WO2017084242A1 - 具有增效作用的植物生长调节剂组合物 - Google Patents

具有增效作用的植物生长调节剂组合物 Download PDF

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Publication number
WO2017084242A1
WO2017084242A1 PCT/CN2016/079851 CN2016079851W WO2017084242A1 WO 2017084242 A1 WO2017084242 A1 WO 2017084242A1 CN 2016079851 W CN2016079851 W CN 2016079851W WO 2017084242 A1 WO2017084242 A1 WO 2017084242A1
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Prior art keywords
brassinolide
composition
active component
plant growth
plant
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PCT/CN2016/079851
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English (en)
French (fr)
Inventor
顾国梁
仲汉根
季红进
张洁
邰少杰
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江苏辉丰农化股份有限公司
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Application filed by 江苏辉丰农化股份有限公司 filed Critical 江苏辉丰农化股份有限公司
Priority to EA201800265A priority Critical patent/EA201800265A1/ru
Priority to AU2016356032A priority patent/AU2016356032A1/en
Priority to EP16865425.9A priority patent/EP3381286A4/en
Priority to BR112018009941A priority patent/BR112018009941A8/pt
Priority to US15/777,171 priority patent/US20180325115A1/en
Priority to CONC2018/0005971A priority patent/CO2018005971A2/es
Priority to MX2018006142A priority patent/MX2018006142A/es
Priority to CA3005489A priority patent/CA3005489A1/en
Publication of WO2017084242A1 publication Critical patent/WO2017084242A1/zh
Priority to PH12018501066A priority patent/PH12018501066A1/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/22—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom rings with more than six members
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture

Definitions

  • the invention belongs to the field of agricultural plant protection, in particular to a plant growth regulator composition with improved properties, in particular to a composition comprising a thidiazuron and a brassinolide pesticide.
  • Brassinolide is a new type of green plant growth regulator, which is treated by soaking seeds with suitable concentration of brassinolide and spraying with stems and leaves. It can promote the growth of vegetables, melons, fruits and other crops, improve quality, increase yield, bright color and thicker leaves. It can also make the tea harvesting time ahead of time, and also make the melon and fruit contain more sugar, the individual is larger, the output is higher, the storage is more resistant, and it is harmless to humans and animals. The normal dosage is very safe and effective. Natural brassinolide can be widely used in various economic crops, and can significantly improve the quality, increase the weight of sugar and fruit, and increase the beauty of flowers. At the same time, it can also improve the drought resistance and cold resistance of crops, and alleviate the symptoms of crop diseases and insect pests, phytotoxicity, fertilizer damage and freezing damage.
  • brassinolide At present, there are more than 30 kinds of brassinolide.
  • the brassinolide is usually used in a similar mixture of one or more structures, and only a few of them have high biological activity and practical value. Its chemical structure is:
  • Pyraclostrobin is a new type of high-efficiency plant growth regulator. When it is absorbed by plants, it can promote the separation of petioles and stems and form natural shedding. It can be widely used in pesticides and fertilizers. It is extremely strong Its biological activity, its ability to induce plant cell division and callus formation is many times higher than that of general cytokinins. Improve crop absorptive capacity and increase photosynthesis, so as to increase production and enhance the purpose. It can be used in various kinds of melons, fruits, vegetables, seedlings, flowers, food, tobacco and other crops, and can also be used for tissue culture, genetic engineering, etc. In production, it can significantly improve crop yield, improve quality and use less, has no pollution to the ecological environment, and is non-toxic to humans, animals, birds, bees and natural enemies.
  • the plant growth regulators currently on the market are mainly based on a single agent, and the effect is single.
  • the inventors have found that there is a significant synergistic effect between brassinolide or a derivative thereof and thifenone in regulating or promoting plant growth.
  • Another object of the present invention is to provide a process for the preparation of a composition comprising two active ingredients A and B plant growth regulators and for regulating and promoting the growth of crops in the agricultural field.
  • the object of the invention can be achieved by the following measures:
  • a synergistic plant growth regulator composition comprising two active components A and B, wherein active component A is thiabendone and active component B is brassinolide or derivative thereof
  • the weight ratio between the two components is a weight ratio of the active component A to the active component B of 1: (0.001 to 0.19).
  • the weight ratio of the active component A to the active component B is 1: (0.001 to 0.17), and the weight ratio may be further preferably 1: (0.0012 to 0.16) or 1: (0.0011 to 0.143).
  • the brassinolide of the present invention may be a natural brassinolide extract or a chemically synthesized brassinolide.
  • the brassinolide of the present invention is a structurally similar mixture of one or more brassinolides, using a common type, such as BR1, BR2, BR3, BR4, BR5 and BR6, alone or in combination. These are all types of brassinolides that are common in the prior art.
  • the derivative of brassinolide may be a novel substance derived from the simple group modification of the brassinolide structure, such as propionyl brassinolide, 24-onorphanin lactone. 22, 23, 24-epi canthate lactone, 28-epi canavanide lactone, 28-high brassinolide and 14-hydrocarbyl brassinosteroid.
  • composition of the present invention is useful for better regulating the growth of crops, promoting the health effects of crops, and increasing crop yield.
  • the present invention provides the use of a composition comprising component A (thiabendazole) and component B (brassinolide or a derivative thereof) for regulating crop growth in the agricultural field, in particular in the regulation of rice, wheat or fruit trees.
  • component A thiabendazole
  • component B brassinolide or a derivative thereof
  • composition of the present invention can also be used in combination with other pesticides (such as fungicides, insecticides, herbicides, plant growth regulators), fertilizers, etc., and these are mixed with Commonly used pesticides or fertilizers disclosed in the art.
  • pesticides such as fungicides, insecticides, herbicides, plant growth regulators
  • fertilizers etc.
  • composition of the present invention can be made into a pesticide-acceptable dosage form from the active ingredient and the pesticide adjuvant.
  • composition may specifically comprise an agrochemical auxiliary, such as one or more of a carrier, a solvent, a dispersing agent, a wetting agent, an adhesive, a thickener, a binder, a surfactant, etc., during the application process.
  • an agrochemical auxiliary such as one or more of a carrier, a solvent, a dispersing agent, a wetting agent, an adhesive, a thickener, a binder, a surfactant, etc.
  • an agrochemical auxiliary such as one or more of a carrier, a solvent, a dispersing agent, a wetting agent, an adhesive, a thickener, a binder, a surfactant, etc.
  • Suitable auxiliaries may be solid or liquid, they are usually materials commonly used in the processing of dosage forms, such as natural or regenerated minerals, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers. .
  • the method of application of the compositions of the invention comprises the use of the compositions of the invention for aerial parts of plants, in particular leaves or foliage. You can choose to soak or apply to the surface of the control object.
  • the frequency of administration and the amount administered will depend on the biological and climatic conditions of the pathogen.
  • the plant growth site such as rice fields, may be wetted with a liquid formulation of the composition, or the composition may be applied to the soil in solid form, such as in the form of granules (soil application), the composition may be passed from the soil to the plant through the roots of the plant. In vivo (systemic action).
  • compositions may be applied only with the active ingredient or may be mixed with an additive (agrochemical adjuvant).
  • composition of the present invention can be prepared into a pesticide-acceptable dosage form such as a liquid, a suspension, a soluble liquid, an oil suspension, a microcapsule, a microemulsion, a wettable powder and the like.
  • a pesticide-acceptable dosage form such as a liquid, a suspension, a soluble liquid, an oil suspension, a microcapsule, a microemulsion, a wettable powder and the like.
  • the compositions may be applied by spraying, misting, dusting, spreading or pouring, and the like.
  • Microcapsule dosage forms suitable for the present invention include: microcapsule suspension, microcapsule suspension-suspension, microcapsule suspension-water emulsion, etc., characterized in that the inner wall of the capsule (ie, the core) contains the active ingredient brassinolide and Thiabendazole is mixed into a microcapsule according to a certain proportion of the mixture.
  • the microcapsules are stably dispersed and suspended in a certain concentration to form a microcapsule suspending agent in water as a continuous phase.
  • one of the active ingredients is prepared as a microcapsule suspension, another active ingredient is prepared into an emulsion, and the prepared two components are mixed, stirred, and shaken to obtain a microcapsule suspension-suspension or microcapsule suspension.
  • Agent-water emulsion Agent-water emulsion.
  • composition of the present invention can be prepared into various dosage forms by a known method, and the active ingredient and the auxiliary agent, such as a solvent, a solid carrier, and, if necessary, can be uniformly mixed and ground together with the surfactant to prepare a desired preparation. Dosage form.
  • the above solvent may be selected from aromatic hydrocarbons, preferably containing from 8 to 12 carbon atoms, such as a mixture of xylenes or substituted benzenes, phthalates such as dibutyl phthalate or dicaprylic acid, aliphatic hydrocarbons such as rings.
  • aromatic hydrocarbons preferably containing from 8 to 12 carbon atoms, such as a mixture of xylenes or substituted benzenes, phthalates such as dibutyl phthalate or dicaprylic acid, aliphatic hydrocarbons such as rings.
  • Alkenes or paraffins, alcohols and glycols and their ethers and esters such as ethanol, ethylene glycol, ethylene glycol monomethyl
  • ketones such as cyclohexanone
  • highly polar solvents such as N-methyl -2-pyrrolidone, dimethyl sulfoxide or dimethylformamide
  • vegetable or vegetable oils such as soybean oil.
  • the above solid carriers are typically natural mineral fillers such as talc, kaolin, montmorillonite or activated clay.
  • a highly dispersible silicic acid or a highly dispersible adsorbent polymer carrier such as a particulate adsorbent carrier or a non-adsorbing carrier, and a suitable particulate adsorbent carrier is porous, such as pumice, bentonite or Bentonite; a suitable non-adsorbing carrier such as calcite or sand.
  • a large amount of pre-granulated materials of inorganic or organic nature can be used as a carrier, in particular dolomite.
  • Suitable surfactants are lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, alkaline earth metal or amine salts, alkylarylsulfonates, alkyl groups Sulfates, alkyl sulfonates, fatty alcohol sulphates, fatty acids and sulfated fatty alcohol glycol ethers, as well as condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, naphthalene or naphthalene sulfonic acid with phenol and formaldehyde Condensate, polyoxyethylene octyl phenyl ether, ethoxylated isooctyl phenol, octyl phenol, nonyl phenol, alkyl aryl polyglycol ether, tributyl benzene poly
  • Plants in the present invention include, but are not limited to, sorghum, wheat or corn, and the like.
  • the two active ingredients in the compositions of the present invention exhibit synergistic effects, the activity of which is more pronounced than the expected sum of activity using a single compound, and the individual activity of a single compound.
  • Other characteristics exhibited by the composition of the present invention are mainly as follows: 1.
  • the composition of the present invention has a significant synergistic effect; 2. Due to the large difference in the chemical structure of the two single agents of the composition, the effect The mechanism is completely different, there is no cross-resistance, which can delay the resistance problem caused by the two single agents alone; 3.
  • the composition of the invention can well regulate crop growth, improve disease resistance and stress resistance, and promote crop health effects. To increase crop yields.
  • Example 2 0.201% thibenone/penicillin lactone suspension
  • Example 4 0.55% thiabendazole-propionyl brassinolide suspension
  • the active ingredient thiablon and the brassinolide are mixed in a certain ratio, that is, the two are mixed to form a microcapsule.
  • the microcapsules are stably dispersed and suspended in a certain concentration to form a microcapsule suspending agent in water as a continuous phase.
  • one of the active ingredients is prepared as a microcapsule suspension, another active ingredient is prepared into an emulsion, and the prepared two components are mixed, stirred, and shaken to obtain a microcapsule suspension-suspension or microcapsule suspension.
  • Agent-water emulsion Agent-water emulsion.
  • Example 7 0.31% thibenone/penicillin lactone microcapsule suspension
  • Thiabendazole 0.3% brassinolide 0.01%, rosin vegetable oil 11%, attractant fatty acid glyceride 4%, polyoxyethylene lauryl ether 5%, ethylene glycol 2.5%, stabilizer potassium dihydrogen phosphate 2%, Forming prepolymerized formaldehyde-urea prepolymer 18%, carrageenan 0.5%, lignin Sodium sulfonate 4%, preservative sodium benzoate 1%, water to 100%.
  • Example 8 0.4027% Thiabendan ⁇ Brassinolide lactone suspension-suspending agent
  • the active ingredient thiablon and the brassinolide are placed in an enamel kettle according to a certain proportion of the mixture, the surfactant, the auxiliary agent and the water, and stirred under a water bath condition until a transparent liquid is obtained, thereby obtaining a soluble liquid agent. .
  • the active ingredient and the auxiliary agent are added to the reaction kettle, and the balance is made up with water, and the mixture is stirred uniformly to obtain a thiabendone/brassinin lactone aqueous solution.
  • Example 13 0.20022% thibenone/bructone lactone aqueous solution
  • Example 14 0.351% thiabendazole-propionyl brassinolide aqueous solution
  • Example 15 0.10125% thidiazuron ⁇ penthrolactone aqueous solution
  • Example 16 0.315% Thiabendan ⁇ Brassica lactone aqueous solution
  • Dithizone and brassinolide were diluted with acetone at a certain concentration, and the crops were sprayed with stems and leaves.
  • the effects of various concentrations on crop growth were determined in the field, including plant height, plant diameter, root length, and disease resistance. Comprehensive evaluation of the situation, fruit quality, and yield.
  • Plant height control rate (clear water control plant height - treated plant height) / clear water control plant height * 100%
  • stem diameter of clear water control plant - stem diameter of treated plant stem diameter of clear water control plant *100%
  • Grain 1000-grain weight increase rate (1000-grain weight of fresh water control - 1000-grain weight of treated grain) / 1000-grain weight of fresh water control *100%
  • the ester single agent and the clear water control have obvious effects on the growth regulation of sorghum, mainly in the following: 1.
  • the invention can effectively increase the plant diameter of sorghum, enhance the nutrient transfer capacity of the plant, and can improve the growth of sorghum by promoting the plant diameter.
  • the product of the present invention is applied during the flowering period of oats, and can effectively regulate the healthy growth of oats.
  • the main performances are as follows: 1. It can increase the ear length of oats and increase the number of grains per ear; 2. It can significantly increase the weight of oat kernels; 3, can dwarf oat plants, effectively control the oats to control the length of the nowadays, prevent wheat from lodging; 4, thiabendazole has a certain role in promoting the growth of oats, and brassinolide has a certain resistance to disease growth The ability, the two have a certain synergistic effect after compounding; 5, the composition of the invention has a significant increase in the unit yield of oats.

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

本发明公开了一种具有增效作用的植物生长调节剂组合物，其有效成分包含A和B，其中活性组分A为噻苯隆，活性组分B为芸苔素内酯或其衍生物。本发明还提供了该组合物的制备方法及用途。试验结果表明，本发明的组合物可很好的调节作物生长，提高抗病抗逆性，促进作物健康作用，提高作物产量。

Description

具有增效作用的植物生长调节剂组合物 技术领域
本发明属于农业植物保护领域，特别是涉及一种具有改进性能的植物生长调节剂组合物，具体地说是涉及一种包含噻苯隆和芸苔素内酯农药的组合物。
背景技术
芸苔素内酯(brassinolide)是一种新型绿色环保植物生长调节剂，其通过适宜浓度芸苔素内酯浸种和茎叶喷施处理。可以促进蔬菜、瓜类、水果等作物生长，可改善品质，提高产量，色泽艳丽，叶片更厚实。也能使茶叶的采叶时间提前，也可令瓜果含糖份更高，个体更大，产量更高，更耐储藏，对人畜都是无害的，正常使用剂量非常安全有效。天然芸苔素可广泛用于应用于各种经济作物，,并能明显改善品质，增加糖份和果实重量，增加花卉艳丽。同时还能提高作物的抗旱，抗寒能力，缓解作物遭受病虫害，药害，肥害，冻害的症状。
目前芸苔素内酯已发现有30多种，芸苔素内酯通常使用时为一种或多种结构相类似的混合使用，其中生物活性较高、有实用价值的只有少数几种。其化学结构式为：
Figure PCTCN2016079851-appb-000001
噻苯隆(pyraclostrobin)是新型高效植物生长调节剂，噻苯隆被植物吸收后，可促进叶柄与茎之间的分离组织，形成自然脱落，在农药、肥料中可被广泛应用。它具有极强 的生物活性，其诱导植物细胞分裂、愈伤组织形成的能力比一般细胞分裂素高许多倍。提高作物吸收能力，增加光合作用，从而达到增产、增优目的。可用于各类瓜、果、蔬菜、苗木、花卉、粮食、烟草等作物，还可用于组织培养、基因工程等。在生产上能显著提高作物产量、改善品质且有用量少、对生态环境无污染，对人、畜、鸟、蜜蜂、天敌无毒等特点。
目前市面上销售的植物生长调节剂主要是以单剂为主，且作用效果单一。
发明内容
本发明的目的是提供一种具有增效作用的植物生长调节剂组合物，以促进作物生长，提高作物的抗病和作物产量。发明人发现，芸苔素内酯或其衍生物与噻苯隆两者之间在调节或促进植物生长方面具有显著的协同增效作用。
本发明的另一个目的是提供包含两种有效成分A和B植物生长调节剂组合物的制备方法及在农业领域调节和促进农作物生长的应用。
本发明的目的可以通过以下措施达到：
一种具有增效作用的植物生长调节剂组合物，该组合物包含A和B两种活性组分，其中活性组分A为噻苯隆，活性组分B为芸苔素内酯或其衍生物，两组分之间的重量比为活性组分A和活性组分B的重量比为1：(0.001～0.19)。
在一种优选方案中，活性组分A和活性组分B的重量比为为1：(0.001～0.17)，为使作用效果更明显两者重量比可进一步优选1：(0.0012～0.16)或1：(0.0011～0.143)。
本发明的芸苔素内酯可采用天然的芸苔素内酯提取物，或化学合成的芸苔素内酯。
本发明的芸苔素内酯为一种或一种以上的芸苔素内酯结构相似的混合物，采用常用的种类，如BR1、BR2、BR3、BR4、BR5和BR6等单独或混合的成份，这些均是现有领域中常见的芸苔素内酯种类。
本发明中，芸苔素内酯的衍生物可以为芸苔素内酯结构式上作简单基团修饰衍生而来的新物质，如丙酰芸苔素内酯、24-表芸苔素内酯、22,23,24-表芸苔素内酯、28-表高芸苔素内酯、28-高芸苔素内酯和14-烃基芸苔素甾醇等。
发明人通过试验发现，本发明的组合物是用于可以更好的调节作物的生长，促进作物的健康作用，提高作物的产量。
本发明提供了包含组分A(噻苯隆)和组分B(芸苔素内酯或其衍生物)的组合物在农业领域调节农作物生长的用途，特别是在水稻、小麦或果树方面调节作物生长提高抗病效果等方面的用途。
为充分发挥本发明的优势效果，本发明的组合物还可以与其他农药(如杀菌剂、杀虫剂、除草剂、植物生长调节剂)、肥料等混合使用，这些与之混用的均为现有技术公开的常用的农药或肥料。
本发明的组合物可以由活性成分和农药助剂制成农药上允许的剂型。
上述组合物具体可包含农药助剂，例如载体、溶剂、分散剂、润湿剂、胶粘剂、增稠剂、粘合剂、表面活性剂等中的一种或几种，在施用的过程中可以混合常用的助剂。
合适的助剂可以是固体或液体，它们通常是剂型加工过程中常用的物质，例如天然的或再生的矿物质，溶剂、分散剂、润湿剂、胶粘剂、增稠剂、粘合剂或肥料。
本发明组合物的施用方法包括将本发明的组合物用于植物生长的地上部分，特别是叶部或叶面。可以选择浸种或涂抹于防治对象表面。施用的频率和施用量取决于病原体的生物学和气候生存条件。可以将植物的生长场所，如稻田，用组合物的液体制剂浸湿，或者将组合物以固体形式施用于土壤中，如以颗粒形式(土壤施用)，组合物可以由土壤经植物根部进入植物体内(内吸作用)。
这些组合物可以仅仅包含活性成分进行施用，也可以与添加剂(农药助剂)一起混合使用。
本发明的组合物可以制备成农药上可接受的剂型，例如水剂、悬浮剂、可溶性液剂、油悬浮剂、微囊剂型、微乳剂、可湿性粉剂等。根据这些组合物的性质以及施用组合物所要达到的目的和环境情况，可以选择将组合物以喷雾、弥雾、喷粉、撒播或泼浇等之类的方法施用。
适合本发明的微囊剂型包括：微囊悬浮剂、微囊悬浮-悬浮剂、微囊悬浮-水乳剂等，其特征在于囊壁内(即囊芯)包含由有效成分芸苔素内酯和噻苯隆按照一定比例的混合物，即将两者混合制成微型胶囊。将微型胶囊以一定的浓度稳定地分散、悬浮在作为连续相的水中形成微囊悬浮剂。或者将其中一种有效成分制备成微囊悬浮剂，将另外一种有效成分制备成乳液，将制备的两种成分在混合，搅拌，摇匀即得微囊悬浮剂-悬浮剂或微囊悬浮剂-水乳剂。
可用已知的方法可以将本发明的组合物制备成各种剂型，可以将有效成分与助剂，如溶剂、固体载体，需要时可以与表面活性剂一起均匀混合、研磨，制备成所需要的剂型。
上述的溶剂可选自芳香烃，优选含8-12个碳原子，如二甲苯混合物或取代的苯，酞酸酯类，如酞酸二丁酯或酞酸二辛酸，脂肪烃类，如环已烷或石蜡，醇和乙二醇和它们的醚和酯，如乙醇，乙二醇，乙二醇单甲基；酮类，如环已酮，强极性的溶剂，如N-甲基 -2-吡咯烷酮，二甲基亚砜或二甲基甲酰胺，和植物油或植物油，如大豆油。
上述的固体载体，如用于可湿性粉剂和可分散剂的通常是天然矿物填料，例如滑石、高岭土，蒙脱石或活性白土。为了管理组合物的物理性能，也可以加入高分散性硅酸或高分散性吸附聚合物载体，例如粒状吸附载体或非吸附载体，合适的粒状吸附载体是多孔型的，如浮石、皂土或膨润土；合适的非吸附载体如方解石或砂。另外，可以使用大量的无机性质或有机性质的预制成粒状的材料作为载体，特别是白云石。
根据本发明的组合物中的有效成分的化学性质，合适的表面活性剂为木质素磺酸、萘磺酸、苯酚磺酸、碱土金属盐或胺盐，烷基芳基磺酸盐，烷基硫酸盐，烷基磺酸盐，脂肪醇硫酸盐，脂肪酸和硫酸化脂肪醇乙二醇醚，还有磺化萘和萘衍生物与甲醛的缩合物，萘或萘磺酸与苯酚和甲醛的缩合物，聚氧乙烯辛基苯基醚，乙氧基化异辛基酚，辛基酚，壬基酚，烷基芳基聚乙二醇醚，三丁基苯聚乙二醇醚，三硬脂基苯基聚乙二醇醚，烷基芳基聚醚醇，乙氧基化蓖麻油，聚氧乙烯烷基醚，氧化乙烯缩合物、乙氧基化聚氧丙烯，月桂酸聚乙二醇醚缩醛，山梨醇酯，木质素亚硫酸盐废液和甲基纤维素。
本发明中的植物包括但不限于高粱、小麦或玉米等。
本发明的组合物中两种有效成分表现为增效效果，该组合物的活性比使用单个化合物的活性预期总和，以及单个化合物的单独活性更为显著。本发明的组合物的表现出的其它特点主要表现为：1、本发明的组合物混配具有明显的协同增效作用；2、由于本组合物的两个单剂化学结构差异很大，作用机理完全不同，不存在交互抗性，可延缓两单剂单独使用所产生的抗性问题；3、本发明的组合物可很好的调节作物生长，提高抗病抗逆性，促进作物健康作用，提高作物产量。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明，凡在本发明的精神和原则之内所做的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。
以下实施例所有配方中百分比均为重量百分比(折百)。本发明组合物各种制剂的加工工艺均为现有技术，根据不同情况可以有所变化。
一、剂型制备实施例
(一)悬浮剂的加工及实施例
将活性成分芸苔素内酯与噻苯隆，与分散剂、润湿剂、增稠剂和水等各组分按配方的 比例混合均匀，经砂磨和/或高速剪切后，得到半成品，分析后补加水混合均匀过滤即得成品。
实施例1：1.001％噻苯隆·芸苔素内酯悬浮剂
噻苯隆1％，芸苔素内酯0.001％，黄原胶3％，乙二醇2％，高岭土6％，硅酸铝镁4％，木质素磺酸钠5％,水补足至100％。
实施例2：0.201％噻苯隆·芸苔素内酯悬浮剂
噻苯隆0.2％，芸苔素内酯0.001％，膨润土6％，丙三醇3％，甲基萘磺酸钠甲醛缩合物6％，水补足至100％。
实施例3：0.58％噻苯隆·芸苔素内酯悬浮剂
噻苯隆0.5％，芸苔素内酯0.08％，白炭黑5％，丙三醇6％，苯甲酸钠3％，脂肪醇聚氧乙烯醚磷酸酯6％,水补足至100％。
实施例4：0.55％噻苯隆·丙酰芸苔素内酯悬浮剂
噻苯隆0.5％，丙酰芸苔素内酯0.05％，白炭黑5％，乙二醇3％，木质素磺酸钠7％,黄原胶2％，水补足至100％。
(二)微囊剂的加工及实施例
将有效成分噻苯隆与芸苔素内酯按照一定比例的混合物，即将两者混合制成微型胶囊。将微型胶囊以一定的浓度稳定地分散、悬浮在作为连续相的水中形成微囊悬浮剂。或者将其中一种有效成分制备成微囊悬浮剂，将另外一种有效成分制备成乳液，将制备的两种成分在混合，搅拌，摇匀即得微囊悬浮剂-悬浮剂或微囊悬浮剂-水乳剂。
实施例5：1.003％噻苯隆·丙酰芸苔素内酯微囊悬浮剂
噻苯隆1％，丙酰芸苔素内酯0.003％，松脂植物油12％，乳酸甘油酯3％，乳化剂聚氧乙烯蓖麻油4％，稳定剂亚磷酸三苯酯3.5％，甲苯二异氰酸酯15％，丙烯酸-丙烯酸酯共聚物5％，二丙二醇3％，防腐剂苯甲酸钠1％，增稠剂黄原胶2.1％，水补足至100％。
实施例6:0.501％噻苯隆·芸苔素内酯微囊悬浮-悬浮剂
噻苯隆0.5％，芸苔素内酯0.001％，甲酯椰子油15％，聚氧乙烯单棕榈酸酯3％，BHT3％、引诱剂氨基酸2％，木质素磺酸盐4％，丙三醇5％，凯松2％，乙酸乙烯乳液4％，黄原胶2％，水补足至100％。
实施例7:0.31％噻苯隆·芸苔素内酯微囊悬浮剂
噻苯隆0.3％，芸苔素内酯0.01％，松脂植物油11％，引诱剂脂肪酸甘油酯4％，聚氧乙烯月桂醚5％，乙二醇2.5％，稳定剂磷酸二氢钾2％，成囊预聚体甲醛-尿素预聚体18％，卡拉胶0.5％，木质素 磺酸钠4％，防腐剂苯甲酸钠1％，水补足至100％。
实施例8:0.4027％噻苯隆·芸苔素内酯囊悬浮-悬浮剂
噻苯隆0.4％，芸苔素内酯0.0027％，明胶15％，乙醇4％，三乙胺2％，乙二胺5％，萘磺酸盐甲醛缩合物4％，水补足至100％。
(三)可溶性液剂的加工及实施例
将有效成分噻苯隆与芸苔素内酯按照一定比例的混合物、表面活性剂、助剂和水，置于搪瓷釜中，在水浴条件下，充分搅拌直至获得透明液体，即得可溶性液剂。
实施例9:0.305％噻苯隆·芸苔素内酯可溶性液剂
噻苯隆0.3％，芸苔素内酯0.005％，烷基苯磺酸钠5％，甲醇12％，乙二醇5％，水补足至100％。
实施例10:0.505％噻苯隆·芸苔素内酯可溶性液剂
噻苯隆0.5％，芸苔素内酯0.005％，烷基酚聚氧乙烯醚聚氧丙烯醚2％、甲醇2％、乙二醇5％，水补足至100％。
实施例11:0.408％噻苯隆·芸苔素内酯可溶性液剂
噻苯隆0.4％，芸苔素内酯0.008％，苄基二甲基酚聚氧乙烯醚4％，环己酮3％，氮氮二甲基甲酰胺5％，乙二醇5％，水补足至100％。
实施例12:0.238％噻苯隆·芸苔素内酯可溶性液剂
噻苯隆0.2％，芸苔素内酯0.038％，乳化剂0203B 10％，异丙醇15％，乙二醇5％，尿素5％，水补足至100％。
(四)水剂的加工及实施例
在反应釜中加入有效成分和助剂，余量用水补足，并搅拌均匀，即可得到噻苯隆·芸苔素内酯水剂。
实施例13:0.20022％噻苯隆·芸苔素内酯水剂
将噻苯隆0.2％、二甲基亚砜5％、乙醇5％混匀、搅拌20分钟，再加入芸苔素内酯0.00022％，搅拌30分钟至芸苔素内酯完全溶解；加入8％烷基醇硫酸钠，余量用水补足，搅拌均匀即可得到0.20022％噻苯隆·芸苔素内酯水剂。
实施例14:0.351％噻苯隆·丙酰芸苔素内酯水剂
在反应釜中加入噻苯隆原药0.3％和乙醇8％，搅拌20分钟；再加入乙酰芸苔素内酯0.051％，搅拌30分钟至乙酰芸苔素内酯完全溶解；加入10％脂肪醇聚氧乙烯醚，余量用水补足，搅拌均匀即可得到0.351％噻苯隆·丙酰芸苔素内酯水剂。
实施例15:0.10125％噻苯隆·芸苔素内酯水剂
在反应釜中加入噻苯隆0.1和乙醇5％，搅拌20分钟；再加入芸苔素内酯0.00125％，搅拌30分 钟至芸苔素内酯完全溶解；加入5％脂肪醇聚氧乙烯醚，余量用水补足，搅拌均匀即可得到0.10125％噻苯隆·芸苔素内酯水剂。
实施例16:0.315％噻苯隆·芸苔素内酯水剂
在反应釜中加入噻苯隆0.3％、四氢呋喃6％、丙二醇3％，搅拌20分钟；再加入芸苔素内酯0.015％，搅拌30分钟至芸苔素内酯完全溶解；加入6％烷基醇硫酸钠，余量用水补足，搅拌均匀即可得到0.3025％噻苯隆·芸苔素内酯水剂。
二、药效验证试验
(一)生物测定实施例
1、噻苯隆与芸苔素内酯复配对高粱生长调节综合测定试验
将噻苯隆与芸苔素内酯用丙酮按照一定浓度稀释，对作物进行茎叶喷雾，在田间测定各个浓度对作物生长的影响，包括对作物的株高、株径、根长、抗病情况、果实品质，以及产量情况等进行综合评价。
株高控制率＝(清水对照株高-处理后的株高)/清水对照株高*100％
茎径提高率＝(清水对照植株茎径-处理后的植株茎径)/清水对照植株茎径*100％
预防效果＝(清水对照的发病指数-处理后的发病指数)/清水对照的发病指数*100％
籽粒千粒重提高率＝(清水对照的籽粒千粒重-处理后的籽粒千粒重)/清水对照的籽粒千粒重*100％
亩产提高率＝(清水对照的亩产量-处理后的亩产量)/清水对照的亩产量*100％
表1.噻苯隆与芸苔素内酯复配对高粱生长调节综合测定汇总表
Figure PCTCN2016079851-appb-000002
Figure PCTCN2016079851-appb-000003
注：表格中“芸”为“芸苔素内酯”缩写，“噻”为“噻苯隆”的缩写。施药时期：喇叭口初期，该阶段高粱植株未发生开始发生高粱褐斑病。施药次数：2次，施药间隔期8天；施药方式：茎叶喷雾；调查时期：高粱抽雄初期；本试验中，株高、茎径、发病指数、籽粒千粒重等指标均为各处理的平均值。
通过实验发明人发现，噻苯隆与芸苔素内酯之间具有很好协同提升作用，噻苯隆与芸苔素内酯混配在不同配比下，相对噻苯隆、芸苔素内酯单剂，以及清水对照，对高粱的生长调节作用明显，主要表现在：1、本发明可有效增加高粱的株径，提升植株上下营养传导能力，而且通过促进株径，可以提高高粱生长的抗倒伏性能；2、噻苯隆在作为单剂使用时对植物生长具有一定的抗病抗逆作用，而芸苔素内酯属于植物内在生长激素，对作物病害具有一定免疫力，芸苔素内酯与噻苯隆之间共同施用具有良好的协同作用，从上表分 析可以看出，噻苯隆与芸苔素内酯之间协同作用对高粱褐斑病的预防效果相对于单剂及清水对照，具有很好的预防效果；3、本发明可有效调节高粱的控旺徒长，即降低高粱株高和穗位，有效平衡营养生长与生殖生长的关系，防止倒伏；4、由于高粱生长前期噻苯隆与芸苔素内酯的协同作用，促进了高粱植株的营养传导、抗病抗逆，在高粱成熟期，对高粱的千粒重以及单位亩产有显著的提升作用，亩产提高率最高达到17.22％；5、噻苯隆与芸苔素内酯在配比(5.2-1000)：1之间时，所表现的两者协同增效作用效果明显，当噻苯隆与芸苔素内酯的比值低于5.2时，两者的协同增效作用效果不明显。
(二)田间药效验证试验
1、噻苯隆与芸苔素内酯混配对燕麦作物调节生长及抗病增产的田间综合试验
施药时期：燕麦灌浆初期，燕麦扬花期易发生白粉病等病害。
施药次数：1次。利用本发明的制剂实施例进行喷施，三个重复，结果取平均值。
表2噻苯隆与芸苔素内酯混配对燕麦调节生长的田间综合实验
Figure PCTCN2016079851-appb-000004
从表2实验数据显示，本发明的产品在燕麦扬花期施用，可以有效调节燕麦的健康生长。主要表现为：1、可以提升燕麦的穗长，提高穗粒数；2、可显著提高燕麦籽粒的重量； 3、可以矮化燕麦植株，有效控制燕麦控旺徒长，防止小麦倒伏；4、噻苯隆对燕麦的生长具有一定的促进作用，而芸苔素内酯对燕麦生长具有一定的抗病抗逆能力，两者混配后具有一定的协同增效作用；5、本发明的组合物对燕麦的单位产量具有显著的提升作用。

Claims (9)

  1. 一种具有增效作用的植物生长调节剂组合物，其特征在于该组合物包含A和B两种活性组分，其中活性组分A为噻苯隆，活性组分B为芸苔素内酯或其衍生物，活性组分A和活性组分B的重量比为1：0.001～0.19。
  2. 根据权利要求1所述的组合物，其特征在于活性组分A和活性组分B的重量比为0.001～0.17。
  3. 根据权利要求2所述的组合物，其特征在于活性组分A和活性组分B的重量比为1：0.0012～0.16。
  4. 根据权利要求2所述的组合物，其特征在于活性组分A和活性组分B的重量比为1：0.0011～0.143。
  5. 根据权利要求1所述的组合物，其特征在于所述芸苔素内酯衍生物选自丙酰芸苔素内酯。
  6. 根据权利要求1所述的组合物，其特征在于该组合物由活性成分和助剂制成农药上允许的剂型。
  7. 根据权利要求6所述的组合物，其特征在于所述剂型为水剂、悬浮剂、可溶液剂或微囊剂型。
  8. 权利要求1～7中任意一项所述的农药组合物在农业领域促进或调节植物生长的用途。
  9. 根据权利要求8所述的用途，其特征在于所述植物选自高粱、小麦或玉米。
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BR112018009941A BR112018009941A8 (pt) 2015-11-17 2016-04-21 composição reguladora de crescimento vegetal com efeito sinergético
US15/777,171 US20180325115A1 (en) 2015-11-17 2016-04-21 Plant growth regulator compostion having synergistic effect
CONC2018/0005971A CO2018005971A2 (es) 2015-11-17 2016-04-21 Composición de regulador de crecimiento vegetal que tiene efecto sinérgico
MX2018006142A MX2018006142A (es) 2015-11-17 2016-04-21 Composicion de regulador de crecimiento vegetal que tiene efecto sinergico.
CA3005489A CA3005489A1 (en) 2015-11-17 2016-04-21 Plant growth regulator composition having synergistic effect
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Families Citing this family (8)

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CN105660671A (zh) * 2016-03-31 2016-06-15 广东中迅农科股份有限公司 含有噻苯隆和芸苔素内酯的农药组合物
CN108271782A (zh) * 2018-03-12 2018-07-13 张轶翔 一种提高内吸传导型除草剂效能的技术方法
CN110663703A (zh) * 2019-10-21 2020-01-10 江西鑫邦生化有限公司 一种复配型生长调节剂及其制备方法和应用
CN111903702A (zh) * 2020-08-14 2020-11-10 南京轩凯生物科技有限公司 一种含泛菌多糖的组合型生长调节剂及其应用
CN111972425A (zh) * 2020-09-07 2020-11-24 安徽省四达农药化工有限公司 噻苯隆单剂、噻苯隆与芸苔素内酯复配组合物及制备工艺
CN112514909A (zh) * 2020-12-17 2021-03-19 多农多收技术研究(江苏)有限公司 一种增产组合物、增产药剂及其应用
CN114916549B (zh) * 2021-07-30 2024-04-19 山东仕邦农化有限公司 一种植物生长调节组合物、制剂及其应用
CN114451165B (zh) * 2022-02-24 2022-12-13 河南农业大学 用于调控烟草生长的氮素增效剂及其使用方法和应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000058338A1 (en) * 1999-03-30 2000-10-05 Agritope, Inc. Brassinosteroid analogs useful as plant growth regulators
CN1478390A (zh) * 2003-07-08 2004-03-03 云大科技股份有限公司 含芸苔素内酯类物质的植物生长调节剂混剂及应用
CN101658167A (zh) * 2009-09-08 2010-03-03 江西省棉花研究所 一种用于棉花抗草甘膦药害的解毒安全剂
CN101856028A (zh) * 2010-06-17 2010-10-13 陕西韦尔奇作物保护有限公司 一种含苄氨基嘌呤与芸苔素内酯的植物生长调节剂
CN102613246A (zh) * 2011-12-13 2012-08-01 四川龙蟒福生科技有限责任公司 一种植物生长调节组合物及其应用

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102438453A (zh) * 2009-04-07 2012-05-02 塔明克股份有限公司 植物生长调节剂添加剂
CN103081773B (zh) * 2013-02-22 2014-04-16 新疆农垦科学院 促进干旱地区枣树坐果的方法及用于该方法的专用制剂
CN104839609A (zh) * 2015-04-29 2015-08-19 潍坊友容实业有限公司 一种盐碱地海芦笋中低铜及低砷植物盐的提取方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000058338A1 (en) * 1999-03-30 2000-10-05 Agritope, Inc. Brassinosteroid analogs useful as plant growth regulators
CN1478390A (zh) * 2003-07-08 2004-03-03 云大科技股份有限公司 含芸苔素内酯类物质的植物生长调节剂混剂及应用
CN101658167A (zh) * 2009-09-08 2010-03-03 江西省棉花研究所 一种用于棉花抗草甘膦药害的解毒安全剂
CN101856028A (zh) * 2010-06-17 2010-10-13 陕西韦尔奇作物保护有限公司 一种含苄氨基嘌呤与芸苔素内酯的植物生长调节剂
CN102613246A (zh) * 2011-12-13 2012-08-01 四川龙蟒福生科技有限责任公司 一种植物生长调节组合物及其应用

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