WO2017092232A1 - 一种高载银含量磷酸锆粉体的制备方法 - Google Patents

一种高载银含量磷酸锆粉体的制备方法 Download PDF

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WO2017092232A1
WO2017092232A1 PCT/CN2016/081471 CN2016081471W WO2017092232A1 WO 2017092232 A1 WO2017092232 A1 WO 2017092232A1 CN 2016081471 W CN2016081471 W CN 2016081471W WO 2017092232 A1 WO2017092232 A1 WO 2017092232A1
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zirconium phosphate
silver
phosphate powder
powder
hours
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PCT/CN2016/081471
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朱美芳
相恒学
陈伟
夏维
孙宾
周哲
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东华大学
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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
    • A01N25/08—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 solids as carriers or diluents
    • 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
    • A01N59/16—Heavy metals; Compounds thereof

Definitions

  • the invention belongs to the field of preparation of antibacterial functional powders, in particular to a preparation method of high-silver content zirconium phosphate powder.
  • antibacterial agents include organic antibacterial agents, organometallic antibacterial agents, compound antibacterial agents, nano metal antibacterial agents, and inorganic powder metal-loaded antibacterial agents.
  • zirconium phosphate is a hot spot of concern and application.
  • the structure of zirconium phosphate is a three-dimensional structure composed of [PO 4 ] tetrahedron and [ZrO 6 ] octahedron by sharing oxygen atoms at the apex angle thereof, has an effective mesoporous structure, and has a hydroxyl group on the surface, which is inorganic.
  • the material contains silver as a good carrier for sustained release antibacterial.
  • the invention patent CN 102239887B discloses a preparation method of a nano-scale zirconium phosphate-loaded silver composite inorganic antibacterial agent; the invention patent CN 102763678B discloses a preparation method of a cubic zirconium phosphate-loaded silver antibacterial powder; the invention patent CN 1240288C discloses a method. Preparation method of layered zirconium phosphate-loaded silver powder; invention patent CN 100345486C discloses a nano-layered zirconium phosphate-loaded silver inorganic antibacterial powder and a novel preparation method thereof; the invention patent CN 1281689C discloses a modified zirconium phosphate Silver powder and its preparation method.
  • the above invention patents all use the method of metal ion replacement to load silver ions in the zirconium phosphate matrix, and the preparation process is complicated.
  • the technical problem to be solved by the present invention is to provide a method for preparing a high-silver content zirconium phosphate powder.
  • the silver-loaded zirconium phosphate prepared by the method has high silver content, and the preparation method is simple and easy.
  • the high-silver content zirconium phosphate of the invention can be preferably used in the fields of antibacterial plastics, antibacterial coatings or antibacterial fibers.
  • the present invention provides a preparation method of a high-silver content zirconium phosphate powder.
  • the method comprises the steps of: dispersing a mesoporous zirconium phosphate powder and a polyfluorenyl compound in an organic solvent; then adding silver nitrate, stirring for 12 to 24 hours, removing the organic solvent by spray drying, and setting the obtained powder
  • the mixture is calcined at 800 to 1200 ° C for 1 to 6 hours to obtain a silver-loaded zirconium phosphate powder having a silver content of 3 to 8%.
  • the silver-loaded zirconium phosphate powder has a diameter of 200 to 800 nm.
  • the polyhydrazino compound is one or more of ethylene glycol dimercaptoacetate, 1,3-dimercaptopropane, pentaerythritol tetradecyl acetate, and pentaerythritol tetrakis-mercaptopropionate.
  • the mass ratio of the mesoporous zirconium phosphate powder, the polyfluorenyl compound and the silver nitrate is from 100:1 to 6:8-20.
  • the organic solvent is one of ethanol, acetone, dichloromethane and chloroform.
  • the specific step of dispersing the mesoporous zirconium phosphate powder and the polyfluorenyl compound in the organic solvent is: adding the zirconium phosphate powder and the polyfluorenyl compound to the organic solvent, and performing the ultrasonic dispersion for 0.5 to 2 hours.
  • the polyfluorenyl compound can be effectively dispersed in the pores and on the surface of the zirconium phosphate, and the mercapto group first bonds with the hydroxyl group on the surface of the mesoporous zirconium phosphate; when the silver nitrate is added, the unreacted mercapto group is not reacted.
  • the group can effectively bond the silver ions, so that a large amount of silver ions enter the mesopores of the zirconium phosphate well and bond to the surface of the zirconium phosphate to form high-silver-loaded zirconium phosphate particles.
  • the high-silver content zirconium phosphate nano powder prepared by the invention has simple preparation process, low preparation cost, low pollution and high silver content, and can be preferably applied to the fields of antibacterial plastics, antibacterial coatings and antibacterial fibers.
  • the mesoporous zirconium phosphate nanopowder used in each of the examples of the present invention is a commercially available product having a particle diameter of 200 to 800 nm and a pore diameter of 4 to 15 nm.
  • a method for preparing a high-silver content zirconium phosphate powder the specific steps are: adding 100 g of mesoporous zirconium phosphate nanopowder and 3 g of pentaerythritol tetradecyl acetate to 100 mL of chloroform, and sealing ultrasonic dispersion at room temperature ( Ultrasonic frequency: 40 KHz) 2 hours; then 20 g of silver nitrate was added and stirred (500 r/min) for 24 hours.
  • the chloroform solvent was removed by spray drying, and the obtained powder was calcined at 1200 ° C for 3 hours to obtain a silver-loaded zirconium phosphate nano powder having a silver content of 8% and a diameter of 200 to 800 nm.
  • a method for preparing a high-silver content zirconium phosphate powder the specific steps are: adding 100 g of mesoporous zirconium phosphate nano powder and 6 g of 1,3-1,3-mercaptopropane to 100 mL of dichloromethane, and sealing the ultrasound at room temperature Dispersion (ultrasonic frequency: 40 KHz) for 0.5 hours; then 10 g of silver nitrate was added and stirred (500 r/min) for 12 hours.
  • the dichloromethane solvent was removed by spray drying, and the obtained powder was calcined at 800 ° C for 6 hours to obtain a silver-loaded zirconium phosphate nano powder having a diameter of 200-800 nm and having a silver content of 4%.
  • a method for preparing high-silver content zirconium phosphate powder the specific steps are: adding 100 g of mesoporous zirconium phosphate nano powder and 1 g of ethylene glycol dimercaptoacetate to 100 mL of ethanol, and sealing ultrasonic dispersion at room temperature (ultrasound) Frequency: 40 KHz) 1 hour; then 15 g of silver nitrate was added and stirred (500 r/min) for 24 hours. The ethanol was removed by spray drying, and then the obtained powder was calcined at 1200 ° C for 3 hours to obtain a silver-loaded zirconium phosphate nano powder having a diameter of 200-800 nm and having a silver content of 6%.
  • a method for preparing a high-silver content zirconium phosphate powder the specific steps are: adding 100 g of mesoporous zirconium phosphate nano powder and 5 g of 1,3-dimercaptopropane to 100 mL of acetone, and sealing ultrasonic dispersion at room temperature (ultrasound) Frequency: 40 KHz) 2 hours; then 8 g of silver nitrate was added and stirred (500 r/min) for 24 hours. The acetone was removed by spray drying, and the obtained powder was calcined at 1,100 ° C for 6 hours to obtain a silver-loaded zirconium phosphate nano powder having a silver content of 3% and a diameter of 200 to 400 nm.
  • a method for preparing a high-silver content zirconium phosphate powder the specific steps are: adding 100 g of mesoporous zirconium phosphate nano powder and 6 g of pentaerythritol tetradecyl acetate to 100 mL of chloroform, and sealing at room temperature Ultrasonic dispersion (ultrasonic frequency: 40 KHz) for 2 hours; then 20 g of silver nitrate was added and stirred (500 r/min) for 24 hours.
  • the chloroform solvent was removed by spray drying, and the obtained powder was calcined at 1200 ° C for 4 hours to obtain a silver-loaded zirconium phosphate nano powder having a silver content of 8% and a diameter of 200 to 400 nm.

Abstract

本发明提供了一种高载银含量磷酸锆粉体的制备方法，其特征在于，包括：将介孔磷酸锆粉体与多巯基化合物分散于有机溶剂中，密闭超声分散0.5～2小时；然后加入硝酸银，搅拌12～24小时，采用喷雾干燥法去除有机溶剂，将获得的粉体置于800～1200℃环境下煅烧1～6小时，得到银质量含量为3～8％的载银磷酸锆粉体。本发明中多巯基化合物可以有效分散到磷酸锆的孔洞中和表面上，巯基基团首先与磷酸锆表面的羟基发生键合作用；在加入硝酸银时，未发生反应的巯基基团可以有效的键接银离子，使大量银离子很好地进入磷酸锆的介孔中和键接在磷酸锆的表面上，形成高载银含量磷酸锆粒子。

Description

一种高载银含量磷酸锆粉体的制备方法 技术领域
本发明属于抗菌功能粉体的制备领域，特别涉及一种高载银含量磷酸锆粉体的制备方法。
背景技术
随着科学技术的进步和生活水平的提高，人们对生活环境的安全防护意识增强。其中，具有抗菌功能的涂料、塑料生活用品、服装和家用纺织品都得到了广大的关注。尤其在与皮肤接触的安全防护方面，抑菌防臭性能尤为重要。当前，抗菌剂种类包含有机抗菌剂、有机金属抗菌剂、化合物型抗菌剂、纳米金属抗菌剂及无机粉体载金属抗菌剂等。
在上述抗菌剂中，载银磷酸锆是人们关注和应用的一个热点。磷酸锆的结构为[PO4]四面体和[ZrO6]八面体通过共用其顶角上的氧原子而构成的三维空间结构，具有有效的介孔结构，且表面含有羟基基团，是无机材料载银缓释抗菌的优良载体。因此发明专利CN 102239887B公开了一种纳米级磷酸锆载银复合无机抗菌剂的制备方法；发明专利CN 102763678B公开了一种立方体磷酸锆载银抗菌粉的制备方法；发明专利CN 1240288C公开了一种制备层状磷酸锆载银粉末的制备方法；发明专利CN 100345486C公开了一种纳米层状磷酸锆载银无机抗菌粉体及其制备新方法；发明专利CN 1281689C公开了一种改性磷酸锆载银粉末及其制备方法。但上述发明专利均采用金属离子置换的方法使磷酸锆基体中负载银离子，制备过程较为繁杂。
发明内容
本发明所要解决的技术问题是提供一种高载银含量磷酸锆粉体的制备方法，该方法制备的载银磷酸锆的银含量高，制备方法简单易行。本发明的高载银含量磷酸锆可较好的应用在抗菌塑料、抗菌涂料或抗菌纤维等领域。
为了解决上述技术问题，本发明提供了一种高载银含量磷酸锆粉体的制备方 法，其特征在于，包括：将介孔磷酸锆粉体与多巯基化合物分散于有机溶剂中；然后加入硝酸银，搅拌12～24小时，采用喷雾干燥法去除有机溶剂，将获得的粉体置于800～1200℃环境下煅烧1～6小时，得到银质量含量为3～8％的载银磷酸锆粉体。
优选地，所述的载银磷酸锆粉体的直径为200～800nm。
优选地，所述的多巯基化合物为二巯基乙酸乙二醇酯、1,3-二巯基丙烷、季戊四醇四巯基乙酸酯和季戊四醇四-3-巯基丙酸酯的一种或几种。
优选地，所述的介孔磷酸锆粉体、多巯基化合物和硝酸银的质量比为100：1～6：8～20。
优选地，所述的有机溶剂为乙醇、丙酮、二氯甲烷和三氯甲烷的一种。
优选地，所述的将介孔磷酸锆粉体与多巯基化合物分散于有机溶剂中的具体步骤为：将磷酸锆粉体与多巯基化合物加入到有机溶剂中，密闭超声分散0.5～2小时。
与现有技术相比，本发明的有益效果是：
(1)本发明中多巯基化合物可以有效分散到磷酸锆的孔洞中和表面上，巯基基团首先与介孔磷酸锆表面的羟基发生键合作用；在加入硝酸银时，未发生反应的巯基基团可以有效的键接银离子，使大量银离子很好地进入磷酸锆的介孔中和键接在磷酸锆的表面上，形成高载银含量磷酸锆粒子。
(2)本发明中多巯基化合物完成载银任务后，包括未反应的巯基基团，都可在煅烧工艺中被去除。
(3)本发明制备的高载银含量磷酸锆纳米粉体，制备工艺简单，制备成本低、污染小、银含量高，可较好的应用于抗菌塑料、抗菌涂料和抗菌纤维领域。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
本发明各实施例所用的介孔磷酸锆纳米粉体为市售产品，粒径为200～800nm，孔径为4～15nm。
实施例1
一种高载银含量磷酸锆粉体的制备方法，具体步骤为：将100g介孔磷酸锆纳米粉体、3g季戊四醇四巯基乙酸酯加入到100mL的三氯甲烷中，室温下密闭超声分散(超声频率：40KHz)2小时；然后加入20g的硝酸银，搅拌(500r/min)24小时。利用喷雾干燥的方式去除三氯甲烷溶剂，然后将获得的粉体置于1200℃环境下煅烧3小时，获得载银质量含量为8％的直径为200～800nm的载银磷酸锆纳米粉体。
实施例2
一种高载银含量磷酸锆粉体的制备方法，具体步骤为：将100g介孔磷酸锆纳米粉体、6g季1,3-二巯基丙烷加入到100mL的二氯甲烷中，室温下密闭超声分散(超声频率：40KHz)0.5小时；然后加入10g的硝酸银，搅拌(500r/min)12小时。利用喷雾干燥的方式去除二氯甲烷溶剂，然后将获得的粉体置于800℃环境下煅烧6小时，获得载银质量含量为4％的直径为200-800nm的载银磷酸锆纳米粉体。
实施例3
一种高载银含量磷酸锆粉体的制备方法，具体步骤为：将100g介孔磷酸锆纳米粉体、1g二巯基乙酸乙二醇酯加入到100mL的乙醇中，室温下密闭超声分散(超声频率：40KHz)1小时；然后加入15g的硝酸银，搅拌(500r/min)24小时。利用喷雾干燥的方式去除乙醇，然后将获得的粉体置于1200℃环境下煅烧3小时，获得载银质量含量为6％的直径为200-800nm的载银磷酸锆纳米粉体。
实施例4
一种高载银含量磷酸锆粉体的制备方法，具体步骤为：将100g介孔磷酸锆纳米粉体、5g 1,3-二巯基丙烷加入到100mL的丙酮中，室温下密闭超声分散(超声频率：40KHz)2小时；然后加入8g的硝酸银，搅拌(500r/min)24小时。利用喷雾干燥的方式去除丙酮，然后将获得的粉体置于1100℃环境下煅烧6小时，获得载银质量含量为3％的直径为200～400nm的载银磷酸锆纳米粉体。
实施例5
一种高载银含量磷酸锆粉体的制备方法，具体步骤为：将100g介孔磷酸锆纳米粉体、6g季戊四醇四巯基乙酸酯加入到100mL的三氯甲烷中，室温下密闭 超声分散(超声频率：40KHz)2小时；然后加入20g的硝酸银，搅拌(500r/min)24小时。利用喷雾干燥的方式去除三氯甲烷溶剂，然后将获得的粉体置于1200℃环境下煅烧4小时，获得载银质量含量为8％的直径为200～400nm的载银磷酸锆纳米粉体。

Claims (6)

  1. 一种高载银含量磷酸锆粉体的制备方法，其特征在于，包括：将介孔磷酸锆粉体与多巯基化合物分散于有机溶剂中；然后加入硝酸银，搅拌12～24小时，采用喷雾干燥法去除有机溶剂，将获得的粉体置于800～1200℃环境下煅烧1～6小时，得到银质量含量为3～8％的载银磷酸锆粉体。
  2. 如权利要求1所述的高载银含量磷酸锆粉体的制备方法，其特征在于，所述的载银磷酸锆粉体的直径为200～800nm。
  3. 如权利要求1所述的高载银含量磷酸锆粉体的制备方法，其特征在于，所述的多巯基化合物为二巯基乙酸乙二醇酯、1,3-二巯基丙烷、季戊四醇四巯基乙酸酯和季戊四醇四-3-巯基丙酸酯的一种或几种。
  4. 如权利要求1所述的高载银含量磷酸锆粉体的制备方法，其特征在于，所介孔述的磷酸锆粉体、多巯基化合物和硝酸银的质量比为100：1～6：8～20。
  5. 如权利要求1所述的高载银含量磷酸锆粉体的制备方法，其特征在于，所述的有机溶剂为乙醇、丙酮、二氯甲烷和三氯甲烷的一种。
  6. 如权利要求1所述的高载银含量磷酸锆粉体的制备方法，其特征在于，所述的将介孔磷酸锆粉体与多巯基化合物分散于有机溶剂中的具体步骤为：将磷酸锆粉体与多巯基化合物加入到有机溶剂中，密闭超声分散0.5～2小时。
PCT/CN2016/081471 2015-12-01 2016-05-09 一种高载银含量磷酸锆粉体的制备方法 WO2017092232A1 (zh)

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CN105325456B (zh) * 2015-12-01 2018-08-03 东华大学 一种高载银含量磷酸锆粉体的制备方法
CN107242233B (zh) * 2017-07-10 2020-12-04 四川蓝博兴科技有限公司 复合皮革防霉除菌剂及其制备方法
CN112674112A (zh) * 2020-12-23 2021-04-20 深圳市世格赛思医疗科技有限公司 一种载银磷酸锆及其制备方法和应用

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