背景技术 Background

[0002] 炔草酯（clodinafop-propargyl)的化学名称为(R)_2_ [4-(5-氯-3-氟-2-批陡氧基）苯氧基]丙酸炔丙基酯，结构式为 [0002] clodinafop-propargyl (clodinafop-propargyl) the chemical name (R) _2_ [4- (5- chloro-3-fluoro-2-approved steep) phenoxy] propionic acid propargyl ester, of formula to

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Topic、Celio、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 Topic, Celio, top, clodinafop, etc., 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。 Its relatively stable in acidic medium, the alkaline hydrolysis medium, the light is easily decomposed in the soil quickly degrade into the free acid phenyl and 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。 Alkyne mexyl mechanism and is characterized by inhibiting acetyl coenzyme A carboxylase (ACCase) activity is an internal uptake herbicide, absorbed by plant leaves and leaf sheaths, the phloem conduction of points accumulated in the plant endogenous tissue, inhibit acetyl coenzyme A carboxylase, fatty acid synthesis stops growth and division of cells is not normal, communication and other lipid-containing membrane-based 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, propargyl ester herbicide grass showed little toxicity; with less; high efficacy; strong metabolism; 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] There are currently on the market alkyne grass herbicides are mainly wettable powder formulations. 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。 Wettable powders mainly composed of clodinafop-propargyl, additives (surfactants, thickeners, etc.) and the solid filler (kaolin, light calcium and diatomaceous earth) 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。 Due to relatively coarse particles wettable powder, which is in the course of larger solid particles attached to the surface of the weeds, easily absorbed by the weeds, loss of pesticide active ingredients are more, which increases 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 jet mill used in the production process will produce dust, pollution of 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 will be due in the course of formation of 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 WP, the Chinese Patent Publication No. CN102428921 A discloses an alkyne mexyl 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 granular acetylene mexyl still use, is not 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。 Thus developed a milky dosage alkyne ester herbicide grass is 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 a patent search, Chinese patent application number: 201010151613.7 patent document discloses an alkyne grass ester 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勻，然后投入比例要求的乳化剂，再搅拌均勻，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 weight percent solvent, cosolvent, and clodinafop-propargyl stirred at 50-200 rev / min speed mixing, then input the required proportion of the emulsifier, and then stir, and finally, water was added and stirring was continued 1- 2 hours, to a uniform transparent solution product, the invention can improve the efficiency of the agent's efficiency.

[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 document discloses an alkyne ester microemulsion grass production methods, the raw material formulation by percentage weight: include clodinafop-propargyl 12-18%, 5-10% solvent, help The solvent 22-28%, 10-15% surfactant, balance water; step 1: clodinafop-propargyl, mixed solvents, co-solvents; Step 2: mixing the surfactant and water; Step 3: Step 1 blended mixture and the mixture of step 2 finally obtained finished clodinafop-propargyl 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, 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10°C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 the alkyne ester grass 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 problems herbicide clodinafop-propargyl efficacy prolonged storage will clodinafop-propargyl significantly reduced; on the other hand, clodinafop-propargyl microemulsion is a common Herbicides, temperature substantially below 10 ° C, the formulation of low dispersion and dilution stability particularly important, above patent no effective solution to 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 issues and low dispersion problems, the present invention provides an alkyne grass ester microemulsion and preparation methods, and application methods, clodinafop-propargyl microemulsions Join detoxification quinoline as a security agent 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。 While for the storage stability of clodinafop-propargyl and security agents, stabilizers added component to ensure the formulation ingredients with 2 years validity and the security agent, no significant degradation of the herbicide of the present invention, it is mainly used in controlling wheat Tanaka part of weeds, wild oats to see the most important annual grass weeds, formulation and efficient emulsifying agent to enhance the alkyne ester of low 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 an alkyne grass ester microemulsion with a wide range of prevention, low toxicity, anti-efficiency and 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 aspect of the present invention is used as follows.

[0011] 一种炔草酯微乳剂，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] A microemulsion clodinafop-propargyl, and its constituent mass percentage: 5-20% clodinafop-propargyl, the safener 1-5%, 15-40% solvent, 1-4% stabilizer, emulsifier 10 -24%, 1-5% efficient dispersant, and the balance 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, the 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, polyether alcohols, alkylphenol ether phosphates, heterogeneous alcohol ethoxylates, triphenylethyl phenol ethoxylates, isopropyl The composition structure of polyether polyol and nonionic block copolymer having a 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% polyether alcohol isomers, balance 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 efficient dispersant is polyethylene glycol monooleate, polyoxyethylene oleate, fatty acid esters, their percent by mass: polyethylene glycol monooleate 10-20% , polyoxyethylene laurate 20-30%, and the balance of fatty acid esters.

[0018] 一种炔草酯微乳剂的制备方法，其步骤为： [0018] A 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) polyether amine fat, triphenyl phosphite and epichlorohydrin mixing evenly into stabilizer, wherein the aliphatic amine polyether 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齐U，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 made efficient mixing uniformly dispersed homogeneous U, wherein the polyethylene glycol monooleate 10-20%, 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, polyether alcohols, alkylphenol ether phosphates, heterogeneous alcohol ethoxylates, triphenylethyl phenol ethoxylates, heterogeneous alcohol polyether and nonionic block copolymer was uniformly mixing emulsifier, wherein the anionic emulsifier 2-10%, 5-10% polyether alcohols, alkylphenol ether phosphate 12-25%, heterogeneous alcohol poly 10-20% polyoxyethylene ether, ethyl triphenyl sub polyoxyethylene ethers 5-15%, 3-15% polyether alcohol isomers, the remainder is a nonionic block copolymer;

[0022] (D)依次将溶剂、炔草酯原药、安全剂、步骤㈧中得到的稳定剂和步骤⑶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) successively adding a solvent, clodinafop-propargyl original drug, safeners, obtained in step (viii) and stabilizer obtained in step ⑶ efficient dispersant formulation kettle into at 50-150 rev / min speed It was dissolved under stirring into a homogeneous transparent liquid, wherein the solvent is 15-40%, 5-20% clodinafop-propargyl, the safener 1-5%, 1-4% stabilizer, dispersing agent 1-5% efficient;

[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/分的转速搅拌均勻形成炔草酯微乳剂； Homogeneous liquid [0023] (E) the step (C) obtained in the emulsifier and water were added step (D) is obtained, continue 50 to 150 rev / min speed stir grass propargyl ester microemulsion form;

[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 steps (E) obtained alkyne grass ester microemulsion detect efficacy, after passing transferred to sedimentation 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) to step (F) obtained alkyne grass ester 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% by mass parts of clodinafop-propargyl.

[0027] -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] - grass seed alkyne ester microemulsion applications, the steps of the alkyne grass 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 is:

[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) The present invention employs environmentally safe and friendly environment-friendly solvent system to water instead of part of the solvent, the active ingredient in a molecular state exists, with the EC and WP compared to better, more environmentally friendly and safer , more economical, environmental and life more secure, while blending before spraying easier, 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) The present invention is added as a security agent quinoline detoxification, effectively improve the safety of the crop, ensure weeding while promoting the growth of crops, the use of more secure;

[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 to ensure the formulation ingredients with a two-year validity period and no significant degradation of the security agents, in addition, this micro-emulsion is Herbicides, for the use of temperature l〇 ° C below, low dispersion and dilution stability of the formulation is particularly important, for adding an efficient emulsifying agent component of the herbicide and at low temperatures still dispersed, high efficacy;

[0033] (4)本发明的一种炔草酯微乳剂制备方法中，先将溶齐IJ、炔草酯原药、安全齐ϋ、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 solution together IJ, clodinafop-propargyl original drug, safe Qi ϋ, stabilizers and highly effective dispersing agent is added to the ingredients into a pot and stirred to dissolve clear homogeneous 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 is a microemulsion clodinafop-propargyl simple, reasonable formula, easy to manufacture environmentally friendly, low production and users toxicity, significantly increased the safety of the crop, Especially preferred dispersion product prepared;

[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 microemulsion method of the present invention is applied in the use of wild oats, foxtail, hard grass, garland grass, grass Polypogon most important annual grass weeds stable control effect on weeds while the grass after alkyne ester microemulsion diluted spray, which will help control the concentration of alkyne ester grass, spray a large area, applicability, the formulation of effective dispersant spraying method overcomes the grass propargyl ester microemulsion uneven dispersion disadvantages.