CN114507359A - 木质素磺酸盐的改性材料制备法及其在纳米农药中的应用 - Google Patents
木质素磺酸盐的改性材料制备法及其在纳米农药中的应用 Download PDFInfo
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- CN114507359A CN114507359A CN202210145722.0A CN202210145722A CN114507359A CN 114507359 A CN114507359 A CN 114507359A CN 202210145722 A CN202210145722 A CN 202210145722A CN 114507359 A CN114507359 A CN 114507359A
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- BQYJATMQXGBDHF-UHFFFAOYSA-N difenoconazole Chemical compound O1C(C)COC1(C=1C(=CC(OC=2C=CC(Cl)=CC=2)=CC=1)Cl)CN1N=CN=C1 BQYJATMQXGBDHF-UHFFFAOYSA-N 0.000 claims description 39
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- PXMNMQRDXWABCY-UHFFFAOYSA-N 1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)pentan-3-ol Chemical compound C1=NC=NN1CC(O)(C(C)(C)C)CCC1=CC=C(Cl)C=C1 PXMNMQRDXWABCY-UHFFFAOYSA-N 0.000 claims description 5
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- PRLVTUNWOQKEAI-VKAVYKQESA-N buprofezin Chemical compound O=C1N(C(C)C)\C(=N\C(C)(C)C)SCN1C1=CC=CC=C1 PRLVTUNWOQKEAI-VKAVYKQESA-N 0.000 claims description 2
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- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 claims description 2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic 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
- 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
- A01N25/10—Macromolecular compounds
-
- 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
- A01N25/22—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 ingredients stabilising the active ingredients
-
- 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
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Agronomy & Crop Science (AREA)
- Plant Pathology (AREA)
- Toxicology (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明公开了一种木质素磺酸盐的改性材料的制备方法:将木质素磺酸盐溶于溶剂中,再加入三乙胺和脂肪族/芳香族物,搅拌条件下反应24±2h,离心取上清液,在上清液加入异丙醇后得到沉淀,将沉淀真空干燥,得到木质素磺酸盐的改性材料。本发明还同时提供了上述木质素磺酸盐的改性材料的用途:以木质素磺酸盐的改性材料为载体材料,负载农药原药,制备成纳米农药。
Description
技术领域
本发明涉及农业纳米材料制备及应用技术领域,尤其涉及一种木质素磺酸盐的疏水性改造纳米材料的制备及其应用。
背景技术
在农业领域中,全世界每年要使用400多万吨农药来保护农作物。然而,近年来,农药的滥用和高残留给环境和人类健康带来了巨大的负担。这些严重的危害不仅是由于农药的低效,而且是由于在常规配方中大量使用有机溶剂和表面活性剂。因此,有必要使用更高效、绿色的农药来保护农作物,促进农业的可持续发展。纳米农药与传统农药相比具有独特的优势,被认为有广泛的应用前景。
纳米农药是近年来出现的一种具有良好发展前景的农药制剂。与传统农药制剂相比,纳米农药具有更小的粒径和更高的比表面积,因此,基于纳米材料构建的纳米农药,在田间使用时,表现出了更好的分散性、渗透性、持效性和抗光解性等性能。在相关报道中,一些种类的无机材料,如介孔硅、金属有机骨架和碳酸钙或有机材料,如人工聚合物、壳聚糖和纤维素,已被用于构建农药纳米载体。在医药领域中,控缓释纳米制剂已经得到了很好的应用,但由于过高的材料成本和繁琐的技术要求,负载农药的控缓释制剂即纳米农药在农业领域中的应用尚不广泛。
木质素是自然界中含量第二丰富的可再生聚合物,是木材的主要成分之一,木质素和它的众多衍生物可从制浆和造纸工业产生的副产品中获得。由于木质素及其衍生物中含有芳香基、羟基和羧基等许多官能团,通过对这些官能团进行接枝共聚、酰化和磺化等改性反应,可以改变它们的化学性质,拓宽木质素及其衍生物的应用领域。近年来,木质素磺酸盐及其改性衍生物因其成本低、生物降解性好、紫外吸收能力强等优点,受到纳米农药领域的关注。但由于木质素磺酸盐的强水溶性。限制了它在制作纳米农药的诸多方法中的使用,比如界面聚合法、溶剂挥发法、溶剂交换法等,对木质素磺酸盐进行改性,提高它的脂溶性,拓宽它的使用范围,成为研究的热点。
发明专利CN110946133A公开了一种以木质素为包裹基质的纳米抗光解控释农药及其制备方法,该发明以木质素磺酸盐为材料,通过交联剂的交联,形成包裹农药的壁材,以农药原药为芯材,得到了一种纳米农药,该制剂具有缓释和抗光降解的功能。但是该方案直接应用了木质素磺酸盐,没有改性,工艺较为繁琐,所用交联剂对苯二胺、间苯二胺已被世界卫生组织列为致癌物质,毒性较大,环保性差;发明专利CN108739807B描述了一种以植物油酸-壳聚糖基多元醇与多元异氰酸酯形成的聚合物为壁材,以农药为芯材制备的纳米微囊制剂,该制剂的粒径达到了纳米级别,但是在一些报道中,异氰酸酯存在与化学式中含有羟基的农药相互反应的问题。
目前所公开的纳米农药仍然存在制备工艺复杂、成本较高、环境中难以降解、颗粒分布不均匀,缓释与抗光降解能力低等缺点,因此,有必要缩减材料成本,开发一种工艺简单,环境友好,能制备持效期长、可缓慢降解的新型纳米农药的木质素磺酸盐疏水性改性纳米材料。
CN113260257A的发明《纳米农药制剂及其制备方法》,公开了纳米农药制剂其制备方法。其助剂中使用了木质素磺酸钠、聚苯乙烯-马来酸酐共聚物,但是并不涉及对载体的改性。
发明内容
本发明要解决的技术问题是提供一种木质素磺酸盐的疏水性改造纳米材料的制备法及其应用。
为解决上述技术问题,本发明提供一种木质素磺酸盐的改性材料(木质素磺酸盐的疏水性纳米改性材料)的制备方法:
将木质素磺酸盐溶于溶剂中,再加入三乙胺和脂肪族/芳香族物,搅拌条件下反应24±2h,离心取上清液,在上清液加入异丙醇后得到沉淀,将沉淀真空干燥(清洗后再真空干燥),得到木质素磺酸盐的改性材料;
所述木质素磺酸盐:脂肪族/芳香族物=1:2~7的重量比;
脂肪族/芳香族物:三乙胺=1:(1±0.05)的摩尔比;
所述脂肪族/芳香族物为以下任一:脂肪族/芳香族酸酐、脂肪族/芳香族酰氯。
说明:木质素磺酸盐的改性材料,即,木质素磺酸盐疏水性纳米改性材料,为木质素磺酸盐与脂肪族/芳香族物形成的聚合物,可作为木质素磺酸盐疏水性纳米载体。
作为本发明的木质素磺酸盐的改性材料的制备方法的改进:
脂肪族/芳香族族酸酐为以下任一:苯甲酸酐(优选)、甲基丙烯酸酐、邻苯二甲酸酐、顺丁烯二酸酐、苯乙酸酐、琥珀酸酐、辛烯基琥珀酸酐(优选);
脂肪族/芳香族酰氯为以下任一:苯甲酰氯(优选)、甲基丙烯酰氯、邻苯二甲酰氯、苯乙酰氯。
作为本发明的木质素磺酸盐的改性材料的制备方法的进一步改进:
木质素磺酸盐(水溶性木质素磺酸盐)为以下任一:木质素磺酸钠、木质素磺酸钙、木质素磺酸钾等。
作为本发明的木质素磺酸盐的改性材料的制备方法的进一步改进:
溶剂为N,N-二甲基甲酰胺、二甲亚砜。
作为本发明的木质素磺酸盐的改性材料的制备方法的进一步改进:搅拌反应的温度为50~70℃。
说明:将木质素磺酸盐溶于溶剂中,可采用加热助溶的形式(例如为90℃的油浴中搅拌),1g木质素磺酸盐一般配用10±3ml的溶剂;而后降至室温后,再加入三乙胺和脂肪族/芳香族物,于50~70℃进行搅拌反应。
作为本发明的木质素磺酸盐的改性材料的制备方法的进一步改进:疏水性纳米改性材料的粒径为1~300nm(约为100nm左右)。
说明:本发明是在木质素磺酸盐结构中引入脂肪族/芳香族酸酐或者脂肪族/芳香族酰氯,来改性木质素磺酸盐的结构,不仅降低了木质素磺酸盐的亲水性,增加了其疏水性,使改性后的木质素磺酸盐具有良好的亲水亲油性能,同时又降低其粒径。
本发明还同时提供了利用上述任一方法制备所得的木质素磺酸盐的改性材料的用途:
以木质素磺酸盐的改性材料为载体材料,负载农药原药,制备成纳米农药。
农药原药选用亲脂性较强的农药。
此纳米农药为具有高稳定性与良好缓释效果的纳米农药;可更好的应用于农业领域。
作为本发明的用途的改进:农药原药为以下的至少一种(即,一种或几种):苯醚甲环唑、吡唑醚菌酯、戊唑醇、丙环唑、高效氯氟氰菊酯、高效氯氰菊酯、三环唑、噻嗪酮、咪鲜胺。
作为本发明的用途的进一步改进:所述纳米农药应用于农作物病虫害防治。
本发明针对现有技术存在的问题,旨在提供一种以木质素磺酸盐为材料,通过木质素磺酸盐中的多个羟基与脂肪族酸酐或芳香族酸酐或其相关酰氯的酯化反应,产生一种新的纳米载体,进而对农药进行包裹,形成具有缓释与抗光降解能力的纳米农药制剂,该方法制作简单,成本低廉,制备的农药缓释和抗光降解效果好,可负载不同的农药制成纳米制剂。
本发明以木质素磺酸盐作为原料,使用不同配比的脂肪族酸酐或芳香族酸酐或其相关酰氯与木质素磺酸盐进行酯化,得到不同亲脂性的木质素磺酸盐疏水性改性材料,经过乳化、溶剂交换法或者溶剂挥发法制备得到具有缓释和抗光降解的农药纳米制剂。
例如:所述木质素磺酸盐疏水性改性材料的结构示意如下:
与现有技术比较,本发明具有如下优势:
(1)本发明的木质素磺酸盐的改性材料(木质素磺酸盐疏水性纳米改性材料),材料来源于造纸工业中的副产品,来源广泛,成本低廉,具有良好的生物可降解性,减少了对环境的污染,由于未使用交联剂,只需要进行一步反应即可合成,工艺简单。
(2)本发明的利用木质素磺酸盐疏水性纳米改性材料制备而得的纳米农药制剂,在减少有毒有机溶剂和表面活性剂使用的情况下,依然具有良好的制剂稳定性(图5),且并未使用有毒的交联剂。
(3)本发明的纳米农药制剂,具有与传统商品化微乳剂相近的稳定性和杀菌效果,但是比商品化微乳剂具有更好的抗光解能力(图4)。
(4)本发明的纳米农药制剂,平均值在100nm左右,粒径小,分散程度良好,对叶片具有很好的亲和力和粘附性(图2)。
(5)本发明的纳米农药制剂,不仅具有与传统商品化微乳剂相近的稳定性和杀菌效果,而且可以缓慢释放包覆的农药原药,具有明显的缓释效果,能够有效减少田间农药的使用次数和用量,大大提高了现有农药的利用率。
(6)本发明的木质素磺酸盐疏水性纳米改性材料,在纳米农药的制作过程中,因为降低了现有木质素磺酸盐的亲水性,有效增加了木质素磺酸盐的疏水性,通过酯化反应大大提高了它的亲油性,从而可以形成相比于空心微囊更坚实的纳米农药颗粒。
附图说明
下面结合附图对本发明的具体实施方式作进一步详细说明。
图1为苯甲酸酯化木质素磺酸盐衍生物核磁氢谱图;
图2为苯醚甲环唑纳米农药制剂的扫描电镜(SEM)图;
图3为苯醚甲环唑纳米农药的释放曲线图;
图4为苯醚甲环唑纳米农药的抗光降解曲线图;
图5为苯醚甲环唑纳米农药的稳定性指数(TSI)图。
具体实施方式
下面结合具体实施例对本发明进行进一步描述,但本发明的保护范围并不仅限于此:
一、木质素磺酸盐的疏水性纳米改性材料的制备:
实施例1、苯甲酸酯化木质素磺酸钠的制备(木质素磺酸钠与苯甲酸酐重量比为1:2):
称取1g木质素磺酸钠(LS)加入到10ml N,N-二甲基甲酰胺(DMF)中,在90℃的油浴中搅拌至木质素磺酸钠完全溶解;
降至室温后加入2g苯甲酸酐(Bma)与1当量(相对于苯甲酸酐)的三乙胺(TEA),60℃下搅拌反应24h。
离心(8000r/min,5min)取上清液;随后,倒入200ml的异丙醇后离心得到沉淀,用异丙醇清洗沉淀两次(每次清洗时,异丙醇的用量为200ml),放入真空干燥箱中,40℃真空干燥(干燥至恒重),制得苯甲酸酯化木质素磺酸钠(即,苯甲酸酯化木质素磺酸钠纳米载体)。粒径为100nm左右。
实施例2、将实施例1中的苯甲酸酐的量由“2g”改成“3g”,三乙胺仍然为1当量(相对于苯甲酸酐);其余等同于实施例1。所得苯甲酸酯化木质素磺酸钠纳米载体的粒径为100nm左右。
实施例3、将实施例1中的苯甲酸酐的量由“2g”改成“5g”,三乙胺仍然为1当量(相对于苯甲酸酐);其余等同于实施例1。所得苯甲酸酯化木质素磺酸钠纳米载体的粒径为100nm左右。
实施例4、将实施例1中的苯甲酸酐的量由“2g”改成“7g”,三乙胺仍然为1当量(相对于苯甲酸酐);其余等同于实施例1。所得苯甲酸酯化木质素磺酸钠纳米载体的粒径为100nm左右。
实施例5、将实施例1中的“2g苯甲酸酐”改成“3g邻苯二甲酸酐”,三乙胺(TEA)的1当量相对于邻苯二甲酸酐而言,其余等同于实施例1。所得邻苯二甲酸酯化木质素磺酸钠纳米载体的粒径为100nm左右。
实施例6、将实施例1中的“2g苯甲酸酐”改成“3g苯甲酰氯”,三乙胺(TEA)的1当量相对于苯甲酰氯而言,其余等同于实施例1。所得苯甲酰化木质素磺酸钠纳米载体的粒径为100nm左右。
实施例7、将实施例1中的“2g苯甲酸酐”改成“5g辛烯基琥珀酸酐”,三乙胺(TEA)的1当量相对于辛烯基琥珀酸酐而言,其余等同于实施例1。所得辛烯基琥珀酸酯化木质素磺酸钠纳米载体的粒径为100nm左右。
二、利用木质素磺酸盐的疏水性纳米改性材料制备纳米农药:
实施例8、以实施例1得到的苯甲酸酯化木质素磺酸钠制备苯醚甲环唑纳米农药
将20mg十二烷基硫酸钠(SDS)溶于10ml水中,制得含0.2%SDS的水溶液,作为水相;
取100mg实施例1得到的苯甲酸酯化木质素磺酸钠纳米载体和20mg苯醚甲环唑,溶于500mg二氯甲烷中,作为油相;
将油相滴入水相中,放入高剪切乳化机,10000r/min剪切1min,放入细胞破碎仪,70W功率下超声处理1min,1000r/min搅拌两小时,将二氯甲烷挥发干净。制得所需要的苯醚甲环唑纳米农药制剂。
实施例9、将实施例8中所用的“实施例1制备而得的纳米载体”改成“实施例2制备而得的纳米载体”,重量保持不变,其余等同于实施例8。
实施例10、将实施例8中所用的“实施例1制备而得的纳米载体”改成“实施例3制备而得的纳米载体”,重量保持不变,其余等同于实施例8。
实施例11、将实施例8中所用的“实施例1制备而得的纳米载体”改成“实施例4制备而得的纳米载体”,重量保持不变,其余等同于实施例8。
实施例12、以实施例3得到的苯甲酸酯化木质素磺酸钠制备戊唑醇纳米农药
取10mg SDS溶于5ml水中,制得含0.2%SDS的水溶液,作为水相;
取50mg实施例3制备的苯甲酸酯化木质素磺酸钠纳米载体(木质素磺酸钠与苯甲酸酐1:5反应所得)和10mg戊唑醇,溶于250mg二氯甲烷中,作为油相;
将油相滴入水相中,放入高剪切乳化机,10000r/min剪切1min,放入细胞破碎仪,70W功率下超声处理1min,1000r/min搅拌两小时。制得所需要的戊唑醇纳米农药制剂。
实施例13、以实施例3得到的苯甲酸酯化木质素磺酸钠制备丙环唑纳米农药
取10mg SDS溶于5ml水中,制得含0.2%SDS的水溶液,作为水相;
取50mg实施例3制备的苯甲酸酯化木质素磺酸钠纳米载体(木质素磺酸钠与苯甲酸酐1:5反应所得)和10mg丙环唑,溶于250mg二氯甲烷中,作为油相;
将油相滴入水相中,放入高剪切乳化机,10000r/min剪切1min,放入细胞破碎仪,70W功率下超声处理1min,1000r/min搅拌两小时。制得所需要的丙环唑纳米农药制剂。
三、以木质素磺酸盐为材料的纳米缓释抗光解农药的核磁氢谱对比图片
图1为实施例3制作的苯甲酸酯化木质素磺酸钠纳米载体与木质素磺酸钠原料的核磁氢谱对比图,与木质素磺酸钠的核磁图谱相比,苯甲酸酯化木质素磺酸钠纳米载体在化学位移δ=7.2-8.2ppm处出现了两个新的吸收峰,为苯甲酰基的苯环峰,即为酯化后产物,苯甲酸酯化木质素磺酸钠纳米载体的苯环上的氢。
四、以苯甲酸酯化木质素磺酸盐衍生物为原料制备得到的纳米农药的形态表征
以实施例10所得到的苯醚甲环唑纳米农药制剂为样品,采用扫描电镜对所制备的纳米农颗粒进行微观形态观察,结果如图2所示。从图中可以看到,本发明的纳米颗粒制剂颗粒呈球形,表面光滑,纳米农药平均粒径大小在100-200nm左右,属于一种纳米颗粒悬浮剂制剂。
五、以木质素磺酸盐为材料的纳米缓释抗光解农药的缓释实验
以实施例10制备得到的苯醚甲环唑纳米农药和从市场上购买的商品化苯醚甲环唑微乳剂(威远生物化工有限公司)为试样进行苯醚甲环唑纳米农药制剂的缓释实验:称取相同苯醚甲环唑含量的纳米农药微乳剂2mL,装入透析袋中,然后在室温磁力搅拌下,置于100mL含1%吐温-80的去离子水中透析。在不同的间隔时间,从1%吐温-80溶液中取1ml样品,加入相同体积的1%吐温-80溶液,采用高效液相色谱法对样品浓度进行测定。
图3显示了实施例10中苯醚甲环唑纳米农药和苯醚甲环唑微乳剂在水溶液中的释放行为。微乳剂在初始阶段释放速度较快,在48h时,微乳剂的累积释放率达到94.6%,96h时达到100%。而纳米农药的释放率呈非常缓慢的增加趋势,120h后,纳米农药的累积释放率仅为34.7%,明显低于微乳剂,证明了纳米农药的缓释性能。
以不同的纳米载体参照实施例10的方法制备纳米农药,不同案例所得的纳米农药,120h后的累积释放率如下表1所示:
表1
因此,可知:以木质素磺酸盐及其衍生物为材料的纳米抗光解控释农药制剂的活性成份也具备一定的缓释性能。
六、以木质素磺酸盐为材料的纳米缓释抗光解农药的抗光降解实验
苯醚甲环唑纳米农药制剂的抗光降解实验:以实施例10的苯醚甲环唑纳米农药和从市场上购买的商品化苯醚甲环唑微乳剂(威远生物化工有限公司)为试样,分别取相同苯醚甲环唑浓度的纳米农药和微乳剂分成等量的1mL溶液,置于离心管中,用254nm,6W的紫外光照射。光源距离悬浮物表面的距离为10cm。定期选择试管进行高效液相色谱分析,检测苯醚甲环唑的剩余浓度。
图4显示了实施例10中苯醚甲环唑纳米农药制剂和苯醚甲环唑微乳剂的抗光降解能力,苯醚甲环唑微乳剂在紫外线照射4h后,降解率达到了89.9%,几乎完全降解。但是,苯醚甲环唑纳米农药在紫外线照射4h后,降解速率为31.4%,12h后,降解速率只有58.1%。上述结果表明,纳米农药可提高苯醚甲环唑的光稳定性,有利于延长苯醚甲环唑的使用时间和提高它的利用效率,从而延长杀菌剂的药效周期,降低喷施频率。
以不同的纳米载体参照实施例10的方法制备纳米农药,不同案例所得的纳米农药,12h光降解率如下表2所示:
表2
七、以木质素磺酸盐为材料的纳米缓释抗光解农药的杀菌活性实验
以实施例10的纳米苯醚甲环唑制剂为试样,以相同浓度的苯醚甲环唑原药、苯醚甲环唑微乳剂和苯醚甲环唑纳米制剂为对照,测试三种试剂对炭疽菌的抑制活性,根据菌丝生长的抑制率计算三种制剂的EC50值,分别为0.404、0.343和0.357μg/mL。结果表明,苯醚甲环唑纳米制剂具有抑菌活性,且与市售的苯醚甲环唑微乳剂抑菌活性无显著差异。测试结果见表3。
表3、几种苯醚甲环唑制剂对炭疽菌生长的抑制毒力测定结果
说明:其他以木质素磺酸盐及其衍生物为材料的纳米抗光解控释农药制剂,均具有一定的杀菌效果。
八、以木质素磺酸盐为材料的纳米缓释抗光解农药的制剂稳定性
以实施例8、9、10、11的纳米苯醚甲环唑制剂为试样,使用多重光散射仪进行制剂稳定性的测试,检测不同比例的木质素磺酸钠与苯甲酸酐反应对纳米农药稳定性的影响。
图5显示了在25℃下,1h内,相同苯醚甲环唑浓度的不同木质素磺酸钠:苯甲酸酐反应比例的纳米农药和微乳剂的稳定性分析仪稳定指数(TSI)。TSI值越高,表明配方样品稳定性越差。从图5中可以观察到,以较低苯甲酸酐比例反应的木质素磺酸钠拥有更差的稳定性,以较高苯甲酸酐比例反应的样品稳定性与微乳剂相近。即,木质素磺酸钠:苯甲酸酐=1:5或=1:7时样品稳定性与微乳剂相近。
以不同的纳米载体参照实施例10的方法制备纳米农药,不同案例所得的纳米农药,按照上述方法进行检测,所得结果如下表4:
表4
纳米载体 | 60min时对应的TSI |
木质素磺酸钠:苯甲酸酐=1:5 | 0.392 |
木质素磺酸钠:邻苯二甲酸酐=1:5 | 0.702 |
木质素磺酸钠:甲基丙烯酸酐=1:5 | 0.671 |
木质素磺酸钠:顺丁烯二酸酐=1:5 | 0.572 |
木质素磺酸钠:琥珀酸酐=1:5 | 0.452 |
木质素磺酸钠:辛烯基琥珀酸酐=1:5 | 0.406 |
苯醚甲环唑微乳剂 | 0.735 |
最后,还需要注意的是,以上列举的仅是本发明的若干个具体实施例。显然,本发明不限于以上实施例,还可以有许多变形。本领域的普通技术人员能从本发明公开的内容直接导出或联想到的所有变形,均应认为是本发明的保护范围。
Claims (9)
1.木质素磺酸盐的改性材料的制备方法,其特征在于:
将木质素磺酸盐溶于溶剂中,再加入三乙胺和脂肪族/芳香族物,搅拌条件下反应24±2h,离心取上清液,在上清液加入异丙醇后得到沉淀,将沉淀真空干燥,得到木质素磺酸盐的改性材料;
所述木质素磺酸盐:脂肪族/芳香族物=1:2~7的重量比;
脂肪族/芳香族物:三乙胺=1:(1±0.05)的摩尔比;
所述脂肪族/芳香族物为以下任一:脂肪族/芳香族酸酐、脂肪族/芳香族酰氯。
2.根据权利要求1所述的木质素磺酸盐的改性材料的制备方法,其特征在于:
脂肪族/芳香族族酸酐为以下任一:苯甲酸酐、甲基丙烯酸酐、邻苯二甲酸酐、顺丁烯二酸酐、苯乙酸酐、琥珀酸酐、辛烯基琥珀酸酐;
脂肪族/芳香族酰氯为以下任一:苯甲酰氯、甲基丙烯酰氯、邻苯二甲酰氯、苯乙酰氯。
3.根据权利要求2所述的木质素磺酸盐的改性材料的制备方法,其特征在于:
木质素磺酸盐为以下任一:木质素磺酸钠、木质素磺酸钙、木质素磺酸钾。
4.根据权利要求3所述的木质素磺酸盐的改性材料的制备方法,其特征在于:
溶剂为N,N-二甲基甲酰胺、二甲亚砜。
5.根据权利要求1~4任一所述的木质素磺酸盐的改性材料的制备方法,其特征在于:搅拌反应的温度为50~70℃。
6.根据权利要求5所述的木质素磺酸盐的改性材料的制备方法,其特征在于:改性材料的粒径为1~300nm。
7.如权利要求1~6任一方法制备所得的木质素磺酸盐的改性材料的用途,其特征在于:
以木质素磺酸盐的改性材料为载体材料,负载农药原药,制备成纳米农药。
8.根据权利要求7所述的用途,其特征在于农药原药为以下的至少一种:苯醚甲环唑、吡唑醚菌酯、戊唑醇、丙环唑、高效氯氟氰菊酯、高效氯氰菊酯、三环唑、噻嗪酮、咪鲜胺。
9.根据权利要求7或8所述的用途,其特征在于:所述纳米农药应用于农作物病虫害防治。
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