背景技术 Background technique

[0002] 炔草酯（clodinafop-propargyl)的化学名称为(R)-2-[4-(5-氯-3-氟-2-吡啶氧基)苯氧基]丙酸块丙基酯，结构式为 [0002] clodinafop-propargyl (clodinafop-propargyl) The chemical name of (R) -2- [4- (5- chloro-3-fluoro-2-pyridyloxy) phenoxy] propionic acid propyl ester blocks, of the formula

它是一种手性的、含氟的、芳香苯氧丙酸类的新型高效除草剂，是Ciba-Geigy公司开发的谷物地芽后除草剂，主要用于防除野燕麦、看麦娘、黑麦草和狗尾草等一年生禾本科杂草。 It is a chiral, fluorine, new efficient phenoxy herbicide aromatic acid and the like, after Ciba-Geigy Corporation to develop cereal herbicide, mainly for the control of wild oats, foxtail, black straw and green foxtail and other annual grass weeds. 商品名称为Top ic、Ce I i 〇、顶尖、炔草酸等，纯品为白色结晶体，熔点59.5 °C，相对密度为1.37 (20 °C)，水中溶解度为4. Omg/L(20 °C)，在甲苯、丙酮和乙醇中溶解度较大。 Trade name Top ic, Ce I i billion, top, clodinafop like, pure white crystals, mp 59.5 ° C, relative density of 1.37 (20 ° C), the water solubility of 4. Omg / L (20 ° C ), greater solubility in toluene, acetone and ethanol. 其在酸性介质中相对稳定、碱性介质中水解，光照下很容易分解，在土壤中很快降解为游离酸苯基和吡啶部分进入土壤以及矿化物，对后茬作物无影响。 Which is relatively stable in an acidic medium, the alkaline hydrolysis medium, the light is easily decomposed in the soil quickly degrade into the free acid and phenyl pyridine moiety into the soil and mineralization, has no effect on the succeeding crop. 炔草酯的作用机理与特点是抑制乙酰辅酶A羧化酶(ACCase)的活性，是一种内吸传导性除草剂，由植物体的叶片和叶鞘吸收，韧皮部传导，积累于植物体的分生组织内，抑制乙酰辅酶A羧化酶，使脂肪酸合成停止，细胞的生长分裂不能正常进行，膜系通等含脂结构破坏，最后导致植物死亡，研究发现炔草酯类除草剂进入植物体内后先水解成酸，然后再以酸的形式发挥除草作用。 Clodinafop-propargyl mechanism of action and is characterized by inhibition of acetyl coenzyme A carboxylase (ACCase) activity is an internal uptake of the herbicide, absorbed by plant leaves and leaf sheaths, and conducting phloem, accumulated in the plant division endogenous tissue, inhibit acetyl coenzyme a carboxylase, fatty acid synthesis stops growth and division of cells can not be normal, and other lipid-containing membrane system through structural damage, leading to plant death, the study found alkyne grass herbicides into the plants after the first hydrolysis to the acid, and then play in the form of acid herbicidal action. 在性能上，炔草酯除草剂表现为毒性小；用量少;药效高;代谢能力强;可抑制多种杂草种子的生长。 In performance, clodinafop-propargyl herbicide showed less toxicity; with less; high efficacy; strong metabolic capability; inhibit the growth of a variety of weed seeds. 首次应用于瑞士、南非和智利，目前已有50多个国家投入使用。 First used in Switzerland, South Africa and Chile, there are more than 50 countries and put into use.

[0003] 目前市场上的炔草酯类除草剂的剂型主要是可湿性粉剂。 [0003] It alkyne grass herbicides on the market a dosage form is mainly a wettable powder. 可湿性粉剂主要是由炔草酯、助剂(表面活性剂、增稠剂等)及固体填料(高岭土、轻钙和硅藻土)等混合后经过气流粉碎得到的农药剂型。 The wettable powder is clodinafop-propargyl, additives (surfactants, thickeners, etc.) and the solid filler (kaolin clay, diatomaceous earth and calcium light) and the like after mixing the pesticide formulation obtained by jet-milling. 由于可湿性粉剂的颗粒比较粗，因而在使用过程中是以较大的固体颗粒附着在杂草的表面，不易被杂草吸收，农药有效成份流失较多，因而相对用量会增大， 容易对环境造成污染。 Since the wettable powder particles are relatively coarse, so that in the course of larger solid particles are attached to the surface of the weeds, the weeds can not easily be absorbed, the active ingredient lost more pesticides, which will increase the relative amount, easy to pollute the environment. 同时可湿性粉剂在加工过程中所采用的气流粉碎，在生产过程中会产生扬尘，污染环境的同时亦危害生产者。 Meanwhile WP in the process used in jet milling, in the production process will generate dust and pollute the environment but also harm producers. 同时可湿性粉剂在使用过程中也会由于产生扬尘而造成对环境的二次污染。 Meanwhile WP in use since the process will generate dust caused by secondary pollution to the environment. 为解决炔草酯可湿性粉剂的这些不足之处，中国专利公开号CN102428921 A公开了一种炔草酯水分散粒剂及其制备方法。 To address these deficiencies clodinafop-propargyl wettable powder, Chinese Patent No. CN102428921 A Publication discloses a clodinafop-propargyl water dispersible granule and preparation method. 该发明克服了炔草酯可湿性粉剂不环保和粉尘漂移等问题，但制备的炔草酯仍以颗粒状使用，不易被杂草吸收，利用率不低。 The invention overcomes clodinafop-propargyl WP is not environmentally friendly and dust drift and other issues, but the preparation of clodinafop-propargyl still use granular, easily absorbed by the weeds, utilization rate is not low. 因此研发一种乳状剂型的炔草酯除草剂具有重要意义。 Therefore, to develop a milky formulation clodinafop-propargyl herbicide important.

[0004] 经过专利检索，中国专利申请号：201010151613.7公开了一种炔草酯微乳剂及其制备方法的专利文件，其微乳剂成份按照重量比为:炔草酯为1-50%，溶剂1-20%，助溶剂1-20%，乳化剂5-30 %，水50-90%。 [0004] After the patent search, Chinese patent application number: 201010151613.7 patent discloses File is clodinafop-propargyl microemulsion and preparation method, and its micro-emulsion composition in a weight ratio of: clodinafop-propargyl 1-50% solvent 1 -20%, 1-20% cosolvent, emulsifier 5-30%, 50-90% water. 制备方法为：首先按重量百分比把溶剂、助溶剂及炔草酯在50-200转/分的转速下搅拌混合均匀，然后投入比例要求的乳化剂，再搅拌均匀，最后加入水继续搅拌1-2小时，即可成为均匀透明的溶液产品，该发明能效提高药剂的使用效率。 Preparation method: First, the percentage by weight of solvent, co-solvent, and clodinafop-propargyl stirred at 50-200 rev / min speed mixing, then input the required proportion of emulsifier, and then stir, and finally water was added and stirring was continued 1- 2 hours, can become a uniform transparent solution product, the invention is the efficient use of energy efficiency agent.

[0005] 中国专利号：201310117910.3公开了一种炔草酯微乳剂的生产方法的专利文件， 其原料配方按重量百分比计算:包括炔草酯12-18%、溶剂5-10%、助溶剂22-28%、表面活性剂10-15%、余量为水;通过步骤1:炔草酯、溶剂、助溶剂的混合;步骤2:表面活性剂和水的混合;步骤3:步骤1的混合物和步骤2的混合物的混合最终制得成品炔草酯微乳剂。 [0005] Chinese patent number: 201310117910.3 patent discloses File is clodinafop-propargyl microemulsion production methods, the raw material formulation by weight percentage include: clodinafop-propargyl 12-18%, 5-10% solvents, solubilizing 22 -28%, 10-15% surfactant, balance water; step 1: clodinafop-propargyl, mixed solvents, cosolvents; step 2: mixing the surfactant and water; step 3: 1 mixture of step and the mixture of step 2 is finally obtained finished mixed grass propargyl ester microemulsion. 该发明具有工艺简单、反应条件温和、无污染废弃物排放、产品质量好等优点。 The invention has simple process, mild reaction conditions, non-polluting waste emissions, good product quality advantages.

[0006] 但这些专利都未考虑到炔草酯除草剂对作物的安全性问题，长期使用会对本季作物以及后茬作物有毒害作用，同时未考虑到炔草酯除草剂的存储稳定性问题，长时间存储会使炔草酯的药效明显降低;另一方面，炔草酯微乳是一种常用的麦田除草剂，使用温度基本在HTC以下，制剂的低温分散性和稀释稳定性尤为重要，以上专利均未有效解决这些问题。 [0006] However, these patents do not consider to clodinafop-propargyl herbicides on crops security issues, as well as long-term use will crop after crop season have toxic effects, while not taking into account the storage stability clodinafop-propargyl herbicide problem efficacy prolonged storage will significantly reduced clodinafop-propargyl; on the other hand, clodinafop-propargyl microemulsion is a common herbicides, HTC temperature substantially below the low-temperature dispersibility and stability of the formulation was diluted particularly important, none of the above patents effectively solve these problems.

[0007] 1.要解决的问题 [0007] 1. To solve the problem

[0008] 针对现有炔草酯除草剂存在的安全性问题，稳定性问题以及低温分散性问题，本发明提供一种炔草酯微乳剂及其制备方法以及应用方法，炔草酯微乳剂中加入解毒喹作为安全剂，以确保除草的同时促进作物的生长。 [0008] the existing presence of the herbicide clodinafop-propargyl security issues, stability and low dispersion problems, the present invention provides a microemulsion clodinafop-propargyl and preparation method and application method, clodinafop-propargyl microemulsions quinoline as a detoxifying agent added security to ensure weeding while promoting the growth of crops. 同时针对炔草酯和安全剂的储存稳定性问题， 添加了稳定剂的组分，以保证制剂成份具有2年的有效期并且安全剂没有明显的降解，本发明的除草剂其主要应用于防除小麦田中的部分禾本科杂草，对野燕麦、看麦娘、硬草、茼草、 棒头草等大多数重要的一年生禾本科杂草，制剂中的高效乳化分散剂增强了炔草酯的低温分散性和稀释稳定性，从而保证了除草剂的药效。 At the same time for the storage stability of clodinafop-propargyl and security agents, stabilizers added component to ensure that the formulation ingredients with 2 years validity and security agents no significant degradation of the herbicide of the present invention is mainly used in controlling wheat Tanaka part weeds, wild oats to see the most important annual grass weeds, the formulation of efficient emulsifying dispersant enhances the alkyne ester cryogenic foxtail grass, hard grass, garland grass, grass Polypogon dispersion and dilution stability, thus ensuring the efficacy of the herbicide. 本发明提供的一种炔草酯微乳剂具有防治范围广，低毒，防效稳定，持效长，安全性好。 The present invention provides a microemulsion clodinafop-propargyl with a wide range of prevention, low toxicity, anti-efficiency stable, long holding effect, good security.

[0009] 2.技术方案 [0009] 2. Technical solutions

[0010] 为了解决上述问题，本发明所采用的技术方案如下。 [0010] In order to solve the above problems, the technical solutions adopted by the invention is as follows.

[0011] -种炔草酯微乳剂，其组成成份及质量百分比为:炔草酯5-20%，安全剂1-5%，溶剂15-40%，稳定剂1-4%，乳化剂10-24%，高效分散剂1-5%，余量为水。 [0011] - the kind of grass propargyl ester microemulsion, and its constituent mass percentage: clodinafop-propargyl 5-20%, 1-5% security agent, solvent 15-40%, 1-4% stabilizers, emulsifiers 10 -24% efficient dispersing agent 1-5%, the balance being water.

[0012] 优选地，所述的炔草酯的纯度为93%。 [0012] Preferably, said clodinafop-propargyl purity was 93%.

[0013]优选地，所述的安全剂为解毒喹。 [0013] Preferably, the safener is cloquintocet-mexyl.

[0014]优选地，所述的溶剂是乙二醇、脂肪酸甲酯、二乙二醇甲醚和二乙二醇丁醚的任意组合。 [0014] Preferably, the solvent is any combination of glycol, fatty acid methyl ester, diethylene glycol monomethyl ether and diethylene glycol butyl ether.

[0015] 优选地，所述的稳定剂是脂肪胺聚醚、亚磷酸三苯酯和环氧氯丙烷的组合物，其质量百分比为:脂肪胺聚醚10-20%，亚磷酸三苯酯0-50%，余量为环氧氯丙烷。 [0015] Preferably, the stabilizer is a polyether aliphatic amine, triphenyl phosphite composition and epichlorohydrin, which is percent by mass: 10-20% polyether aliphatic amine, triphenyl phosphite 0-50%, the balance being epichlorohydrin.

[0016] 优选地，所述的乳化剂是阴离子乳化剂、脂肪醇聚醚、烷基酚聚氧乙烯醚磷酸酯、 异构醇聚氧乙烯醚、三苯乙基酚聚氧乙烯醚、异构醇聚醚和非离子嵌段共聚物的组合物，其质量百分比为：阴离子乳化剂2-10%，脂肪醇聚醚5-10%，烷基酚聚氧乙烯醚磷酸酯12-25%，异构醇聚氧乙烯醚10-20%、三苯乙基酚聚氧乙烯醚5-15%，异构醇聚醚3-15%，余量为非离子嵌段共聚物。 [0016] Preferably, the emulsifier is an anionic emulsifier, fatty alcohol polyethers, alkylphenol ether phosphate, heterogeneous alcohol ethoxylates, triphenyl ethyl phenol ethoxylates, isopropyl the composition structure of polyether polyol and a nonionic block copolymer, the weight percentage of: anionic emulsifier 2-10%, 5-10% polyether alcohols, alkylphenol ether phosphate 12-25% , heterogeneous alcohol polyoxyethylene ether 10-20%, triphenyl ethyl phenol polyoxyethylene ether 5-15%, 3-15% laureth isomer, and the balance a non-ionic block copolymer.

[0017] 优选地，所述的高效分散剂是聚乙二醇单油酸酯、聚氧乙烯油酸酯、脂肪酸酯，其质量百分比为:聚乙二醇单油酸酯10-20%，聚氧乙烯月桂酸酯20-30%，余量为脂肪酸酯。 [0017] Preferably, the efficiency of the dispersant is polyethylene glycol monooleate, polyoxyethylene oleate, fatty acid esters, which mass percentage: polyethylene glycol monooleate 10-20% , polyoxyethylene laurate 20-30%, and the balance of fatty acid esters.

[0018] -种炔草酯微乳剂的制备方法，其步骤为： [0018] - the kind of grass propargyl ester microemulsion preparation method comprises the following steps:

[0019] (A)将脂肪胺聚醚、亚磷酸三苯酯和环氧氯丙烷混合搅拌均匀制成稳定剂，其中脂肪胺聚醚10-20%，亚磷酸三苯酯0-50%，余量为环氧氯丙烷； [0019] (A) the polyether aliphatic amine, triphenyl phosphite and epichlorohydrin mixing evenly formed stabilizers, polyether amine wherein the fat 10-20%, 0-50% triphenyl phosphite, the balance of epichlorohydrin;

[0020] (B)将聚乙二醇单油酸酯、聚氧乙烯油酸酯、脂肪酸酯混合搅拌均匀制成高效分散剂，其中聚乙二醇单油酸酯10-20%，聚氧乙烯月桂酸酯20-30%，余量为脂肪酸酯； [0020] (B) a polyethylene glycol monooleate, polyoxyethylene oleate, fatty acid esters prepared efficient mixing uniformly dispersing agent, wherein the polyethylene glycol monooleate 10-20%, poly polyoxyethylene laurate 20-30%, and the balance of fatty acid esters;

[0021] (C)将阴离子乳化剂、脂肪醇聚醚、烷基酚聚氧乙烯醚磷酸酯、异构醇聚氧乙烯醚、 三苯乙基酚聚氧乙烯醚、异构醇聚醚和非离子嵌段共聚物混合搅拌均匀制成乳化剂，其中阴离子乳化剂2-10%，脂肪醇聚醚5-10%，烷基酚聚氧乙烯醚磷酸酯12-25%，异构醇聚氧乙烯醚10-20%、三苯乙基分聚氧乙烯醚5-15%，异构醇聚醚3-15%，余量为非离子嵌段共聚物； [0021] (C) an anionic emulsifier, fatty alcohol polyethers, alkylphenol ether phosphate, heterogeneous alcohol ethoxylates, triphenyl ethyl phenol ethoxylates, heterogeneous alcohol and polyether nonionic block copolymer made uniform mixing emulsifier, wherein the anionic emulsifier 2-10%, 5-10% polyether alcohols, alkylphenol ether phosphate 12-25% isomeric alcohol poly 10-20% ethylene oxide ether, ethyl triphenyl sub polyoxyethylene ethers 5-15%, 3-15% laureth isomer, and the balance is a nonionic block copolymer;

[0022] (D)依次将溶剂、炔草酯原药、安全剂、步骤(A)中得到的稳定剂和步骤(B)中得到的高效分散剂添加到配料釜中，在50-150转/分的转速下搅拌溶解成透明均相液体，其中溶剂15-40%，炔草酯5-20%，安全剂1-5%，稳定剂1-4%，高效分散剂1-5% ; [0022] (D) followed by the solvent, clodinafop-propargyl original drug, security agents, in step (A) obtained in stabilizer and step (B) obtained in highly effective dispersing agent is added to the ingredients in the pot, turn 50-150 under / min speed stirring to dissolve into a transparent homogeneous liquid, wherein the solvent is 15-40%, clodinafop-propargyl 5-20%, 1-5% security agents, stabilizers 1-4%, 1-5% efficient dispersant;

[0023] (E)将步骤(C)中得到的乳化剂和水加入步骤(D)中得到的均相液体中，继续以50- 150转/分的转速搅拌均勾形成炔草酯微乳剂； Homogeneous liquid [0023] (E) in step (C) obtained in the emulsifier and water were added in step (D) are obtained, continue to be 50-150 rev / min speed stirring hook are formed clodinafop-propargyl microemulsion ;

[0024] (F)取步骤(E)中得到的炔草酯微乳剂检测药效，合格后，转移到沉降釜中静置24h； [0024] (F) take the step (E) obtained clodinafop-propargyl microemulsion detect efficacy, after passing transferred to a settling vessel was allowed to stand 24h;

[0025] (G)将步骤(F)中得到的炔草酯微乳剂分装入库。 [0025] (G) in step (F) obtained clodinafop-propargyl microemulsion dispensing storage.

[0026]优选地，所述的安全剂为解毒喹，炔草酯原药为纯度是质量份数为93%的炔草酯。 [0026] Preferably, the safener is cloquintocet-mexyl, clodinafop-propargyl original drug purity is 93% of the mass fraction of clodinafop-propargyl. [0027] 一种炔草酯微乳剂的应用方法，其步骤为将炔草酯微乳剂稀释200-400倍后对杂草进行喷雾。 [0027] A microemulsion clodinafop-propargyl application methods, the steps of the grass propargyl ester microemulsion diluted 200-400 fold weed spray.

[0028] 3.有益效果 [0028] 3. The beneficial effect

[0029] 相比于现有技术，本发明的有益效果为： [0029] Compared to the prior art, the beneficial effects of the present invention are as follows:

[0030] (1)本发明采用对环境安全友好的绿色环保型溶剂体系，以水代替部分溶剂，有效成份以分子状态存在，跟乳油和可湿性粉剂相比较效果更好，更环保，更安全，更经济，对环境和生命更安全，同时在喷施前的勾兑更容易，分散性好； [0030] (1) of the present invention to adopt environmentally safe and friendly environment-friendly solvent system to replace part of the water solvent, the active ingredient in the presence of molecular state, with EC and WP compared to better, more environmentally friendly and safer , more economical and safer for the environment and life, while blending before spraying easier, good dispersion;

[0031] (2)本发明添加了解毒喹作为安全剂，有效地提高了对作物的安全性，确保除草的同时促进作物的生长，使用更安全； [0031] (2) of the present invention is added as a security agent quinoline detoxification, effectively improve the safety of the crop, to ensure weeding while promoting the growth of crops, the use of safer;

[0032] (3)本发明中添加了稳定剂的组分，以保证制剂成份具有2年的有效期并且安全剂没有明显的降解，另外，此微乳剂是麦田除草剂，对于使用温度在l〇°C以下，制剂的低温分散性和稀释稳定性尤为重要，为此添加了高效乳化分散剂的组分，使除草剂在低温条件下仍能分散均匀，药效高； [0032] (3) of the present invention is added to the stabilizer components, in order to ensure the formulation ingredients with 2 years validity and security agents no significant degradation. In addition, this micro-emulsion is a wheat field herbicide for use in temperature l〇 ° C or less, low dispersion and dilution stability of the formulation is particularly important, for the efficient emulsifying and dispersing agent added components, the herbicide at a low temperature conditions can still uniformly dispersed, high efficacy;

[0033] (4)本发明的一种炔草酯微乳剂制备方法中，先将溶剂、炔草酯原药、安全剂、稳定剂和高效分散剂添加到配料釜中搅拌溶解成透明均相液体，使炔草酯充分稳定的溶解在溶剂中，然后加入乳化剂和水，搅拌得到炔草酯微乳液，更稳定，分散性更好，提高了炔草酯的药效； [0033] (4) A plant of the present invention alkyne ester microemulsion preparation, the first solvent, clodinafop-propargyl original drug, security agents, stabilizers and efficient dispersing agent is added to the kettle and stirred to dissolve the ingredients into a homogeneous transparent liquids, clodinafop-propargyl sufficiently stable dissolved in the solvent, then adding an emulsifier and water, stirring to obtain a microemulsion clodinafop-propargyl, more stable, better dispersion improves the efficacy of clodinafop-propargyl;

[0034] (5)本发明中的一种炔草酯微乳剂制备工艺简单，配方合理，易于制造，对环境友好，对生产和使用者的毒性较低，明显提高了对作物的安全性，尤其是制备的产品的分散度较好； [0034] (5) The preparation process of the present invention, a grass propargyl ester microemulsion simple, reasonable formula, easy to manufacture, environmentally friendly, low production and users of toxicity, significantly increased the safety of the crop, especially preferred product prepared dispersion;

[0035] (6)本发明的炔草酯微乳剂的应用方法在使用时，对野燕麦、看麦娘、硬草、茼草、 棒头草等大多数重要的一年生禾本科杂草有稳定的防效，同时将炔草酯微乳剂稀释后对杂草进行喷雾，利于控制炔草酯的浓度，可大面积喷洒，适用性强，配方中的高效分散剂克服了喷雾法中炔草酯微乳剂分散不均匀的缺点。 [0035] (6) clodinafop-propargyl micro emulsion of the present invention is applied when using the methods of wild oats, foxtail, hard grass, garland grass, grass Polypogon most important annual grass weeds have a stable control effect on weeds while after clodinafop-propargyl microemulsion diluted spray, which will help control the concentration of grass propargyl ester, a large area can be sprayed, applicability, formulation of highly efficient dispersant spray method overcomes clodinafop-propargyl microemulsion uniform dispersion disadvantages.