CN116396414A - 一种壳聚糖基农药增溶剂的制备方法及其增溶方法 - Google Patents
一种壳聚糖基农药增溶剂的制备方法及其增溶方法 Download PDFInfo
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- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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Abstract
本发明涉及一种壳聚糖基农药增溶剂的制备方法,包括如下步骤:步骤1:将壳聚糖与3‑氯‑2‑羟基丙磺酸钠反应得到N‑磺化壳聚糖;步骤2:将步骤1得到的N‑磺化壳聚糖分散于无水N‑甲基吡咯烷酮中得到第一液体;步骤3:以乙酸乙酯为溶剂,加入卤代羧酸和N,N‑二甲基辛胺,得到第一产物;步骤4:将第一产物溶于氯化亚砜,反应得到第二产物;步骤5:将第二产物溶于无水N‑甲基吡咯烷酮中得到第二液体;步骤6:将第一液体缓慢滴加于第二液体中,室温反应,冷冻干燥得到N‑磺化‑O‑十二烷基苯甜菜碱化壳聚糖。本发明的制备方法得到的壳聚糖衍生物可溶解于水中,具有良好的生物相容性。采用本发明的增溶方法对难溶性农药进行增溶,其操作简单。
Description
技术领域
本发明涉及一种壳聚糖基农药增溶剂的制备方法及其增溶方法。
背景技术
在农业发展所面临的风险挑战中,农药的使用是较为突出的。据报道,在全球范围内,每年农作物因病虫害而导致的农业减产可高达10%-16%,为了保护农作物免受害虫、杂草和病原体的危害,人类使用各种农药来保证农作物的产量。但农药普遍存在利用率低、错误施药、非靶向施药等严重问题,同时为了保证农药的有效性,往往得过度使用。最重要的是由于挥发、药液漂移、光解、微生物降解等问题,这些农药在使用过程中绝大部分会流失到周围环境中,仅有10%~30%农药真正发挥了药效,给生态环境造成了极其严重的污染及破坏。
鉴于此,本案发明人对上述问题进行深入研究,遂有本案产生。
发明内容
本发明的目的在于提供一种相容性更好的壳聚糖基农药增溶剂的制备方法,本发明的另一目的在于提出采用壳聚糖基农药增溶剂的增容方法,其操作简单、便于推广应用。
为了达到上述目的,本发明采用这样的技术方案:
一种壳聚糖基农药增溶剂的制备方法,包括如下步骤:
步骤1:将壳聚糖与3-氯-2-羟基丙磺酸钠或2,3-环氧丙基-3-甲基氯化铵反应得到N-磺化壳聚糖;
步骤2:将步骤1得到的N-磺化壳聚糖分散于无水N-甲基吡咯烷酮中得到第一液体,其中N-磺化壳聚糖的质量百分浓度为0.05%-0.5%;
步骤3:以乙酸乙酯为溶剂,加入卤代羧酸和N,N-二甲基辛胺,或加入卤代羧酸和N,N-二甲基十二烷基胺,或加入卤代羧酸和N,N-二甲基十四烷基胺,得到第一产物;
步骤4:将第一产物溶于氯化亚砜,反应得到第二产物;
步骤5:在0-5℃下,将第二产物溶于无水N-甲基吡咯烷酮中得到第二液体;
步骤6:将第一液体缓慢滴加于第二液体中,室温反应,冷冻干燥得到N-磺化-O-十二烷基苯甜菜碱化壳聚糖。
作为本发明的优选方式,步骤1中壳聚糖和3-氯-2-羟基丙磺酸钠的摩尔比为1:1-1:5。
作为本发明的优选方式,步骤1中反应温度为60-100℃,反应时间为6-24h。
作为本发明的优选方式,所述卤代羧酸为对氯甲基苯甲酸、对溴甲基苯甲酸、氯乙酸、溴乙酸、氯丁酸、溴丁酸、氯己酸或溴己酸。
作为本发明的优选方式,对氯甲基苯甲酸和N,N-二甲基十二烷基胺的摩尔比为1:0.8-1:2。
作为本发明的优选方式,步骤4中,第一产物和氯化亚砜的摩尔比为1:1-1:6,反应温度为40-100℃,反应时间为0.5-5h。
作为本发明的优选方式,步骤6中N-磺化壳聚糖和第一产物的摩尔比为1:0.5-1:5。
作为本发明的优选方式,步骤6的反应时间为12-36h。
壳聚糖基农药增溶剂的增溶方法,包括如下步骤:
步骤A,室温下配制N-磺化-O-十二烷基苯甜菜碱化壳聚糖水溶液,将难溶性农药有机溶液加入N-磺化-O-十二烷基苯甜菜碱化壳聚糖水溶液,得到第三液体,其中,N-磺化-O-十二烷基苯甜菜碱化壳聚糖和难溶性农药的质量比范围为1:0.05-1:1.2;步骤B,将步骤A的第三液体超声波处理后,过滤,滤液经过真空冷冻干燥,制得负载农药的壳聚糖基增溶剂。
作为本发明的优选方式,所述难溶性农药为灭幼脲。
本发明的制备方法得到的壳聚糖衍生物可溶解于水中,具有良好的生物相容性,可达到对难溶性农药增溶的目的。具体表现为利用自组装作用,带苯环的烷烃长链与难溶性农药的相互作用从而将农药包裹在胶束的内部,磺酸基团作为亲水性基团以提高胶束的水溶性,具有广阔的应用前景。采用本发明的增溶方法对难溶性农药进行增溶,其操作简单,可以很大程度地减少农药制剂对有机溶剂的依赖,增大难溶性农药在水中的溶解度和提高农药药液在作物叶片表面的润湿性能,在农业生产中具有广阔的应用前景。
具体实施方式
为了进一步解释本发明的技术方案,下面结合实施例进行详细阐述。
(1)称1g壳聚糖(CS)溶解在50mL的2%质量百分比醋酸水溶液中,CS可以直接从市面上购买,称取2.44g3-氯-2-羟基丙磺酸钠溶于20mL去离子水中形成磺酸盐溶液,待CS充分溶解后,将CS溶液升温至85℃,将磺酸盐溶液缓慢滴加至上述CS溶液中,反应10h,透析,冷冻干燥得到N-磺化壳聚糖;
(2)取N-磺化壳聚糖1g分散于50mL无水N-甲基吡咯烷酮中,得到第一液体;
(3)称取10g对氯甲基苯甲酸和15g N,N-二甲基十二烷基胺溶于100mL乙酸乙酯,升温至85℃,反应10h。冷却至室温,抽滤,用乙酸乙酯洗涤滤饼,真空干燥,得到苯甲酸化十二烷基季铵盐。
(4)称取1.79g苯甲酸化十二烷基季铵盐溶于2mL氯化亚砜,75℃回流反应2h,旋蒸除去氯化亚砜得到第二产物。
(5)在0-5℃下,将第二产物溶于20mL无水N-甲基吡咯烷酮中得到第二液体;
(6)将第一液体缓慢滴加于第二液体中,室温反应24h,经透析和冷冻干燥得到N-磺化-O-十二烷基苯甜菜碱化壳聚糖。
本发明一种使用上述壳聚糖基农药增溶剂的增溶方法,包括以下步骤:
步骤A,配制1mg/mL的N-磺化-O-十二烷基苯甜菜碱化壳聚糖水溶液,配制1.5mg/mL灭幼脲乙醇溶液;将难溶性农药的有机溶液按照一定质量比(W增溶剂/W灭幼脲=1:0.05、1:0.1、1:0.4、1:0.6、1:0.8、1:1、1:1.2)加入到N-磺化-O-十二烷基苯甜菜碱化壳聚糖的水溶液中,得到第三液体;(此处增溶剂指N-磺化-O-十二烷基苯甜菜碱化壳聚糖)
将步骤(B)第三液体室温超声波处理0.5h后,去离子水透析2h,10000r/min离心10min,通过0.45μm滤膜,滤液经真空冷冻干燥,即制得负载灭幼脲农药的壳聚糖基增溶剂。N-磺化-O-十二烷基苯甜菜碱化壳聚糖对灭幼脲的载药量和包封率如下表:
按照此技术,利用壳聚糖基表面活性剂自组装形成的纳米胶束对农药灭幼脲进行增溶研究,制备的农药制剂不含任何有机溶剂且易溶于水。载灭幼脲测试表明该纳米胶束的最大载药量为16.67%,包封率为25.00%,增溶后的灭幼脲在水中的溶解度提高到80.00μg/mL,显著高于传统灭幼脲原药(灭幼脲在水中的溶解度仅为0.20μg/mL)。对应的水溶液在甘蓝叶片上的接触角为104°,相比纯水的139°接触角,其农药药液在甘蓝叶片上的润湿性能大幅提升。
本发明的合成路线如下:
本发明的产品形式并非限于本案实施例,任何人对其进行类似思路的适当变化或修饰,皆应视为不脱离本发明的专利范畴。
Claims (10)
1.一种壳聚糖基农药增溶剂的制备方法,其特征在于,包括如下步骤:
步骤1:将壳聚糖与3-氯-2-羟基丙磺酸钠或2,3-环氧丙基-3-甲基氯化铵反应得到N-磺化壳聚糖;
步骤2:将步骤1得到的N-磺化壳聚糖分散于无水N-甲基吡咯烷酮中得到第一液体,其中N-磺化壳聚糖的质量百分浓度为0.05%-0.5%;
步骤3:以乙酸乙酯为溶剂,加入卤代羧酸和N,N-二甲基辛胺,或加入卤代羧酸和N,N-二甲基十二烷基胺,或加入卤代羧酸和N,N-二甲基十四烷基胺,得到第一产物;
步骤4:将第一产物溶于氯化亚砜,反应得到第二产物;
步骤5:在0-5℃下,将第二产物溶于无水N-甲基吡咯烷酮中得到第二液体;
步骤6:将第一液体缓慢滴加于第二液体中,室温反应,冷冻干燥得到N-磺化-O-十二烷基苯甜菜碱化壳聚糖。
2.如权利要求1所述的一种壳聚糖基农药增溶剂的制备方法,其特征在于,步骤1中壳聚糖和3-氯-2-羟基丙磺酸钠的摩尔比为1:1-1:5。
3.如权利要求2所述的一种壳聚糖基农药增溶剂的制备方法,其特征在于,步骤1中反应温度为60-100℃,反应时间为6-24h。
4.如权利要求3所述的一种壳聚糖基农药增溶剂的制备方法,其特征在于,所述卤代羧酸为对氯甲基苯甲酸、对溴甲基苯甲酸、氯乙酸、溴乙酸、氯丁酸、溴丁酸、氯己酸或溴己酸。
5.如权利要求4所述的一种壳聚糖基农药增溶剂的制备方法,其特征在于,对氯甲基苯甲酸和N,N-二甲基十二烷基胺的摩尔比为1:0.8-1:2。
6.如权利要求5所述的一种壳聚糖基农药增溶剂的制备方法,其特征在于,步骤4中,第一产物和氯化亚砜的摩尔比为1:1-1:6,反应温度为40-100℃,反应时间为0.5-5h。
7.如权利要求6所述的一种壳聚糖基农药增溶剂的制备方法,其特征在于,步骤6中N-磺化壳聚糖和第一产物的摩尔比为1:0.5-1:5。
8.如权利要求7所述的一种壳聚糖基农药增溶剂的制备方法,其特征在于,步骤6的反应时间为12-36h。
9.壳聚糖基农药增溶剂的增溶方法,其特征在于,包括如下步骤:
步骤A,室温下配制N-磺化-O-十二烷基苯甜菜碱化壳聚糖水溶液,配制难溶性农药有机溶液,将难溶性农药有机溶液加入N-磺化-O-十二烷基苯甜菜碱化壳聚糖水溶液,得到第三液体,其中,N-磺化-O-十二烷基苯甜菜碱化壳聚糖和难溶性农药的质量比范围为1:0.05-1:1.2;
步骤B,将步骤A的第三液体超声波处理后,过滤,滤液经过真空冷冻干燥,制得负载农药的壳聚糖基增溶剂。
10.如权利要求9所述的壳聚糖基农药增溶剂的增溶方法,其特征在于,所述难溶性农药为灭幼脲。
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