CN102487967A - Preparation method of biopesticide - Google Patents

Abstract

Translated fromChinese

本发明属于化学发明技术领域，公开了一种应用麻疯树生物柴油油脚制备生物农药的方法。麻疯树生产生物柴油后的油脚在40-100℃加入20-60%的氢氧化钾或氢氧化钠溶液，调节pH值为12制备为乳液；或将油脚用乳化剂、分散剂、防冻剂、稳定剂分散而做成的水乳液；该水乳液即为生物农药。本发明方法生产的生物农药具有较好地杀灭福寿螺和菜青虫等农作物害虫的作用，具有成本低，效果好，减少环境污染等优点。The invention belongs to the technical field of chemical inventions, and discloses a method for preparing biopesticides using Jatropha curcas biodiesel oil. Add 20-60% potassium hydroxide or sodium hydroxide solution at 40-100°C to the oil foot after producing biodiesel from Jatropha curcas, and adjust the pH value to 12 to prepare an emulsion; or use an emulsifier, dispersant, Water emulsion made by dispersing antifreeze and stabilizer; the water emulsion is biological pesticide. The biological pesticide produced by the method of the invention has the effect of killing crop pests such as apple snails and cabbage caterpillars, and has the advantages of low cost, good effect, and reduced environmental pollution.

Description

Translated fromChinese

一种生物农药的制备方法A kind of preparation method of biological pesticide

技术领域technical field

本发明属于化学发明技术领域，具体涉及一种来自于麻疯树油制取生物柴油后的油脚作为农药，应用于杀灭植物害虫。The invention belongs to the technical field of chemical inventions, and in particular relates to a kind of oil residue from jatropha curcas oil produced from biodiesel as a pesticide, which is applied to kill plant pests.

技术背景technical background

众所周知，与化学农药比较，植物农药有环境友好、对人畜毒害低、不易产生抗药性等优点，是农药研究与应用的热点。As we all know, compared with chemical pesticides, plant pesticides have the advantages of being environmentally friendly, less toxic to humans and animals, and less likely to produce drug resistance. They are hot spots in pesticide research and application.

麻疯树是一种耐贫瘠干旱、适应性强的植物，其种仁含油量高，是生物柴油的理想原料，被认为是一种最有发展前途的能源植物。关于麻疯树作为生物柴油开发已经有大量的研究，同时其中的毒性成分作为天然杀虫剂的潜在价值也得到关注。如李育川等人报道了小桐子果壳提取物的杀虫活性[广西植物，2011，31(1)：129]，王兆玉等人研究了小油桐叶甲醇提取物对福寿螺的药效[南方医科大学学报，2009；29(6)1235-1237]，李静等报道了从种子中提取的麻疯树萜醇I作为生物农药的应用(中国专利号：200610020278.0)。Jatropha curcas is a barren and drought-tolerant plant with strong adaptability. Its seeds have high oil content and are ideal raw materials for biodiesel. It is considered to be the most promising energy plant. There has been a lot of research on the development of Jatropha curcas as biodiesel, and the potential value of its toxic components as natural insecticides has also been paid attention to. People such as Li Yuchuan reported the insecticidal activity of Jatropha jatropha husk extract [Guangxi Plants, 2011, 31 (1): 129], and Wang Zhaoyu et al. studied the drug effect of Jatropha jatropha leaf methanol extract on apple snails [Southern Medical Sciences University Journal, 2009; 29(6)1235-1237], Li Jing et al. reported the application of Jatrophol I extracted from seeds as a biopesticide (Chinese Patent No.: 200610020278.0).

福寿螺(Pomacea canaliculata，Lamarck)属于软体动物门，腹足纲，中腹足目，瓶螺科，原产于南美洲亚马逊河流域。1981年作为食用螺引入中国，因其适应性强，繁殖迅速，成为危害巨大的外来入侵物种，对农作物，尤其是水稻，危害极大，严重时可造成水稻等水生作物减产50％以上，甚至绝产。同时，螺体还能传播引发人类嗜酸性脑膜炎的广东管园线虫。Apple snail (Pomacea canaliculata, Lamarck) belongs to the mollusk phylum, Gastropoda, Mesogastropoda, Piracea family, and is native to the Amazon River Basin in South America. It was introduced into China as an edible snail in 1981. Because of its strong adaptability and rapid reproduction, it has become a hugely harmful alien invasive species. It is extremely harmful to crops, especially rice. In severe cases, it can cause more than 50% of rice and other aquatic crops. extinct. At the same time, the spirochete can also transmit the tuberculosis nematode cantonensis that causes eosinophilic meningitis in humans.

菜青虫(Pieris rapae L)又称菜粉蝶，属鳞翅目粉蝶科。世界各地几乎均有分布，在我国分布普遍各省均有。该虫主要危害甘蓝、花椰菜、白菜、萝卜、油菜等十字花科蔬菜，偏嗜厚叶类蔬菜，板蓝根等中药材也易受害。其幼虫咬食寄主叶片，2龄前仅啃食叶肉，留下一层透明表皮，3龄后蚕食叶片孔洞或缺刻，严重时叶片全部被吃光，只残留粗叶脉和叶柄，造成绝产，同时菜青虫排出的粪便，又容易传染软腐病。Cabbage caterpillar (Pieris rapae L), also known as cabbage butterfly, belongs to the family Lepidoptera. It is distributed almost all over the world, and it is widely distributed in all provinces in my country. The insect mainly harms cruciferous vegetables such as cabbage, cauliflower, Chinese cabbage, radish, and rapeseed, and prefers thick leafy vegetables. The larvae bite the leaves of the host. Before the 2nd age, they only eat the mesophyll, leaving a layer of transparent epidermis. After the 3rd age, they eat the holes or notches of the leaves. At the same time, the feces discharged by cabbage caterpillars are easy to infect soft rot.

来源于植物的生物农药常常比较昂贵，难以普及用于附加值低的农产品生产中。用麻疯树油脚制备的生物农药对上述两种害虫都有较好的杀灭作用。而麻疯树油脚作为一种废弃物几乎没有成本，加工为农药的工艺过程也比较简单，可作为一种廉价生物农药使用。Biopesticides derived from plants are often expensive and difficult to be widely used in the production of agricultural products with low added value. The biopesticide prepared from Jatropha curcas oil foot has a good killing effect on the above two kinds of pests. As a kind of waste, Jatropha curcas oil foot has almost no cost, and the process of processing it into pesticide is relatively simple, so it can be used as a cheap biopesticide.

发明内容Contents of the invention

本发明的特色是将麻疯树生产生物柴油后的废弃物油脚作为生物农药使用。这种油脚的利用不仅解决了废弃物的处理，还可将其用作廉价而有效的生物农药。The characteristic of the present invention is that the waste oil leftover after producing biodiesel from jatropha curcas is used as biopesticide. The utilization of this oil foot not only solves the disposal of waste, but also can be used as a cheap and effective biological pesticide.

麻疯树油有杀虫活性，经过强酸强碱处理后其结构可能发生变化，油脚中未检测到文献所报道的几种有杀虫活性的二萜。实验证明水溶性成分活性很低，而脂溶性部分杀虫活性仍然有较好的活性。由于油脚仍然是油脂，难溶于水，不能有效杀灭害虫，所以需要分散在水中。由于油脚中含有大量的未酯化的长链脂肪酸，所以加入强碱形成的脂肪酸盐可作为表面活性剂利于将具有杀虫活性的脂溶性成分分散于水中。其它能够将脂溶性成分分散在水中的乳化剂也可以用于将杀虫剂的分散。Jatropha curcas oil has insecticidal activity, and its structure may change after being treated with strong acid and strong alkali. Several diterpenes with insecticidal activity reported in the literature were not detected in the oil foot. Experiments have proved that the activity of water-soluble components is very low, while the insecticidal activity of fat-soluble components still has good activity. Since the oil foot is still oil, it is difficult to dissolve in water and cannot effectively kill pests, so it needs to be dispersed in water. Since the oil foot contains a large amount of unesterified long-chain fatty acid, the fatty acid salt formed by adding a strong base can be used as a surfactant to disperse the fat-soluble ingredients with insecticidal activity in water. Other emulsifiers capable of dispersing fat-soluble ingredients in water can also be used to disperse the insecticide.

本发明利用麻疯树生产生物柴油后的油脚在40-100℃加入20-60％的氢氧化钾或氢氧化钠溶液，调节pH值为12制备为乳液；或将油脚用乳化剂、分散剂、防冻剂、稳定剂分散而做成的水乳液；该水乳液即为生物农药。The present invention utilizes Jatropha curcas to produce biodiesel oil bottoms, add 20-60% potassium hydroxide or sodium hydroxide solution at 40-100°C, adjust pH value to 12 to prepare emulsion; or use emulsifier, A water emulsion made by dispersing a dispersant, an antifreeze agent, and a stabilizer; the water emulsion is a biological pesticide.

按照农药的水乳液的通常制备方法，所选乳化剂为烷基酚聚氧乙烯醚，如苯乙烯基酚聚氧乙烯醚、甲基苄基聚氧乙烯醚，也可选用烷基磷酸盐等；分散剂为三聚磷酸钠和亚甲基双萘磺酸钠；防冻剂为丙二醇；稳定剂为苯基缩水甘油醚；分散介质为水。According to the usual preparation method of the aqueous emulsion of pesticides, the selected emulsifier is alkylphenol polyoxyethylene ether, such as styrylphenol polyoxyethylene ether, methylbenzyl polyoxyethylene ether, or alkyl phosphate, etc. ; The dispersant is sodium tripolyphosphate and sodium methylene bis-naphthalene sulfonate; the antifreeze is propylene glycol; the stabilizer is phenyl glycidyl ether; the dispersion medium is water.

具体实施方式Detailed ways

下面通过实施例对本发明进行具体描述。The present invention is specifically described below by way of examples.

实施例1：取甲醇/硫酸/麻疯树油酯交换制备的生物柴油的油脚样品55g加入500ml圆底烧瓶中加热到80℃，搅拌条件下滴加45g 20％氢氧化钾溶液，继续搅拌30分钟，配制成为乳液。Embodiment 1: get the oil bottoms sample 55g of the biodiesel oil bottom sample 55g that methyl alcohol/sulfuric acid/jatropha oil transesterification prepares and add in the 500ml round-bottomed flask and be heated to 80 ℃, drip 45g 20% potassium hydroxide solution under stirring condition, continue to stir For 30 minutes, formulate into an emulsion.

实施例2：取甲醇/硫酸/麻疯树油酯交换制备的生物柴油的油脚样品55g加入500ml圆底烧瓶中加热到80℃，搅拌条件下滴加15g 60％氢氧化钾溶液，继续搅拌30分钟，加水30g配制成为乳液。Embodiment 2: get the oil bottoms sample 55g of the biodiesel oil bottom sample 55g that methyl alcohol/sulfuric acid/jatropha oil transesterification prepares and add in the 500ml round bottom flask and be heated to 80 ℃, drip 15g 60% potassium hydroxide solution under stirring condition, continue to stir After 30 minutes, add 30 g of water to prepare an emulsion.

实施例3：取甲醇/硫酸/麻疯树油酯交换制备的生物柴油的油脚样品55g，将苯乙烯基酚聚氧乙烯醚10g、三聚磷酸钠6g、苯基缩水甘油醚6g、丙二醇3g和水20g依次加入高速剪切混合乳化器内，采用高速剪切混合制备成为含水20％的麻疯树籽油脚乳液。Embodiment 3: get the oil foot sample 55g of the biodiesel oil bottom sample that methanol/sulfuric acid/jatropha oil transesterification prepares, with styrylphenol polyoxyethylene ether 10g, sodium tripolyphosphate 6g, phenyl glycidyl ether 6g, propylene glycol 3g and 20g of water were sequentially added into a high-speed shear mixing emulsifier, and high-speed shear mixing was used to prepare a jatropha seed oil foot emulsion with a water content of 20%.

实施例4：福寿螺毒杀实验采用WHO“杀螺剂实验室终筛方法”中的浸泡法。将两种麻疯树籽油脚乳液分别配制成不同浓度的水溶液，置于容量1L的玻璃容器中，每组投放10只健康福寿螺，完全浸没，在容器上加盖纱网，于24、48、72h时分别取出，用脱氯水冲洗3次，于饲养条件下放置72h，然后检查：开厣爬行者为活体，余下敲碎螺壳并用解剖针刺其软体，无反应者为死体。同时设置20mg.L^-1的四聚乙醛和空白组作为对照，每个处理设3个重复。试验温度20～25℃。结果见表一。Example 4: The poisoning experiment of apple snails adopts the soaking method in the WHO "Molluscicide Laboratory Final Screening Method". Two kinds of jatropha seed oil foot emulsions were prepared into aqueous solutions of different concentrations, and placed in glass containers with a capacity of 1L. Each group was put into 10 healthy apple snails, completely submerged, and the container was covered with a gauze, and at 24 and 48 Take them out at 72 hours respectively, wash them with dechlorinated water three times, and place them under feeding conditions for 72 hours, and then check: those who were opened and crawled are living, and the remaining shells are crushed and the soft body is punctured with dissecting needles. Those who do not respond are dead. At the same time, 20mg.L^-1 metaldehyde and blank group were set as controls, and each treatment was set up with 3 repetitions. The test temperature is 20-25°C. The results are shown in Table 1.

表一杀福寿螺实验结果Table 1 Experimental results of killing apple snails

实施例5：菜青虫毒杀实验采用浸渍叶碟饲喂法。将新鲜甘蓝叶片洗净晾干，用方形打孔器打成2cm×2cm的叶碟，分别放入不同浓度的麻疯树油脚乳液稀释液中浸渍5s，取出晾干后，放入直径为9cm的垫有保湿滤纸的培养皿中，每皿放5个处理叶碟，接入饥饿3h的菜青虫3龄幼虫，每皿1头，每处理10头，进行3次重复，同时以0.1％十二烷基硫酸钠水溶液稀释后的丙酮溶液为阴性对照，以50％辛硫磷乳油作为阳性对照。然后把供试幼虫放于温度为(25±1)℃、相对湿度为60％～70％的生化培养箱中饲养，分别于12、24、48、72h后检测菜青虫死亡率，实验结果见表二。Example 5: The poisoning experiment of Pieris rapae adopts the method of feeding with dipped leaf discs. Wash and dry the fresh cabbage leaves, punch them into 2cm×2cm leaf discs with a square hole puncher, put them in different concentrations of jatropha curcas oil-foot emulsion dilutions and soak them for 5s, take them out and dry them, put them in In a 9cm petri dish with moisturizing filter paper, put 5 treated leaf discs in each dish, insert the 3rd instar larvae of Pieris rapae larvae starved for 3 hours, 1 head per dish, 10 heads for each treatment, repeat 3 times, and at the same time add 0.1% Acetone solution diluted with sodium lauryl sulfate aqueous solution was used as negative control, and 50% phoxim EC was used as positive control. Then put the tested larvae in a biochemical incubator with a temperature of (25 ± 1) °C and a relative humidity of 60% to 70% to raise them, and detect the mortality of cabbage caterpillars after 12, 24, 48, and 72 hours respectively. The experimental results are shown in Table II.

表二毒杀菜青虫实验结果Table 2 The results of the poisonous killing experiment on Pieris rapae

Claims (3)

1. the preparation method of a biopesticide is characterized in that: the oil foot after the Jatropha curcas production biodiesel is at 40-100 ℃ of potassium hydroxide or sodium hydroxide solution that adds 20-60%, regulates the pH value and is 12 and be prepared as emulsion; Or oil foot disperseed with emulsifier, dispersant, antifreezing agent, stabilizing agent and the aqueous emulsion made; This aqueous emulsion is biopesticide.

2. according to the preparation method of the biopesticide described in the claim 1, it is characterized in that: described emulsifier is APES or alkylphosphonic or styryl phenol polyethenoxy ether or methyl-benzyl APEO; Dispersant is sodium phosphate trimer or sodium methylene bis-naphthalene sulfonate; Antifreezing agent is a propane diols; Stabilizing agent is a phenyl glycidyl ether; Dispersion medium is a water.

3. the biopesticide of method preparation according to claim 1 is killed the purposes of cabbage caterpillar or Pomacea canaliculata insect in agricultural production.