CN104621102B - Method for preparing adhesive abamectin polydopamine microcapsule by emulsion interface polymerization method - Google Patents
Method for preparing adhesive abamectin polydopamine microcapsule by emulsion interface polymerization method Download PDFInfo
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- 239000005660 Abamectin Substances 0.000 title claims abstract description 25
- 239000003094 microcapsule Substances 0.000 title claims abstract description 23
- IBSREHMXUMOFBB-JFUDTMANSA-N 5u8924t11h Chemical compound O1[C@@H](C)[C@H](O)[C@@H](OC)C[C@@H]1O[C@@H]1[C@@H](OC)C[C@H](O[C@@H]2C(=C/C[C@@H]3C[C@@H](C[C@@]4(O3)C=C[C@H](C)[C@@H](C(C)C)O4)OC(=O)[C@@H]3C=C(C)[C@@H](O)[C@H]4OC\C([C@@]34O)=C/C=C/[C@@H]2C)/C)O[C@H]1C.C1=C[C@H](C)[C@@H]([C@@H](C)CC)O[C@]11O[C@H](C\C=C(C)\[C@@H](O[C@@H]2O[C@@H](C)[C@H](O[C@@H]3O[C@@H](C)[C@H](O)[C@@H](OC)C3)[C@@H](OC)C2)[C@@H](C)\C=C\C=C/2[C@]3([C@H](C(=O)O4)C=C(C)[C@@H](O)[C@H]3OC\2)O)C[C@H]4C1 IBSREHMXUMOFBB-JFUDTMANSA-N 0.000 title claims abstract description 22
- 229950008167 abamectin Drugs 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 11
- 229920001690 polydopamine Polymers 0.000 title claims abstract description 10
- 239000000839 emulsion Substances 0.000 title claims abstract description 9
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 6
- 239000000853 adhesive Substances 0.000 title claims abstract description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims abstract description 4
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- RRZXIRBKKLTSOM-XPNPUAGNSA-N avermectin B1a Chemical compound C1=C[C@H](C)[C@@H]([C@@H](C)CC)O[C@]11O[C@H](C\C=C(C)\[C@@H](O[C@@H]2O[C@@H](C)[C@H](O[C@@H]3O[C@@H](C)[C@H](O)[C@@H](OC)C3)[C@@H](OC)C2)[C@@H](C)\C=C\C=C/2[C@]3([C@H](C(=O)O4)C=C(C)[C@@H](O)[C@H]3OC\2)O)C[C@H]4C1 RRZXIRBKKLTSOM-XPNPUAGNSA-N 0.000 claims abstract 3
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 10
- 229960003638 dopamine Drugs 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims 2
- 238000003756 stirring Methods 0.000 claims 2
- 238000001035 drying Methods 0.000 claims 1
- 238000013270 controlled release Methods 0.000 abstract description 13
- 239000012071 phase Substances 0.000 abstract description 5
- 239000008346 aqueous phase Substances 0.000 abstract description 3
- 238000009472 formulation Methods 0.000 abstract description 3
- 238000010907 mechanical stirring Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000012695 Interfacial polymerization Methods 0.000 abstract description 2
- 239000000575 pesticide Substances 0.000 description 9
- 241000196324 Embryophyta Species 0.000 description 4
- 230000003592 biomimetic effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000002552 dosage form Substances 0.000 description 2
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- 230000003993 interaction Effects 0.000 description 2
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- 238000001291 vacuum drying Methods 0.000 description 2
- 108010062877 Bacteriocins Proteins 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000004495 emulsifiable concentrate Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
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- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000010983 kinetics study Methods 0.000 description 1
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Abstract
本发明涉及一种乳液界面聚合法制备粘附性阿维菌素聚多巴胺微胶囊的方法。针对阿维菌素见光易分解，且其大多数剂型不能有效停留在植物叶面的问题。本发明以含十六烷基三甲基氯化铵(1.5％m/v水相)的Tris‑HCl缓冲液为水溶液，含阿维菌素的正丁醇溶液为油相；通过多巴胺(浓度为1mg/mL)在乳液界面上进行氧化自聚合，室温下机械搅拌24h，离心洗涤得到具有粘附性和光稳定性的阿维菌素聚多巴胺微胶囊，且该微胶囊具有温度和pH控释性。本发明采用的方法可制得尺寸均一，高负载量，具有粘附性的阿维菌素控释聚多巴胺微胶囊，产率高，步骤简单，可用于工业化。The invention relates to a method for preparing adhesive abamectin polydopamine microcapsules by an emulsion interfacial polymerization method. In view of the problem that abamectin is easily decomposed when exposed to light, and most of its formulations cannot effectively stay on the leaves of plants. In the present invention, the Tris-HCl buffer containing cetyltrimethylammonium chloride (1.5% m/v aqueous phase) is an aqueous solution, and the n-butanol solution containing avermectin is an oil phase; 1 mg/mL) on the emulsion interface to carry out oxidative self-polymerization, mechanical stirring at room temperature for 24h, centrifugal washing to obtain avermectin polydopamine microcapsules with adhesion and photostability, and the microcapsules have temperature and pH controlled release sex. The method adopted in the present invention can prepare abamectin controlled-release polydopamine microcapsules with uniform size, high loading and adhesion, high yield, simple steps, and can be used for industrialization.
Description
技术领域technical field
本发明涉及一种先将阿维菌素进行乳化，然后通过多巴胺及其衍生物在乳液界面上进行氧化自聚合，得到具有粘附性、温度控释、pH控释和光稳定性的微胶囊的方法。The invention relates to a method for firstly emulsifying abamectin, and then performing oxidative self-polymerization on the interface of the emulsion through dopamine and its derivatives to obtain microcapsules with adhesiveness, temperature-controlled release, pH-controlled release and light stability. method.
背景技术Background technique
中国是农业大国，有害生物多发、频发、重发。施用化学农药防治病、虫、草害是目前最主要而有效的防治手段。然而目前喷洒出去的农药仅有20％～30％持留沉积在靶标上，另外70％～80％飘失或流失到土壤中，对动物和人类的生存环境造成污染。造成农药浪费和流失的原因主要有两个：其一，施用在农作物上的农药，不能根据农作物生长需给求药，经过日晒雨淋后，大多数能挥发或被分解而无法有效利用；其二，常用的农药剂型在作物表面不能形成有效的铺展和停留，导致了大多数农药在施药后很快流失。China is a big agricultural country, and harmful organisms are prone to frequent, frequent and re-emergence. The application of chemical pesticides to control diseases, insects and weeds is currently the most important and effective means of control. However, only 20% to 30% of the pesticides sprayed at present remain deposited on the target, and the other 70% to 80% are lost or lost to the soil, causing pollution to the living environment of animals and humans. There are two main reasons for the waste and loss of pesticides: First, the pesticides applied to crops cannot be given according to the needs of crop growth. Second, the commonly used pesticide formulations cannot effectively spread and stay on the crop surface, resulting in the loss of most pesticides soon after application.
阿维菌素是一种高效、低毒、高选择性的新型农畜两用抗生素，为我国高毒农药的替代产品。然而，阿维菌素是一种遇光易分解的物质，提高其光稳定性对于阿维菌素的农用开发，延长持效期具有重要的意义。目前，采用负载技术将阿维菌素包埋在控释材料中是延缓其光分解并能进行缓慢释放的有效途径。其中，聚乙二醇、空心多孔纳米SiO2、明胶、TiO2、介孔活性炭、无机矿物质硅藻土以及天然及合成高分子材料都常用作阿维菌素的稳定缓释载体来制备缓释制剂。但是，目前文献报道的阿维菌素缓控释剂型都集中于研究提高阿 维菌素的光稳定性和缓慢释放，而根据外界环境条件变化而改变释放规律的控制释放型阿维菌素剂型还鲜见报道。尤其是很少有研究者会注意到这些杀虫剂与不同植物叶面的相互作用。因此，开发同植物叶面之间具有较强的作用力，延长其在农作物表面的停留时间，同时具有光稳定性和控释性的新型农药剂型尤为重要。Abamectin is a high-efficiency, low-toxicity and high-selectivity new dual-purpose antibiotic for agriculture and livestock, which is an alternative product for highly toxic pesticides in my country. However, abamectin is a substance that is easily decomposed in the presence of light, and improving its photostability is of great significance for the agricultural development of abamectin and prolonging the lasting period. At present, the use of loading technology to encapsulate abamectin in controlled-release materials is an effective way to delay its photolysis and enable slow release. Among them, polyethylene glycol, hollow porous nano-SiO 2 , gelatin, TiO 2 , mesoporous activated carbon, inorganic mineral diatomaceous earth, and natural and synthetic polymer materials are commonly used as stable slow-release carriers for abamectin to prepare slow-release carriers. release formulation. However, the sustained and controlled release dosage forms of abamectin reported in the literature all focus on the research to improve the photostability and slow release of abamectin, and the controlled release abamectin dosage forms that change the release law according to changes in external environmental conditions There are few reports. In particular, few researchers have noticed the interaction of these pesticides with the foliage of different plants. Therefore, it is particularly important to develop new pesticide formulations that have strong interaction with plant leaves, prolong their residence time on the surface of crops, and at the same time have photostability and controlled release.
发明内容SUMMARY OF THE INVENTION
针对阿维菌素见光易分解，常用乳油剂型有机物使用量大且在不同植物叶面停留时间各异而造成利用率低下、使用量大和环境污染的问题，拟从仿生学角度出发，结合控制释放技术，基于多巴胺化学，通过乳液聚合的方法，制备了仿生粘附性阿维菌素聚多巴胺微胶囊；其释放动力学研究表明该微胶囊具有控缓释和光稳定性；通过扫描电镜验证仿生聚多巴胺微胶囊水悬浮体系在棉花和玉米叶面上具有粘附性能。本研究为仿生粘附性阿维菌素聚多巴胺控释农药的研制及应用奠定理论基础。同时，为适宜于新疆作物及环境特点的控释农药的研发和应用提供技术支持。本发明所采用的技术方案步骤如下：In view of the problems that Abamectin is easily decomposed when exposed to light, the commonly used emulsifiable concentrate formulations use a large amount of organic matter and stay on the leaves of different plants for different times, resulting in low utilization rate, large amount of use and environmental pollution. From the perspective of bionics, combined with control The release technology, based on dopamine chemistry, prepared biomimetic adhesive abamectin polydopamine microcapsules by emulsion polymerization; the release kinetics study showed that the microcapsules had controlled release and photostability; the biomimetic microcapsules were verified by scanning electron microscopy The polydopamine microcapsule water suspension system has adhesive properties on cotton and corn leaves. This study lays a theoretical foundation for the development and application of biomimetic adhesive abamectin-polydopamine controlled-release pesticides. At the same time, it provides technical support for the development and application of controlled-release pesticides suitable for Xinjiang crops and environmental characteristics. The technical solution steps adopted by the present invention are as follows:
先将1.5g十六烷基三甲基氯化铵(1.5％m/v水相)溶于100mL Tris-HCl(pH＝8.5)缓冲溶液中得到表面活性剂的水溶液，0.1g阿维菌素溶于10mL正丁醇中得到油相；然后将油相迅速加入到上面的水溶液中，激烈搅拌30min；随后加入0.1g多巴胺(浓度为1mg/mL)在乳液界面上进行氧化自聚合，室温下300r/min机械搅拌24h。水离心洗涤3-4次，45℃真空干燥得到具有粘附性和光稳定性的微胶囊，且该微胶囊具有温度和pH控释性。该微胶囊中阿维菌素的负载量可达到66.5％，产率可达75％～85％。First, dissolve 1.5 g of cetyltrimethylammonium chloride (1.5% m/v aqueous phase) in 100 mL of Tris-HCl (pH=8.5) buffer solution to obtain an aqueous solution of surfactant, 0.1 g of abamectin Dissolved in 10 mL of n-butanol to obtain an oil phase; then the oil phase was quickly added to the above aqueous solution, stirred vigorously for 30 min; then 0.1 g of dopamine (concentration of 1 mg/mL) was added to carry out oxidative self-polymerization on the emulsion interface, at room temperature 300r/min mechanical stirring for 24h. Centrifugal washing with water for 3-4 times, and vacuum drying at 45° C. to obtain microcapsules with adhesion and photostability, and the microcapsules have temperature and pH controlled release properties. The loading amount of abamectin in the microcapsules can reach 66.5%, and the yield can reach 75%-85%.
附图说明Description of drawings
通过场发射扫描电镜观察了乳液界面聚合法得到的阿维菌素聚多巴胺微胶 囊，从图中可以看出微胶囊尺寸均一，粒径在215nm左右，具有很好的粘附性。附图1为阿维菌素聚多巴胺微胶囊的SEM照片。The abamectin polydopamine microcapsules obtained by the emulsion interfacial polymerization method were observed by field emission scanning electron microscope, and as can be seen from the figure, the microcapsules were uniform in size, and the particle diameter was about 215nm, with good adhesion. Accompanying drawing 1 is the SEM photograph of abamectin polydopamine microcapsules.
具体实施方式Detailed ways
下面结合实施例对本发明做进一步说明，但本发明的内容不仅限于实施例中所涉及的内容。The present invention will be further described below with reference to the embodiments, but the content of the present invention is not limited to the content involved in the embodiments.
实施例1先将1.5g十六烷基三甲基氯化铵(1.5％m/v水相)溶于100mLTris-HCl(pH＝8.5)缓冲溶液中得到表面活性剂的水溶液，0.1g阿维菌素溶于10mL正丁醇中得到油相；然后将油相迅速加入到上面的水溶液中，激烈搅拌30min；随后加入0.1g多巴胺(浓度为1mg/mL)在乳液界面上进行氧化自聚合，室温下300r/min机械搅拌24h。水离心洗涤3-4次，45℃真空干燥得到具有粘附性和光稳定性的微胶囊，且该微胶囊具有温度和pH控释性。该微胶囊中阿维菌素的负载量可达到66.5％，产率可达75％～85％。Example 1 First, 1.5 g of cetyltrimethylammonium chloride (1.5% m/v aqueous phase) was dissolved in 100 mL of Tris-HCl (pH=8.5) buffer solution to obtain an aqueous solution of surfactant, 0.1 g of Avi The bacteriocin was dissolved in 10 mL of n-butanol to obtain an oil phase; then the oil phase was rapidly added to the above aqueous solution, stirred vigorously for 30 min; then 0.1 g of dopamine (concentration of 1 mg/mL) was added to carry out oxidative self-polymerization on the emulsion interface, 300r/min mechanical stirring at room temperature for 24h. Centrifugal washing with water for 3-4 times, and vacuum drying at 45° C. to obtain microcapsules with adhesion and photostability, and the microcapsules have temperature and pH controlled release properties. The loading amount of abamectin in the microcapsules can reach 66.5%, and the yield can reach 75%-85%.
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