米二氧化硅作抗菌性的耐磨助剂鲜有报道。
发明内容
为克服现有技术的缺点和不足，本发明的目的旨在提供一种核壳结构的抗菌纳米TiO2/SiO2水分散体。
本发明所述的一种核壳结构的抗菌纳米TiO2/SiO2水分散体，为具有核壳结构的纳米TiO2包覆纳米SiO2粒子，二者以-Si-O-Ti化学键相连，如图 1所示。
所述的一种核壳结构的抗菌纳米TiO2/SiO2水分散体，其制备方法如下：
在100份乙醇中加入2～6份去离子水、30份有机硅单体、1～3份阳离子表面活性剂，常温下搅拌10～30min后，加入1～3份氨水，继续搅拌12h；分别滴加8～14份冰乙酸、20～30份钛酸酯单体、100份乙醇，在0.5～2h滴加完毕，继续搅拌反应3～6h得淡蓝色溶胶，加水或乙醇兑稀，得所述的一种核壳结构的抗菌纳米TiO2/SiO2水分散体。
其中，所述的有机硅单体为正硅酸乙酯、正硅酸甲酯、正硅酸丁酯、四氯化硅中的一种或几种的组合。
所述的钛酸酯单体为钛酸四丁酯、钛酸四乙酯、钛酸四异丙醇酯中的一种或几种的组合。
所述的阳离子表面活性剂为十六烷基三甲基溴化铵、十二烷基三甲基氯化铵、十二烷基二甲基苄基氯化铵、十二烷基二甲基叔胺醋酸盐、十八烷基三甲基氯化铵、十六烷基氯化吡啶、十六烷基溴化吡啶中的一种或几种的组合。
本发明所述的一种核壳结构的抗菌纳米TiO2/SiO2水分散体，其制备原理为：首先有机硅单体在氨的催化作用下缩聚成纳米二氧化硅，然后钛酸四丁酯与二氧化硅表面的羟基反应形成-Si-O-Ti键，钛(Ⅳ)通过化学键结合在纳米二氧化硅表面，最后钛酸四丁酯发生自交联反应生成核壳结构的二氧化钛包裹二氧化硅纳米微球。
本发明制得的核壳结构的抗菌纳米TiO2/SiO2水分散体，核芯为纳米 SiO2粒子，核壳为纳米TiO2粒子层，在可见光或紫外线照射下，具有很强的氧化还原能力，能将甲醛、甲苯、二甲苯、氨、氡、TVOC、细菌、微生物等有害物进行分解，而且具有去除持久性。因此本发明的核壳结构的抗菌纳米TiO2/SiO2水分散体可在涂料、油墨、表面处理以及陶瓷抛光上具有广阔的应用前景。
附图说明
图1为核壳结构的抗菌纳米TiO2包覆纳米SiO2粒子的结构示意图，图中nano-SiO2为核芯，nano-TiO2为核壳，-Si-O-Ti-表示纳米TiO2粒子与纳米 SiO2粒子以化学键方式相连。
具体实施方式
下面结合实施例对本发明的一种核壳结构的抗菌纳米TiO2/SiO2水分散体做进一步的描述。可以理解的是，此处所描述的具体实施例仅仅用于解释相关发明，而非对该发明的限定。
实施例1
一种核壳结构的抗菌纳米TiO2/SiO2水分散体A，其制备工艺如下：
在100份乙醇中加入4份去离子水、30份正硅酸甲酯、2份十六烷基三甲基溴化铵，常温下搅拌10min后，加入15％质量份数2份氨水，继续搅拌 12h；分别滴加10份冰乙酸、25份钛酸四乙酯、100份乙醇，在1h滴加完毕，继续搅拌反应4h得淡蓝色溶胶，加水或乙醇兑稀至10％固含量的核壳结构的抗菌纳米TiO2/SiO2水分散体A。
实施例2
一种核壳结构的抗菌纳米TiO2/SiO2水分散体B，其制备工艺如下：
在100份乙醇中加入5份去离子水、30份正硅酸甲酯、1份十二烷基三甲基氯化铵，常温搅拌15min后加入3份质量份数20％氨水，继续搅拌12h；分别滴加10份冰乙酸、11份钛酸四丁酯、100份乙醇，在2h滴加完毕，继续搅拌反应6h得淡蓝色溶胶，加水或乙醇兑稀为10％固含量的核壳结构的抗菌纳米TiO2/SiO2水分散体B。
实施例3
一种核壳结构的抗菌纳米TiO2/SiO2水分散体C，其制备工艺如下：
在100份乙醇中加入4份去离子水、30份正硅酸丁酯、2份十六烷基三甲基溴化铵，常温搅拌30min后加入3份氨水，继续搅拌12h；分别滴加8 份冰乙酸、25份钛酸四乙酯、100份乙醇，在1.5h滴加完毕，继续搅拌反应4h 得淡蓝色溶胶，加水或乙醇兑稀至15％固含量的核壳结构的抗菌纳米TiO2/SiO2水分散体C。
将实施例中的核壳结构的抗菌纳米TiO2/SiO2水分散体添加到水性涂料中，按照GB/T 21866-2008标准测试涂料的抗菌性能，测试数据如表1所示：
表1抗菌涂料表面抗菌性能技术指标
将实施例中的核壳结构的抗菌纳米TiO2/SiO2水分散体添加到陶瓷抛光液中，按照JC/T 897-2002测试瓷砖的抗菌性能，测试数据如表2所示：
表2抛光瓷砖表面抗菌性能技术指标
尽管本发明已作了详细说明并引证了实施例，但对于本领域的普通技术人员，显然可以按照上述说明而做出的各种方案、修改和改动，都应该包括在权利要求的范围之内。
Claims (4)
1.一种核壳结构的抗菌纳米TiO2/SiO2水分散体，其特征在于：为核壳结构的纳米TiO2包覆纳米SiO2微球，其中，核芯为纳米SiO2粒子，核壳为纳米TiO2粒子层，二者以-Si-O-Ti化学键相连；
所述的一种核壳结构的抗菌纳米TiO2/SiO2水分散体，其制备方法如下：
在100份乙醇中加入2～6份去离子水、30份有机硅单体、1～3份阳离子表面活性剂，常温下搅拌10～30min后，加入1～3份氨水，继续搅拌12h；分别滴加8～14份冰乙酸、20～30份钛酸酯单体、100份乙醇，在0.5～2h滴加完毕，继续搅拌反应3～6h得淡蓝色溶胶，加水或乙醇兑稀，得所述的一种核壳结构的抗菌纳米TiO2/SiO2水分散体。
2.根据权利要求1所述的核壳结构的抗菌纳米TiO2/SiO2水分散体，其特征在于：所述的有机硅单体为正硅酸乙酯、正硅酸甲酯、正硅酸丁酯、四氯化硅中的一种或几种的组合。
3.根据权利要求1所述的核壳结构的抗菌纳米TiO2/SiO2水分散体，其特征在于：所述的钛酸酯单体为钛酸四丁酯、钛酸四乙酯、钛酸四异丙醇酯中的一种或几种的组合。
4.根据权利要求1所述的核壳结构的抗菌纳米TiO2/SiO2水分散体，其特征在于：所述的阳离子表面活性剂为十六烷基三甲基溴化铵、十二烷基三甲基氯化铵、十二烷基二甲基苄基氯化铵、十二烷基二甲基叔胺醋酸盐、十八烷基三甲基氯化铵、十六烷基氯化吡啶、十六烷基溴化吡啶中的一种或几种的组合。
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