WO2021203833A1 - 一种凹凸棒石基pH响应抗菌材料的制备方法 - Google Patents

一种凹凸棒石基pH响应抗菌材料的制备方法 Download PDF

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WO2021203833A1
WO2021203833A1 PCT/CN2021/076254 CN2021076254W WO2021203833A1 WO 2021203833 A1 WO2021203833 A1 WO 2021203833A1 CN 2021076254 W CN2021076254 W CN 2021076254W WO 2021203833 A1 WO2021203833 A1 WO 2021203833A1
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attapulgite
antibacterial
chitosan
responsive
antibacterial material
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French (fr)
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王爱勤
惠爱平
杨芳芳
康玉茹
牟斌
汪琴
朱永峰
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中国科学院兰州化学物理研究所
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Priority to US17/781,667 priority Critical patent/US11700849B2/en
Publication of WO2021203833A1 publication Critical patent/WO2021203833A1/zh

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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
    • A01N25/12—Powders or granules
    • 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
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing aliphatically bound aldehyde or keto groups, or thio analogues thereof; Derivatives thereof, e.g. acetals
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/10—Organic substances
    • A23K20/105—Aliphatic or alicyclic compounds
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/10—Organic substances
    • A23K20/111—Aromatic compounds
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/10—Organic substances
    • A23K20/116—Heterocyclic compounds
    • A23K20/121—Heterocyclic compounds containing oxygen or sulfur as hetero atom
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/10—Organic substances
    • A23K20/163—Sugars; Polysaccharides
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/20—Inorganic substances, e.g. oligoelements
    • A23K20/28—Silicates, e.g. perlites, zeolites or bentonites
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K40/00—Shaping or working-up of animal feeding-stuffs
    • A23K40/10—Shaping or working-up of animal feeding-stuffs by agglomeration; by granulation, e.g. making powders
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K40/00—Shaping or working-up of animal feeding-stuffs
    • A23K40/30—Shaping or working-up of animal feeding-stuffs by encapsulating; by coating
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K50/00—Feeding-stuffs specially adapted for particular animals
    • A23K50/70—Feeding-stuffs specially adapted for particular animals for birds
    • A23K50/75—Feeding-stuffs specially adapted for particular animals for birds for poultry

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  • the invention relates to a preparation method of an attapulgite-based pH-responsive antibacterial material, which is mainly used to replace antibiotics in the process of livestock and poultry breeding, and belongs to the field of nano-mineral functional materials and animal feed additives.
  • natural antibacterial agents such as plant extracts have unlimited potential for antimicrobial replacement, and they are also one of the most common functional additives for feed antimicrobial applications in the EU (Northern Animal Husbandry, 2019, 09, 17).
  • Plant extracts are mainly used to directly inhibit pathogenic bacteria.
  • aldehydes such as cinnamaldehyde are a commonly used feed additive. Adding it to feed has a good antibacterial effect (Journal of Animal Nutrition, 2019, 1-8).
  • aldehydes are easy to oxidize, have strong volatility, and are accompanied by a certain pungent odor, so they need to be stabilized.
  • Attapulgite is a natural one-dimensional nano-hydrous magnesium-rich aluminum silicate clay mineral. Attapulgite has zeolite-like pores of 0.37nm ⁇ 0.64nm. Through mechanochemical action, organic molecules can reside in the pores. But the aldehydes residing in the attapulgite pores still have a certain pungent odor.
  • the present invention uses the principle of forming Schiff bases between amino groups of chitosan and aldehydes on the basis of aldehydes residing in attapulgite pores to prepare pH-responsive antibacterial materials. .
  • the purpose of the present invention is to provide a method for preparing attapulgite-based pH-responsive antibacterial materials, which on the one hand solves the problems of aldehydes natural antibacterial agents that are easy to oxidize, have strong volatility and are accompanied by certain pungent odors, and on the other hand, use
  • the pH responsiveness of chitosan solves the continuous release of natural antibacterial agents of aldehydes in animal intestines, and can be directly used as animal feed for safe animal breeding.
  • the preparation method of the attapulgite-based pH-responsive antibacterial material of the present invention is to directly spray the aldehyde-based natural antibacterial agent on the surface of the attapulgite powder under stirring, continue stirring for 20-30 minutes, and then place it in a ball mill to grind for 30-60 minutes. Then put the chitosan-citric acid aqueous solution in a stirring tank; after spraying, continue to stir for 30-120 minutes, and finally the obtained material is dried, sieved, and packaged to obtain the antibacterial material.
  • the attapulgite is a pure attapulgite with a purity of ⁇ 90% obtained by pulverization, acidification and sand removal, and its particle size is above 200 mesh.
  • the aldehydes natural antibacterial agent is citral, lauric aldehyde, glycol cinnamaldehyde, cinnamaldehyde, benzaldehyde, perillaldehyde, vanillin, furfural, 2,4-octadienal, 2,4-nonadiene At least one of aldehyde, 2,4-heptadienal and 2,4-decadienal; the amount of aldehyde natural antibacterial agent is 10-50% of the mass of attapulgite.
  • the ball-to-material ratio in the grinding working state of the ball mill is 1:10.
  • the mass concentration of chitosan is 5-10%, the concentration of citric acid is 1-5%; the amount of chitosan is 7.5-20% of the mass of attapulgite.
  • Figure 1 is a thermogravimetric diagram of the antibacterial material prepared in Example 2 of the present invention. Compared with the attapulgite, it can be seen that the organic loading of the obtained antibacterial material is 22.9%. It shows that attapulgite as a carrier material can effectively realize the reaction of aldehyde and chitosan to prepare Schiff base antibacterial material.
  • Figure 2 is an infrared spectrum of the antibacterial material prepared by the present invention.
  • the -C N absorption peaks appeared at 1 and 1656 cm -1 , indicating that the aldehyde and chitosan were combined through carbon-nitrogen double bonds.
  • the infrared results show that the Schiff base antibacterial material was successfully prepared.
  • the antibacterial performance is evaluated by the minimum inhibitory concentration method. Among them, set up experimental group, negative control group, positive control group and blank control group.
  • test sample agar plates with different concentrations evenly disperse the samples treated with different pH values into nutrient agar medium, the Escherichia coli group 2.5mg/mL, 1.5mg/mL, 1mg/mL, 0.5 mg/mL, 2.5 mg/mL, 1.5 mg/mL, 1 mg/mL, 0.5 mg/mL of Staphylococcus aureus group.
  • Table 1 shows the minimum inhibitory concentration test results of the samples obtained in Examples 1 to 6 after treatment with different pH values against Escherichia coli and Staphylococcus aureus.
  • the results show that the samples obtained in Examples 1-6 of the present invention have minimum inhibitory concentrations of 0.5 mg/mL and 1 mg/mL against Escherichia coli and Staphylococcus aureus, respectively, and against Gram-negative bacteria and Gram-positive bacteria. Both show strong antibacterial activity. Comparing the minimum inhibitory concentrations of samples treated with different pHs, it can be seen that the samples prepared by the present invention show weak antibacterial activity under acidic conditions, and show stronger antibacterial activity under neutral conditions.
  • the present invention uses mechanochemical methods to reside aldehydes in the attapulgite pores, and then spray chitosan solution on the surface of the attapulgite, so that the aldehydes react with the chitosan to form Schiff Alkali overcomes the shortcomings of aldehydes natural antibacterial agents such as easy volatility and strong irritating odor, and improves the palatability of animals when they are used in safe animal breeding, thereby increasing the utilization efficiency of aldehydes natural antibacterial agents; improving the natural antibacterial agents of aldehydes Utilization efficiency of antibacterial agents; using chitosan to impart pH responsiveness to antibacterial materials: under acidic conditions, chitosan amino groups are protonated, and antibacterial substances are not released, while under neutral and weakly alkaline conditions, after Schiff base hydrolysis Continuous release of antibacterial substances, therefore, it can be directly used as animal feed for safe animal breeding.
  • Figure 1 is the thermogravimetric analysis result of the antibacterial material obtained in Example 2 of the present invention.
  • Figure 2 is an infrared spectrum of the antibacterial material obtained in Example 2 of the present invention.
  • Spray cinnamaldehyde with a mass fraction of 25% relative to the attapulgite on the surface of the attapulgite under stirring continue to stir for 30 minutes, and place it in a ball mill for 40 minutes (ball-to-material ratio 1:10), and then place it in a stirring tank.
  • the antibacterial properties of antibacterial materials are shown in Table 1.
  • the attapulgite is a product with a purity of ⁇ 90% obtained by sulfuric acid acidification treatment of 2 to 3% relative to the mass fraction of the attapulgite, and a product with a purity of ⁇ 90% is obtained, and the product is crushed to 200 mesh before use.
  • Table 1 The minimum inhibitory concentration of antibacterial materials prepared in Examples 1-6 with different pH values

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Abstract

一种凹凸棒石基pH响应抗菌材料的制备方法，是在搅拌状态下，将醛类天然抗菌剂直接喷洒于凹凸棒石粉末表面，再置于球磨机研磨，然后于搅拌罐中喷雾壳聚糖‑柠檬酸水溶液；喷雾结束后持续搅拌30~120min，所得物料烘干、过筛、包装即得。

Description

一种凹凸棒石基pH响应抗菌材料的制备方法 技术领域
本发明涉及一种凹凸棒石基pH响应抗菌材料的制备方法，主要用于畜禽养殖过程中替代抗生素，属于纳米矿物功能材料和动物饲料添加剂领域。
背景技术
2019年7月9日，农业农村部发布第194号公告，公布了药物饲料添加剂退出计划和相关管理政策，明确提出2020年7月1日“全面禁抗”。为此，开发安全、高效饲料抗生素替代产品，成为动物健康养殖的迫切需求。
在诸多替抗产品中，天然抗菌剂如植物提取物替抗潜力无限，也是欧盟饲料替抗应用最普遍的功能性添加剂产品之一(北方牧业，2019，09，17)。植物提取物主要表现为直接的抑杀病原菌，其醛类物质如肉桂醛是一种常用的饲料添加剂，将其添加于饲料中具有良好的抗菌效果(动物营养学报，2019，1-8)。但醛类物质易氧化，挥发性强，并伴随有一定的刺激性气味，需要对其进行稳定化处理。
凹凸棒石是一种天然一维纳米含水富镁铝硅酸盐黏土矿物。凹凸棒石有0.37nm×0.64nm的沸石状孔道，通过机械力化学作用，可将有机分子驻留在孔道中。但将醛类物质驻留在凹凸棒石孔道中仍有一定的刺激性气味。为了进一步解决醛类天然抗菌剂的缺陷，本发明在醛类物质驻留凹凸棒石孔道中的基础上，采用壳聚糖的氨基与醛类物质形成席夫碱原理，制备了pH响应抗菌材料。
发明内容
本发明的目的是提供一种凹凸棒石基pH响应抗菌材料制备方法，一方面解决醛类天然抗菌剂易氧化、挥发性强和伴随有一定的刺激性气味等的问题，另一方面，利用壳聚糖pH响应性，解决醛类天然抗菌剂在动物肠道中的持续释放性，可直接作为动物饲料用于动物安全养殖。
一、凹凸棒石基pH响应抗菌材料制备
本发明凹凸棒石基pH响应抗菌材料的制备方法，是在搅拌状态下，将醛类天然抗菌剂直接喷洒于凹凸棒石粉末表面，持续搅拌20～30min，再置于球磨机 研磨30～60min，然后置于搅拌罐中喷雾壳聚糖-柠檬酸水溶液；喷雾结束后持续搅拌30～120min，最后将所得物料烘干、过筛、包装即得抗菌材料。
所述凹凸棒石是经粉碎、酸化处理、除砂得到的纯度≥90％的纯凹凸棒石，其粒径在200目以上。
所述醛类天然抗菌剂为柠檬醛、月桂醛、乙二醇缩肉桂醛、肉桂醛、苯甲醛、紫苏醛、香草醛、糠醛、2,4辛二烯醛、2,4壬二烯醛、2,4庚二烯醛、2,4癸二烯醛中的至少一种；醛类天然抗菌剂用量为凹凸棒石质量的10～50％。
所述球磨机研磨工作状态的球料比为1:10。
所述壳聚糖-柠檬酸水溶液中，壳聚糖的质量浓度为5～10％，柠檬酸的浓度为1～5％；壳聚糖的用量为凹凸棒石质量的7.5～20％。
二、抗菌材料的结构表征
以实施例2制备的肉桂醛-壳聚糖席夫碱为例，对本发明制备的抗菌材料的结构进行表征。图1为本发明实施例2所制备抗菌材料的热重图。与凹凸棒石对比可知，所得抗菌材料有机物担载量为22.9％。表明凹凸棒石作为载体材料，可以有效实现醛与壳聚糖的反应来制备席夫碱抗菌材料。
图2为本发明所制备抗菌材料的红外谱图。可以看出，在1456cm -1处存在C－H吸收及874cm -1处存在苯环的C－H吸收峰，说明醛-壳聚糖席夫碱结构中存在着苯环结构；1632峰cm -1和1656cm -1处出现-C＝N吸收峰，说明醛与壳聚糖通过碳氮双键结合。红外结果表明成功制备了席夫碱抗菌材料。
三、抗菌材料抑菌性能评价
抗菌性能评价采用最小抑菌浓度法。其中，设置实验组、阴性对照组、阳性对照组和空白对照组。
(1)标准菌株的准备：大肠埃希菌标准菌株ATCC 25922，金黄色葡萄球菌标准菌株ATCC 25923。取-20℃保存的大肠埃希菌ATCC 25922及金黄色葡萄球菌ATCC 25923，解冻后接种到LB肉汤培养基中，在35℃振荡箱中孵育12h，震荡频率160r/min，复活菌株后，再次转接至营养琼脂培养基中，置于恒温培养箱中37℃孵育，3h后细菌传代进入对数期后。选取进入对数期的标准菌株的单个菌落配置菌悬液，将菌悬液浊度调至0.5McFarland标准浊度，再用PBS缓冲液1:10依次稀释，使之含菌量分别为10 7CFU/mL、10 6CFU/mL、10 5CFU/mL、10 4CFU/mL。
(2)制备不同浓度的待测样琼脂平板：将调节不同pH值处理的样品均匀分散到营养琼脂培养基中，大肠埃希菌组2.5mg/mL、1.5mg/mL、1mg/mL、0.5mg/mL，金黄色葡萄球菌组2.5mg/mL、1.5mg/mL、1mg/mL、0.5mg/mL。
(3)点种：用移液枪吸取1μL的上述菌悬液(含菌量约为1×10 4CFU/mL，点种于含待测样的琼脂平板平皿内，每个平皿分别点种在3个不同的位置，并进行2次重复试验。将所有平板移至恒温培养箱中培养，在37℃下培养24h后，观察细菌生长情况。
表1为实施例1～6所得样品在不同pH值处理后对大肠埃希菌和金黄色葡萄球菌的最小抑菌浓度测试结果。结果表明，本发明实施例1-6所得样品对大肠埃希菌和金黄色葡萄球菌的最小抑菌浓度分别为0.5mg/mL和1mg/mL，对革兰氏阴性菌和革兰氏阳性菌均表现出强的抗菌活性。对比不同pH处理样品的最小抑菌浓度可以看出，利用本发明制备的样品在酸性条件下表现为较弱的抗菌活性，在中性条件下表现为较强的抗菌活性。
综上所述，本发明利用机械力化学法，将醛类物质驻留在凹凸棒石孔道中，然后在凹凸棒石表面喷涂壳聚糖溶液，使得醛类物质与壳聚糖反应形成席夫碱，克服了醛类天然抗菌剂易挥发和刺激性气味浓烈等不足，改进其在动物安全养殖中使用时动物的适口性，进而提高醛类天然抗菌剂的利用效率；提高了醛类天然抗菌剂的利用效率；利用壳聚糖赋予抗菌材料pH响应性：在酸性条件下，壳聚糖氨基被质子化，抗菌物质不释放，而在中性和弱碱性条件下，席夫碱水解后持续释放抗菌物质，因此，可直接作为动物饲料用于动物安全养殖。
附图说明
图1为本发明实施例2所得抗菌材料的热重分析结果。
图2为本发明实施例2所得抗菌材料的红外谱图。
具体实施方式
下面结合具体实施例对本发明pH响应抗菌材料的制备方法及抗菌性能进行详细说明。
实施例1
在搅拌下将相对于凹凸棒石质量分数30％的柠檬醛喷洒于凹凸棒石表面，持续搅拌30min后置于球磨机中研磨时间30min(球料比1:10)；再置于搅拌罐中， 喷洒相对于凹凸棒石质量7.5％壳聚糖的壳聚糖-柠檬酸水溶液(体系中壳聚糖浓度为5％，柠檬酸浓度为2.5％)，喷洒结束后持续搅拌30min，最后将物料烘干、过筛、包装即得抗菌材料。抗菌材料的抗菌性能见表1。
实施例2
在搅拌下将相对于凹凸棒石质量分数25％的肉桂醛喷洒于凹凸棒石表面，持续搅拌30min后置于球磨机中研磨时间40min(球料比1:10)，再置于搅拌罐中，喷洒相对于凹凸棒石质量分数10％壳聚糖的壳聚糖-柠檬酸水溶液(体系中壳聚糖浓度7.5％，柠檬酸浓度1％)，喷洒结束后持续搅拌45min，最后将物料烘干、过筛、包装即得抗菌材料。抗菌材料的抗菌性能见表1。
实施例3
在搅拌下将相对于凹凸棒石质量分数40％的月桂醛喷洒于凹凸棒石表面，持续搅拌30min后置于球磨机中研磨50min(球料比1:10)，再将物料置于搅拌罐中，喷洒相对于凹凸棒石质量15％壳聚糖的壳聚糖-柠檬酸水溶液(体系中壳聚糖浓度10％，柠檬酸浓度2.5％)，喷洒结束后持续搅拌60min，最后将物料烘干、过筛、包装即得抗菌材料。抗菌材料的抗菌性能见表1。
实施例4
在搅拌下将相对于凹凸棒石质量分数10％的糠醛喷洒于凹凸棒石表面，持续搅拌30min后置于球磨机中研磨30min(球料比1:10)；再将物料置于搅拌罐中，喷洒相对于凹凸棒石质量7.5％壳聚糖的壳聚糖-柠檬酸水溶液(体系中壳聚糖浓度7.5％，柠檬酸浓度5％)，喷洒结束后持续搅拌80min，最后将物料烘干、过筛、包装即得抗菌材料。抗菌材料的抗菌性能见表1。
实施例5
在搅拌下将相对于凹凸棒石质量分数50％的2,4庚二烯醛喷洒于凹凸棒石表面，持续搅拌30min后置于球磨机中研磨60min(球料比1:10)，再将物料置于搅拌罐中，喷洒相对于凹凸棒石质量20％壳聚糖的壳聚糖-柠檬酸水溶液(体系中壳聚糖浓度10％，柠檬酸浓度5％)，喷洒结束后持续搅拌120min，最后将物料烘干、过筛、包装即得抗菌材料。抗菌材料的抗菌性能见表1。
实施例6
在搅拌下将相对于凹凸棒石质量分数25％的肉桂醛喷洒于凹凸棒石表面，持 续搅拌30min后置于球磨机中研磨30min(球料比1:10)，再将物料置于搅拌罐中，喷洒相对于凹凸棒石质量17.5％壳聚糖的壳聚糖-柠檬酸水溶液(体系中壳聚糖浓度7.5％，柠檬酸浓度5％)，喷洒结束后持续搅拌60min，然后将物料烘干、过筛、包装即得抗菌材料。抗菌材料的抗菌性能见表1。
上述各实施例中，凹凸棒石是经相对于凹凸棒石质量分数2～3％的硫酸酸化处理、除砂得到纯度≥90％的产品，使用前粉碎过200目。
表1 实施例1-6制备的抗菌材料的不同pH值最小抑菌浓度
Figure PCTCN2021076254-appb-000001
Figure PCTCN2021076254-appb-000002

Claims (6)

  1. 一种凹凸棒石基pH响应抗菌材料的制备方法，是在搅拌状态下，将醛类天然抗菌剂直接喷洒于凹凸棒石粉末表面，持续搅拌20～30min，再置于球磨机研磨30～60min，然后置于搅拌罐中喷雾壳聚糖-柠檬酸水溶液；喷雾结束后持续搅拌30～120min，最后将所得物料烘干、过筛、包装即得抗菌材料。
  2. 如权利要求1所述一种凹凸棒石基pH响应抗菌材料的制备方法，其特征在于：所述凹凸棒石是经粉碎、酸化处理、除砂得到的纯度≥90％的凹凸棒石，其粒径在200目以上。
  3. 如权利要求1所述一种凹凸棒石基pH响应抗菌材料的制备方法，其特征在于：所述醛类天然抗菌剂为柠檬醛、月桂醛、乙二醇缩肉桂醛、肉桂醛、苯甲醛、紫苏醛、香草醛、糠醛、2,4辛二烯醛、2,4壬二烯醛、2,4庚二烯醛、2,4癸二烯醛中的至少一种；醛类天然抗菌剂用量为凹凸棒石质量的10～50％。
  4. 如权利要求1所述一种凹凸棒石基pH响应抗菌材料的制备方法，其特征在于：所述球磨机研磨工作状态的球料比为1:10。
  5. 如权利要求1所述一种凹凸棒石基pH响应抗菌材料的制备方法，其特征在于：所述壳聚糖-柠檬酸水溶液中，壳聚糖的质量浓度为5～10％，柠檬酸的浓度为1～5％。
  6. 如权利要求1所述一种凹凸棒石基pH响应抗菌材料的制备方法，其特征在于：壳聚糖水溶液的用量为凹凸棒石质量的7.5～20％。
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