| Publication number | CN103210952 B |
| Publication type | Grant |
| Application number | CN 201210376780 |
| Publication date | 3 Dec 2014 |
| Filing date | 29 Sep 2012 |
| Priority date | 29 Sep 2012 |
| Also published as | CN103210952A |
| Publication number | 201210376780.0, CN 103210952 B, CN 103210952B, CN 201210376780, CN-B-103210952, CN103210952 B, CN103210952B, CN201210376780, CN201210376780.0 |
| Inventors | 吴华悦, 高文霞, 刘妙昌, 陈久喜, 韩丹丹, 狄安利, 池艳艳, 金杰 |
| Applicant | 温州大学 |
| Export Citation | BiBTeX, EndNote, RefMan |
| Patent Citations (3), Classifications (3), Legal Events (3) | |
| External Links: SIPO, Espacenet | |
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技术领域 Technical Field
[0001] 本发明涉及农药制剂领域，特别是涉及一种杀扑磷纳米乳剂及其制备方法。 [0001] The present invention relates to the field of pesticide formulations, particularly to a Methidathion nano emulsions and their preparation methods.
(二) (B)
背景技术 Background
[0002] 杀扑磷，化学名称为:S-2，3-二氢-5-甲氧基-2-氧代-1,3，4-噻二唑-3-基甲基0,0-二甲基二硫代磷酸酯，英文通用名:Methidath1n，CAS编号:950-37_8，分子式:C6H11N2O4PS3，分子量:302.32，结构式如下: [0002] methidathion, chemical name: S-2,3- dihydro-5-methoxy-2-oxo-1,3,4-thiadiazol-3-ylmethyl O, O dimethyl phosphorothioate, English common name: Methidath1n, CAS Number: 950-37_8, molecular formula: C6H11N2O4PS3, molecular weight: 302.32, the formula is as follows:
[0004] 杀扑磷，是一种广谱的有机磷杀虫剂，活性较高，药效迅速，喷洒后耐雨水冲刷，具有触杀、胃毒和渗透作用，能渗入植物组织内，对咀嚼式和刺吸式口器害虫均有杀灭效力，尤其对介壳虫有特效，对螨类有一定的控制作用。 [0004] methidathion, it is a broad-spectrum organophosphate insecticide, higher activity, rapid efficacy, resistance to rain erosion after spraying with contact and stomach poison and infiltration, can penetrate the plant tissue, chewing and sucking mouthparts are killing effect, in particular, have effects on the scale insects, mites have some control. 适用于果树、棉花、茶树、蔬菜等作物上防治多种害虫。 Apply to control a variety of pests on fruit trees, cotton, tea, vegetables and other crops. 适用于花生、大豆、棉花、果树、蔬菜的害虫。 Suitable for peanuts, soybeans, cotton, fruit trees, vegetables pests. 防治农作物害虫如麦蚜、吸浆虫、粘虫、玉米螟、大豆蚜虫、大豆食心虫等。 Control crop pests such as Aphids, midge, armyworms, corn borer, soybean aphid, soybean borer. 防治蔬菜害虫如小菜蛾、甘蓝夜蛾、斜纹夜蛾、菜螟坐寸ο Control vegetable pests such as diamondback moth, cabbage armyworm, Spodoptera exigua, vegetables borer sit inch ο
[0005] 杀扑磷主要剂型为20%、40%乳油，使用时将40%乳油兑水800~1000倍，有机溶剂用量高达70%以上。 [0005] methidathion main formulations of 20%, 40% EC, 40% EC when watered using 800 to 1000 times the amount of organic solvent as high as 70%. 传统杀扑磷乳油制剂由于乳油中含有大量的易燃有机溶剂，在长期的使用过程中，大量的有机溶剂挥发到大气中，对环境造成了严重的污染。 Traditional methidathion EC because the EC formulation contains large amounts of flammable organic solvents, in the long-term use, a large amount of volatile organic solvents into the atmosphere, causing serious environmental pollution. 水乳剂则是以水为介质，既可以改善工厂的操作环境，避免了有机溶剂对操作工人的毒害，又避免了大量有机溶剂的浪费和对大自然的污染。 EW is based on water as the medium, both to improve the plant's operating environment, avoiding organic solvents on operating workers poisoned, but also avoid wasting large amounts of organic solvents and the pollution of nature. 不过，虽然目前国内出现了一些农药水乳剂，但是其稳定性得不到保证，储存过程中容易出现分层、絮凝等现象。 However, although there have been some domestic pesticide water emulsion, but its stability is not guaranteed, the storage process prone to delamination, flocculation phenomenon.
[0006] 纳米乳剂是一类新型制剂，粒径为20-500 nm，其动力学稳定性高、光学透明度好、粘度低，是一类理想的新型水性农药制剂。 [0006] The nanoemulsion is a new class of agents with particle size of 20-500 nm, high kinetic stability, optical clarity, low viscosity, is a kind of ideal new water-based pesticide formulations.
(三) (Iii)
发明内容 DISCLOSURE
[0007] 本发明的目的是制备杀扑磷的纳米乳剂，通过加入乳化剂、助溶剂、增稠剂、抗冻剂和消泡剂制备得到稳定的杀扑磷的纳米乳剂。 Objective [0007] The present invention is the preparation of methidathion nanoemulsion, by adding emulsifying agents, solvents, thickeners, antifreeze agents and defoamers prepared methidathion stable nanoemulsions.
[0008] 本发明采用的技术方案如下: [0008] The technical solution of the present invention is used as follows:
[0009] 一种杀扑磷纳米乳剂，以杀扑磷为有效成分，制备所述杀扑磷纳米乳剂的原料包括下列重量百分比的成分: [0009] A nanoemulsion methidathion to methidathion as an active ingredient, the preparation of the starting material methidathion kill nanoemulsion comprises the following weight percent composition:
[0010] [0010]
[0012] 制备所述杀扑磷纳米乳的方法包括以下步骤:(1)按上述重量百分比称取各组分原料，先将杀扑磷原药与有机溶剂、部分乳化剂A搅拌均匀并溶解，充分分散均匀，制成第一相；(2)将剩下的乳化剂B和其他余下的试剂溶于水生成第二相；(3)第二相在700-2000转/分钟转速的搅拌下，将第一相缓慢滴加入第二相，继续搅拌30-60分钟，制成所述杀扑磷纳米乳剂； The methidathion nanoemulsion method [0012] The preparation includes the following steps: (1) according to the above weight percentages of the components weighed raw materials, methidathion first drug and organic solvents, emulsifiers part A and stir to dissolve , fully dispersed, forming the first phase; (2) the rest of the remaining emulsifiers B and other reagents dissolved in water to generate a second phase; (3) a second phase in the 700-2000 rev / min stirring speed Under the first phase was slowly dropped into the second phase and continue stirring for 30-60 minutes, made the methidathion nanoemulsion;
[0013] 本发明所述的有机溶剂为甲苯、己烷、甲苯、丙酮、乙醇、正辛醇，优选为甲苯。 [0013] The organic solvent according to the present invention is toluene, hexane, toluene, acetone, ethanol, n-octanol, preferably toluene.
[0014] 本发明所述的助溶剂为聚乙二醇类化合物，优选为PEG-200、PEG-400或PEG-600。 [0014] The present invention is the co-solvent is a polyethylene glycol-based compound, preferably PEG-200, PEG-400 or PEG-600.
[0015] 本发明所述乳化剂是乳化剂A和乳化剂B的总和；也就是说，乳化剂A和乳化剂B的总的质量分数为所有原料的3.5-13%，其中，所述乳化剂A的质量用量通常为乳化剂的总质量用量的10~35%。 [0015] The emulsifier of the present invention is the sum of emulsifier A and B of the emulsifier; that is, the total mass fraction of emulsifier A to emulsifier B 3.5-13% of all raw materials, wherein the emulsion A generally used in an amount by mass of the total mass of the emulsifier 10 to 35%.
[0016] 本发明所述的乳化剂为磺酸盐类乳化剂、聚醚类乳化剂或他们的任意比例复配的混合乳化剂。 Emulsifier [0016] The present invention is an emulsifier sulfonates, polyether emulsifier or mixed emulsifier their compound in any ratio. 其中，所述的磺酸盐类乳化剂优选为烷基苯磺酸钙(如农乳500)或烷基苯磺酸钠；所述的聚醚类乳化剂优选为烷基酚聚氧乙烯醚(如农乳100)、聚氧乙烯聚氧丙烯共聚物、脂肪醇聚氧乙烯醚、失水山梨醇油酸酯聚氧乙烯醚(如吐温-60、吐温-80)或失水山梨醇脂肪酸酯(司盘-60、司盘-80 )。 Wherein said emulsifier is preferably alkyl benzene sulfonate calcium sulfonate (such as dairy farming and 500) or benzene sulfonate; wherein the emulsifier is preferably a polyether alkyl phenol ethoxylates (eg Nongru 100), polyoxyethylene polyoxypropylene copolymers, fatty alcohol ethoxylates, sorbitan monooleate polyoxyethylene ethers (such as Tween -60, Tween-80) or sorbitan fatty acid esters (Span -60, Span -80).
[0017] 具体的，更优选所述乳化剂为农乳500、农乳100、吐温-60、吐温-80、司盘-60或司盘-80中的一种或两种以上任意比例的组合。 [0017] Specifically, more preferably, the emulsifier is 500 dairy farming, dairy farming 100, Tween -60, Tween 80, Span Span -80 -60 or one or two or more in any proportion combination.
[0018] 本发明所述的抗冻剂为乙二醇、丙二醇或丙三醇中的一种或两种以上的任意组口ο [0018] The antifreeze agent of the present invention are ethylene glycol, propylene glycol or glycerol in one or two or more of any group of ports ο
[0019] 本发明所述制备所述杀扑磷纳米乳剂的原料包括下列重量百分比的成分，是指上述成分是为达到本发明技术目的必不可少的成分，但也可以为了一些特殊功能要求加入一些对纳米乳剂没有负面影响的功能添加剂，例如增稠剂、消泡剂等。 [0019] The nanoemulsion methidathion feedstock comprising by weight percent composition of the present invention is prepared, the above-described components means a technical object is to achieve an essential component of the present invention, it may be added to some special functional requirements Some have no negative impact on the nanoemulsion functional additives, such as thickening agents, defoamers.
[0020] 具体的，本发明制备所述杀扑磷纳米乳剂的原料还可以包括质量百分分数0-0.5%增稠剂和/或质量百分分数0-0.25%的消泡剂；所述增稠剂和/或消泡剂用于步骤(2)中作为其他余下的试剂部分与剩下的乳化剂B和其他余下的试剂溶于水生成第二相； [0020] Specifically, the present invention is prepared methidathion nanoemulsion feedstock may also include mass fraction of 0-0.5% percent thickening and / or mass fraction 0-0.25% percent defoamers; the thickening and / or anti-foaming agent used in step (2) as the other remaining portion of the rest of the emulsifying agents B and other reagents were dissolved in the remaining water to produce a second phase;
[0021] 本发明所述的增稠剂为纤维素醚及其衍生物类增稠剂或聚乙二醇双硬脂酸酯，具体优选所述增稠剂为羟乙基纤维素、甲基羟乙基纤维素、乙基羟乙基纤维素、甲基羟丙基纤维素、羧甲基纤维素或聚乙二醇6000双硬脂酸酯(简称PEG6000DS)，更优选为PEG6000DS、 [0021] The thickener of the present invention are cellulose ethers and derivatives thickener or polyethylene glycol distearate, particularly preferably the thickening agent is hydroxyethyl cellulose, methyl hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl methyl cellulose, carboxymethylcellulose or polyethylene glycol 6000 distearate (abbreviated PEG6000DS), more preferably PEG6000DS,
乙基羟乙基纤维素或羧甲基纤维素。 Ethyl hydroxyethyl cellulose or carboxymethyl cellulose.
[0022] 本发明所述的消泡剂优选为有机硅消泡剂，更优选为乳液型硅油消泡剂，如上海立奇化工助剂有限公司生产的L-101、L-1000系列，上海箭宇化工有限公司生产的JY-810-1型号等。 [0022] defoamers according to the invention is preferably a silicone anti-foaming agent, and more preferably silicone emulsion defoamers, such as the Shanghai Chemical Agents Limited Li Qi production of L-101, L-1000 series, Shanghai Arrow-Chemical Co., Ltd. of JY-810-1 models and so on.
[0023] 所述质量百分分数0-0.5%增稠剂是指增稠剂在所有原料组分中的重量百分比为0-0.5%，其中的O是指无限接近于O而不为0，质量百分分数是增稠剂相对于所有原料成分的百分比，也就是说，在其他组分百分比不变的情况下，加入0-0.5%增稠剂，相应的水的用量减少，水的用量保证所有组分的总和为100%即可。 [0023] The mass fraction of 0 to 0.5% thickener percentage refers to the percentage by weight of thickener in all raw material components in the 0 to 0.5%, which means that O O without infinitely close to 0, Quality score is the percentage of the thickener with respect to the percentage of all ingredients, that is, the percentage in other components remain unchanged, added 0-0.5% thickener, to reduce the amount of water corresponding to the amount of water to ensure that the sum of all components is 100% can be.
[0024] 所述质量百分分数0-0.25%的消泡剂是指消泡剂在所有原料组分中的重量百分比为0-0.25%，其中的O是指无限接近于O而不为0，质量百分分数是增稠剂相对于所有原料成分的百分比，也就是说，在其他组分百分比不变的情况下，加入0-0.5%增稠剂，相应的水的用量减少，水的用量保证所有组分的总和为100%即可。 [0024] The percentage of the mass fraction of 0-0.25% defoamer defoamers percentage refers to the weight of all the feed composition of 0-0.25%, which means that infinitely close to O O instead of 0 Quality percentile scores are relative to the percentage of all ingredients thickeners, that is, the percentage in other components remain unchanged, added 0-0.5% thickener, a corresponding reduction in the amount of water, water The amount that the sum of all components is 100% can be.
[0025] 本发明所用的水可以为自来水或是去离子水。 The water used herein [0025] This may be water or deionized water.
[0026] 所述步骤(1)中，充分分散均匀可利用常规搅拌手段，优选在超声波下震荡5-20分钟。 [0026] The step (1), fully dispersed using conventional stirring means, preferably 5-20 minutes under ultrasonic vibration.
[0027] 所述的步骤(3)中，所述将第一相缓慢滴加入第二相，其中的缓慢滴加是为了有利于形成纳米乳，通常滴加速度为0.15^0.25mL/min。 Said step of [0027] (3), the first phase of the second phase was slowly added dropwise, which was slowly dropped in order to facilitate the formation of a nanoemulsion, usually dropping to 0.15 ^ 0.25mL / min.
[0028] 进一步，优选本发明所述杀扑磷纳米乳剂由下列重量百分比的成分制备而成: [0028] Further, the present invention is preferably the nanoemulsion methidathion by the following percentages by weight of the composition prepared from:
[0031] 所述制备方法为:(1)按上述重量百分比称取各组分原料，先将杀扑磷原药与有机溶剂、部分乳化剂A搅拌均匀并溶解，在超声波下震荡5-20分钟，制成第一相；(2)再将剩下的乳化剂B、助溶剂、增稠剂、抗冻剂、消泡剂溶于水生成第二相；(3)第二相在700-2000转/分钟转速的搅拌下，将第一相缓慢滴加入第二相，继续搅拌30-60分钟，制成所述杀扑磷纳米乳剂。 [0031] The preparation method as follows: (1) according to the above weight percentages of the components weighed raw materials, methidathion first drug and organic solvents, emulsifiers part A and stir to dissolve, under ultrasonic shock 5-20 minutes, forming the first phase; (2) then the rest of the emulsifier B, cosolvents, thickeners, antifreeze agents, antifoaming agents dissolved in water to generate a second phase; (3) a second phase 700 Under -2000 rev / min stirring speed, the first phase was slowly dropped into the second phase and continue stirring for 30-60 minutes, made the methidathion nanoemulsion.
[0032] 本发明还提供一种杀扑磷纳米乳剂的制备方法，所述杀扑磷纳米乳剂由下列重量百分比的成分制备而成: [0032] The present invention also provides a method for preparing a nanoemulsion methidathion, methidathion the killing ingredient nanoemulsion percentage by weight of the preparation made by the following:
[0033] [0033]
[0034] 所述制备方法为:(1)按上述重量百分比称取各组分原料，先将杀扑磷原药与有机溶剂、部分乳化剂A搅拌均匀并溶解，在超声波下震荡5-20分钟，制成第一相；(2)再将剩下的乳化剂B、助溶剂、增稠剂、抗冻剂、消泡剂溶于水生成第二相；(3)第二相在700-2000转/分钟转速的搅拌下，将第一相缓慢滴加入第二相，继续搅拌30-60分钟，制成所述杀扑磷纳米乳剂； [0034] The preparation method as follows: (1) according to the above weight percentages of the components weighed raw materials, methidathion first drug and organic solvents, emulsifiers part A and stir to dissolve, under ultrasonic shock 5-20 minutes, forming the first phase; (2) then the rest of the emulsifier B, cosolvents, thickeners, antifreeze agents, antifoaming agents dissolved in water to generate a second phase; (3) a second phase 700 -2000 rev / min stirring speed, the first phase of the second phase was slowly added dropwise, stirring was continued for 30 to 60 minutes to prepare the nanoemulsion methidathion;
[0035] 所述的有机溶剂为甲苯、己烷、甲苯、丙酮、乙醇或正辛醇； [0035] The organic solvent is toluene, hexane, toluene, acetone, ethanol, or n-octanol;
[0036] 所述的助溶剂为聚乙二醇类化合物； [0036] The co-solvent is polyethylene glycol compounds;
[0037] 所述的乳化剂为磺酸盐类乳化剂或聚醚类乳化剂或他们的任意比例复配混合乳化剂； Emulsifiers [0037], wherein the emulsifier or polyether sulfonate type emulsifiers or any proportion of their complex mixed emulsifier;
[0038] 所述乳化剂是乳化剂A和乳化剂B的总和； [0038] The emulsifier is the sum of emulsifiers and emulsifier B of A;
[0039] 所述的抗冻剂为乙二醇、丙二醇或丙三醇中的一种或两种以上的任意组合。 [0039] ethylene glycol, propylene glycol or glycerol in an arbitrary combination of said two or more cryoprotectants.
[0040] 本发明与现有技术相比，其有益效果体现在: [0040] The present invention over the prior art, and its beneficial effects reflected in:
[0041] 1、本发明利用纳米乳这类水性制剂替代了传统杀扑磷乳油制剂中有毒有害的有机溶剂，降低了毒性，实现绿色环保。 [0041] 1, the present invention utilizes such aqueous nanoemulsion formulation replaces the traditional preparation methidathion EC for hazardous organic solvents, reduced toxicity, go green.
[0042] 2、利用纳米乳剂的动力学稳定性高的性能提高了杀扑磷水性制剂的稳定性。 [0042] 2, the use of nanoemulsion high kinetic stability of the performance and improve the stability methidathion aqueous formulation.
[0043] 3、在水乳剂中添加水溶性较好的多糖化合物或衍生物作为增稠剂，由于多糖衍生物具有较好的生物可降解性，因此使制备的杀扑磷纳米乳剂稳定性提高的同时依然保持绿色化。 [0043] 3, adding a water-soluble polysaccharide is preferably a compound or a derivative thereof as a thickening agent in an aqueous emulsion, since the polysaccharide derivative has good biodegradability, thus making methidathion prepared to improve the stability of the nanoemulsion at the same time remain green.
(四) (Iv)
附图说明 Brief Description
[0044] 图1实施例1制得的杀扑磷纳米乳剂的粒径分布图 [0044] FIG. 1 embodiment of the particle size distribution obtained in Example 1 methidathion nanoemulsion
(五)具体实施方式: (E) the specific embodiments:
[0045] 以下以具体实施例来说明本发明的技术方案，但本发明的保护范围不限于此: [0045] In the following specific examples to illustrate the technical solution of the present invention, but are not limited to the scope of the invention:
[0046] 本发明所述的纳米乳的粒径的检测方法如下:取所制备的杀扑磷纳米乳样品用去离子水稀释100倍,用激光粒度仪(Zetasizer Nano-ZS, Malvern, UK)测量纳米乳的平均粒径和粒径分布。 [0046] The detection method of the present invention nanoemulsion particle size as follows: Methidathion take nanoemulsion prepared sample was diluted 100-fold with deionized water, using a laser particle size analyzer (Zetasizer Nano-ZS, Malvern, UK) The average particle size and particle size distribution measuring nanoemulsion.
[0047] 实施例1 [0047] Example 1
[0048] [0048]
[0049] 制备过程如下: [0049] was prepared as follows:
[0050] 1、称取上述配方的原药、乳化剂、助溶剂、增稠剂、抗冻剂、消泡剂及水。 [0050] 1. Weigh the above formulation of the original drug, emulsifying agents, solvents, thickeners, antifreeze agents, defoamers and water.
[0051] 2、将杀扑磷加入锥形瓶中，加入甲苯搅拌溶解之后，再加入司盘80搅拌均匀，再在超声波(50 W，40 kHz )下震荡10分钟，形成第一相。 [0051] 2, methidathion join conical flask, toluene and after stirring to dissolve, then add Span 80 Stir, then in an ultrasonic (50 W, 40 kHz) shock for 10 minutes to form a first phase.
[0052] 3、将PEG-400、吐温60、PEG6000DS、乙二醇、消泡剂加到锥形瓶内，加水至100g，搅拌均匀至溶解，形成第二相。 [0052] 3, PEG-400, Tween 60, PEG6000DS, ethylene glycol, a defoaming agent was added to a conical flask, add water to 100g, stir until dissolved, to form a second phase.
[0053] 4、第二相在1000转/分钟转速的搅拌下，将第一相缓慢滴加入第二相(滴加速度为0.2mL/min)，继续搅拌30分钟，形成均匀的纳米乳，纳米乳的粒径分布如图1所示。 [0053] 4, the second phase at 1000 rev / min stirring speed, the first phase of the second phase was slowly added dropwise (dropping of 0.2mL / min), stirring was continued for 30 minutes to form a uniform nanoemulsion, nano Milk particle size distribution as shown in Fig. 所述的纳米乳的粒径的检测方法如下:取所制备的杀扑磷纳米乳样品用去离子水稀释100倍，用激光粒度仪(Zetasizer Nano-ZS, Malvern, UK)测量纳米乳的平均粒径和粒径分布。 Detection method according to particle size nanoemulsion as follows: Methidathion take nanoemulsion prepared sample was diluted 100-fold with deionized water, using a laser particle size analyzer (Zetasizer Nano-ZS, Malvern, UK) measuring nanometer average milk particle size and particle size distribution.
[0054] 上述方法制备的杀扑磷纳米乳剂，经O~4 °C冷藏2周无结晶析出，54±2 °C热储2周后仍然呈现透明状态，无析油现象；纳米乳液稀释后，呈现淡蓝色荧光，乳液稳定性好。 [0054] The above method methidathion nanoemulsion by O ~ 4 ° C refrigerated two weeks without crystallization, 54 ± 2 ° C thermal storage two weeks later still showing a transparent state, no analysis of oil phenomenon; nanoemulsion after dilution , showing a pale blue fluorescence, good emulsion stability.
[0055] 实施例2 [0055] Example 2
[0056] [0056]
[0057] 制备过程如下: [0057] was prepared as follows:
[0058] 1、称取上述配方的原药、乳化剂、助溶剂、增稠剂、抗冻剂、消泡剂及水。 [0058] 1. Weigh the above formulation of the original drug, emulsifying agents, solvents, thickeners, antifreeze agents, defoamers and water.
[0059] 2、将杀扑磷加入锥形瓶中，加入甲苯搅拌溶解之后，再加入司盘80搅拌均匀，再在超声波(50 W，40 kHz )下震荡5分钟，形成第一相。 [0059] 2, methidathion join conical flask, toluene and after stirring to dissolve, then add Span 80 Stir, then in an ultrasonic (50 W, 40 kHz) shock for 5 minutes to form the first phase.
[0060] 3、将PEG-200、吐温60、PEG6000DS、丙三醇、消泡剂加到锥形瓶内，加水至100g，搅拌均匀至溶解，形成第二相。 [0060] 3, PEG-200, Tween 60, PEG6000DS, glycerol, defoamer was added to a conical flask, add water to 100g, stir until dissolved, to form a second phase.
[0061] 4、第二相在1200转/分钟转速的搅拌下，将第一相缓慢滴加入第二相(滴加速度为0.25mL/min),继续搅拌50分钟，形成均匀的纳米乳，按实施例1的方法测纳米乳的粒径，测得平均粒径80 nm，低温稳定性合格，热储稳定性(54±2 °C，2周)分解率≤10%。 [0061] 4, the second phase at 1200 rev / min stirring speed, the first phase of the second phase was slowly added dropwise (dropping of 0.25mL / min), stirring was continued for 50 minutes to form a uniform nanoemulsion, by implementation of the method of measuring particle size nanoemulsion cases, the measured average particle size of 80 nm, qualified low temperature stability, thermal storage stability (54 ± 2 ° C, 2 weeks) decomposition rate ≤10%.
[0062] 实施例3 [0062] Example 3
[0063] [0063]
[0065] 制备过程如下: [0065] was prepared as follows:
[0066] 1、称取上述配方的原药、乳化剂、助溶剂、增稠剂、抗冻剂、消泡剂及水。 [0066] 1. Weigh the above formulation of the original drug, emulsifying agents, solvents, thickeners, antifreeze agents, defoamers and water.
[0067] 2、将杀扑磷加入锥形瓶中，加入甲苯搅拌溶解之后，再加入农乳500搅拌均匀，再在超声波(50 W，40 kHz )下震荡10分钟，形成第一相。 [0067] 2, methidathion join conical flask, toluene and after stirring to dissolve, then add the dairy farming 500 Stir, then in an ultrasonic (50 W, 40 kHz) shock for 10 minutes to form a first phase.
[0068] 3、将PEG-400、吐温60、乙基羟乙基纤维素、丙二醇、消泡剂加到锥形瓶内，加水至100g，搅拌均匀至溶解，形成第二相。 [0068] 3, PEG-400, Tween 60, ethyl hydroxyethyl cellulose, propylene glycol, a defoaming agent was added to a conical flask, add water to 100g, stir until dissolved, to form a second phase.
[0069] 4、第二相在700转/分钟转速的搅拌下，将第一相缓慢滴加入第二相(滴加速度为 [0069] 4, the second phase at 700 rev / min speed under stirring, the first phase was slowly dropped into the second phase (dropping the
0.2mL/min)，继续搅拌50分钟，形成均匀的纳米乳，按实施例1的方法测纳米乳的粒径，测得平均粒径110 nm。 0.2mL / min), stirring was continued for 50 minutes to form a uniform nanoemulsion according to the method of Example 1 was measured nanoemulsion particle diameter, measured by the average particle diameter of 110 nm. 低温稳定性合格，热储稳定性(54±2 °C，2周)分解率≤10%。 Qualified low temperature stability, thermal storage stability (54 ± 2 ° C, 2 weeks) decomposition rate ≤10%.
[0070] 实施例4 [0070] Example 4
[0071] [0071]
[0073] 制备过程如下: [0073] was prepared as follows:
[0074] 1、称取上述配方的原药、乳化剂、助溶剂、增稠剂、抗冻剂、消泡剂及水。 [0074] 1. Weigh the above formulation of the original drug, emulsifying agents, solvents, thickeners, antifreeze agents, defoamers and water.
[0075] 2、将杀扑磷加入锥形瓶中，加入甲苯搅拌溶解之后，再加入农乳500搅拌均匀，再在超声波(50 W，40 kHz )下震荡20分钟，形成第一相。 [0075] 2, methidathion join conical flask, toluene and after stirring to dissolve, then add the dairy farming 500 Stir, then in an ultrasonic (50 W, 40 kHz) shock for 20 minutes to form the first phase.
[0076] 3、将PEG-400、吐温80、羧甲基纤维素、乙二醇、消泡剂加到锥形瓶内，加水至100g，搅拌均匀至溶解，形成第二相。 [0076] 3, PEG-400, Tween 80, carboxymethyl cellulose, ethylene glycol, a defoaming agent was added to a conical flask, add water to 100g, stir until dissolved, to form a second phase.
[0077] 4、第二相在700转/分钟转速的搅拌下，将第一相缓慢滴加入第二相(滴加速度为 [0077] 4, the second phase at 700 rev / min speed under stirring, the first phase was slowly dropped into the second phase (dropping the
0.2mL/min)，继续搅拌60分钟，形成均匀的纳米乳，按实施例1的方法测纳米乳的粒径，测得平均粒径70 nm。 0.2mL / min), stirring was continued for 60 minutes to form a uniform nanoemulsion according to the method of Example 1 was measured nanoemulsion particle diameter, measured by the average particle diameter of 70 nm. 低温稳定性合格，热储稳定性(54±2 °C，2周)分解率≤10%。 Qualified low temperature stability, thermal storage stability (54 ± 2 ° C, 2 weeks) decomposition rate ≤10%.
[0078] 实施例5 [0078] Example 5
[0079] [0079]
[0080] [0080]
[0081] 制备过程如下: [0081] was prepared as follows:
[0082] 1、称取上述配方的原药、乳化剂、助溶剂、增稠剂、抗冻剂、消泡剂及水。 [0082] 1. Weigh the above formulation of the original drug, emulsifying agents, solvents, thickeners, antifreeze agents, defoamers and water.
[0083] 2、将杀扑磷加入锥形瓶中，加入甲苯搅拌溶解之后，再加入司盘60搅拌均匀，再在超声波下震荡15分钟，形成第一相。 [0083] 2, methidathion join conical flask, toluene and after stirring to dissolve, then add Span 60 Stir, then ultrasonic vibration for 15 minutes to form the first phase.
[0084] 3、将PEG-200、吐温80、PEG6000DS、丙三醇、消泡剂加到锥形瓶内，加水至100g，搅拌均匀待溶解，形成第二相。 [0084] 3, PEG-200, Tween 80, PEG6000DS, glycerol, defoamer was added to a conical flask, add water to 100g, stir until dissolved, to form a second phase.
[0085] 4、第二相在1500转/分钟转速的搅拌下，将第一相缓慢滴加入第二相(滴加速度为0.2mL/min)，继续搅拌35分钟，形成均匀的纳米乳，按实施例1的方法测纳米乳的粒径，测得平均粒径150 nm。 [0085] 4, the second phase at 1500 rev / min stirring speed, the first phase of the second phase was slowly added dropwise (dropping of 0.2mL / min), stirring was continued for 35 minutes to form a uniform nanoemulsion, by Example 1 measured nanoemulsion particle diameter, the average particle size measured 150 nm. 低温稳定性合格，热储稳定性(54±2 °C，2周)分解率≤10%。 Qualified low temperature stability, thermal storage stability (54 ± 2 ° C, 2 weeks) decomposition rate ≤10%.
[0086] 实施例6 [0086] Example 6
[0087] [0087]
[0089] 制备过程如下: [0089] was prepared as follows:
[0090] 1、称取上述配方的原药、乳化剂、助溶剂、增稠剂、抗冻剂、消泡剂及水。 [0090] 1. Weigh the above formulation of the original drug, emulsifying agents, solvents, thickeners, antifreeze agents, defoamers and water.
[0091] 2、将杀扑磷加入锥形瓶中，加入甲苯搅拌溶解之后，再加入司盘80搅拌均匀，再在超声波(50 W，40 kHz )下震荡10分钟，形成第一相。 [0091] 2, methidathion join conical flask, toluene and after stirring to dissolve, then add Span 80 Stir, then in an ultrasonic (50 W, 40 kHz) shock for 10 minutes to form a first phase.
[0092] 3、将PEG-600、吐温60、PEG6000DS、乙二醇、消泡剂加到锥形瓶内，加水至100g，搅拌均匀至溶解，形成第二相。 [0092] 3, PEG-600, Tween 60, PEG6000DS, ethylene glycol, a defoaming agent was added to a conical flask, add water to 100g, stir until dissolved, to form a second phase.
[0093] 4、第二相在1200转/分钟转速的搅拌下，将第一相缓慢滴加入第二相(滴加速度为0.2mL/min)，继续搅拌50分钟，形成均匀的纳米乳，按实施例1的方法测纳米乳的粒径，测得平均粒径180 nm。 [0093] 4, the second phase at 1200 rev / min stirring speed, the first phase of the second phase was slowly added dropwise (dropping of 0.2mL / min), stirring was continued for 50 minutes to form a uniform nanoemulsion, by Example 1 measured nanoemulsion particle diameter, measured by the average particle diameter of 180 nm. 低温稳定性合格，热储稳定性(54±2 °C，2周)分解率10%。 Qualified low temperature stability, thermal storage stability (54 ± 2 ° C, 2 weeks) decomposition rate of 10%.
[0094] 实施例7 [0094] Example 7
[0095] [0095]
[0097] 制备过程如下: [0097] was prepared as follows:
[0098] 1、称取上述配方的原药、乳化剂、助溶剂、增稠剂、抗冻剂、消泡剂及水。 [0098] 1. Weigh the above formulation of the original drug, emulsifying agents, solvents, thickeners, antifreeze agents, defoamers and water.
[0099] 2、将杀扑磷加入锥形瓶中，加入甲苯搅拌溶解之后，再加入农乳500搅拌均匀，再在超声波(50 W，40 kHz )下震荡20分钟，形成第一相。 [0099] 2, methidathion join conical flask, toluene and after stirring to dissolve, then add the dairy farming 500 Stir, then in an ultrasonic (50 W, 40 kHz) shock for 20 minutes to form the first phase.
[0100] 3、将PEG-400、吐温60、PEG6000DS、乙二醇、消泡剂加到锥形瓶内，加水至100g，搅拌均匀至溶解，形成第二相。 [0100] 3, PEG-400, Tween 60, PEG6000DS, ethylene glycol, a defoaming agent was added to a conical flask, add water to 100g, stir until dissolved, to form a second phase.
[0101] 4、第二相在1000转/分钟转速的搅拌下，将第一相缓慢滴加入第二相(滴加速度为0.15mL/min)，继续搅拌40分钟，形成均匀的纳米乳，按实施例1的方法测纳米乳的粒径，测得平均粒径160 nm。 [0101] 4, the second phase at 1000 rev / min stirring speed, the first phase of the second phase was slowly added dropwise (dropping of 0.15mL / min), stirring was continued for 40 minutes to form a uniform nanoemulsion, by Example 1 measured nanoemulsion particle diameter, measured by the average particle diameter of 160 nm. 低温稳定性合格，热储稳定性(54±2 °C，2周)分解率10%。 Qualified low temperature stability, thermal storage stability (54 ± 2 ° C, 2 weeks) decomposition rate of 10%.
[0102] 实施例8 [0102] Example 8
[0103] [0103]
[0105] 制备过程如下: [0105] was prepared as follows:
[0106] 1、称取上述配方的原药、乳化剂、助溶剂、增稠剂、抗冻剂、水。 [0106] 1. Weigh the above formulation of the original drug, emulsifying agents, solvents, thickeners, antifreeze, water.
[0107] 2、将杀扑磷加入锥形瓶中，加入甲苯搅拌溶解之后，再加入司盘80搅拌均匀，再在超声波下震荡5分钟,形成第一相。 [0107] 2, methidathion join conical flask, toluene and after stirring to dissolve, then add Span 80 Stir, then the ultrasonic shock for 5 minutes to form a first phase.
[0108] 3、将PEG-200、吐温60、乙基羟乙基纤维素、丙二醇、消泡剂加到锥形瓶内，加水至100g，搅拌均匀至溶解，形成第二相。 [0108] 3, PEG-200, Tween 60, ethyl hydroxyethyl cellulose, propylene glycol, a defoaming agent was added to a conical flask, add water to 100g, stir until dissolved, to form a second phase.
[0109] 4、第二相在1500转/分钟转速的搅拌下，将第一相缓慢滴加入第二相(滴加速度为0.15mL/min)，继续搅拌30分钟，形成均匀的纳米乳，按实施例1的方法测纳米乳的粒径，测得平均粒径90 nm。 [0109] 4, the second phase at 1500 rev / min stirring speed, the first phase of the second phase was slowly added dropwise (dropping of 0.15mL / min), stirring was continued for 30 minutes to form a uniform nanoemulsion, by Example 1 measured nanoemulsion particle size, measured by the average particle size 90 nm. 低温稳定性合格，热储稳定性(54±2 0C, 2周)分解率10%。 Qualified low temperature stability, thermal storage stability (54 ± 2 0C, 2 weeks) decomposition rate of 10%.
[0110] 实施例9 [0110] Example 9
[0111] [0111]
[0112] 制备过程如下: [0112] was prepared as follows:
[0113] 1、称取上述配方的原药、乳化剂、助溶剂、抗冻剂、水。 [0113] 1. Weigh the above formulation of the original drug, emulsifying agents, solvents, antifreeze, water.
[0114] 2、将杀扑磷加入锥形瓶中，加入甲苯搅拌溶解之后，再加入司盘80搅拌均匀，再在超声波(50 W，40 kHz )下震荡5分钟，形成第一相。 [0114] 2, methidathion join conical flask, toluene and after stirring to dissolve, then add Span 80 Stir, then in an ultrasonic (50 W, 40 kHz) shock for 5 minutes to form the first phase.
[0115] 3、将PEG-400、吐温60、乙二醇加到锥形瓶内，加水至100g，搅拌均匀至溶解，形成第二相。 [0115] 3, PEG-400, Tween 60, ethylene glycol was added to a conical flask, add water to 100g, stir until dissolved, to form a second phase.
[0116] 4、第二相在2000转/分钟转速的搅拌下，将第一相缓慢滴加入第二相(滴加速度为0.2mL/min)，继续搅拌30分钟，形成均匀的纳米乳，按实施例1的方法测纳米乳的粒径，测得平均粒径130 nm。 [0116] 4, a second phase in 2000 rev / min stirring speed, the first phase of the second phase was slowly added dropwise (dropping of 0.2mL / min), stirring was continued for 30 minutes to form a uniform nanoemulsion, by Example 1 measured nanoemulsion particle size, measured by the average particle size 130 nm. 低温稳定性合格，热储稳定性(54±2 °C，2周)分解率彡10%。 Qualified low temperature stability, thermal storage stability (54 ± 2 ° C, 2 weeks) San decomposition rate of 10%.
| Cited Patent | Filing date | Publication date | Applicant | Title |
|---|---|---|---|---|
| CN101683593A * | 14 Aug 2009 | 31 Mar 2010 | 赢创戈尔德施米特有限公司 | Nano-emulsions and method of producing them, and their use |
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| Date | Code | Event | Description |
|---|---|---|---|
| 24 Jul 2013 | C06 | Publication | |
| 21 Aug 2013 | C10 | Request of examination as to substance | |
| 3 Dec 2014 | C14 | Granted |
