WO2022205753A1 - 一种烷基酯基盐衍生物、其制备方法和应用 - Google Patents

一种烷基酯基盐衍生物、其制备方法和应用 Download PDF

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WO2022205753A1
WO2022205753A1 PCT/CN2021/114507 CN2021114507W WO2022205753A1 WO 2022205753 A1 WO2022205753 A1 WO 2022205753A1 CN 2021114507 W CN2021114507 W CN 2021114507W WO 2022205753 A1 WO2022205753 A1 WO 2022205753A1
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alkyl ester
base salt
ester base
hydroxyethylethylenediamine
formula
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PCT/CN2021/114507
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English (en)
French (fr)
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平原
李寅
马敏
任鹏
任莉
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苏州丰倍生物科技股份有限公司
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Priority to JP2023559019A priority Critical patent/JP2024516932A/ja
Publication of WO2022205753A1 publication Critical patent/WO2022205753A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/22—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated the carbon skeleton being further substituted by oxygen atoms
    • 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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • 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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • 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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals

Definitions

  • the invention belongs to the technical field of pesticide adjuvants, and specifically relates to an alkyl ester base salt derivative, a preparation method and application thereof.
  • glyphosate As the herbicide product with the largest market share in the industry, glyphosate has a large market scale and many manufacturers, but the preparations are generally water preparations, and its synergists generally use alkyl glycosides, tallow amines, polysiloxanes and other products. compound.
  • tallow amine has certain disadvantages, polysiloxanes are unstable and easy to decompose, and the effect of alkyl glycosides cannot meet the needs of customers.
  • the first technical problem to be solved by the present invention is to provide an alkyl ester base salt derivative that is both hydrophilic and lipophilic, not easily decomposed, and has strong adsorption.
  • the second technical problem to be solved by the present invention is to provide a preparation method of the above-mentioned alkyl ester salt derivatives.
  • the third technical problem to be solved by the present invention is to provide an application of the above-mentioned alkyl ester base salt derivative in a glyphosate herbicide, so as to improve the herbicidal effect of the herbicide.
  • the technical scheme adopted in the present invention is:
  • the first aspect of the present invention provides an alkyl ester base salt derivative, and the general structural formula of the alkyl ester base salt derivative is shown in formula (1):
  • the R 1 is any one of (CH 2 ) 7 , (CH 2 ) 10 , and (CH 2 ) 11
  • the R 2 is CH 3 , CH 3 CH 2 , CH(CH 3 ) 2
  • the R 3 is any one of CH 3 (CH 2 ) 7 , CH 3 (CH 2 ) 4 , CH 3 (CH 2 ) 5
  • the X n- is any one of hydrochloride, sulfate, and dihydrogen phosphate.
  • the presence of ammonium ions in the alkyl ester base salt derivatives of the present invention can effectively resist the structural decomposition caused by ions in high-salt systems, and has good structural stability and good water solubility; It is fused with oils and esters, and has good fat solubility. For example, when it acts on crops, it can effectively penetrate the waxy layer of plant leaves, thereby acting on the interior of plants.
  • the alkyl ester base salt derivative is one or more of the substances represented by the following structural formula:
  • the second aspect of the present invention provides a preparation method of the above-mentioned alkyl ester base salt derivative, which comprises performing an epoxidation reaction on a substance represented by the formula (2) to obtain an epoxy ester substance, Then, the epoxy esters are reacted with hydroxyethylethylenediamine to obtain hydroxyethylethylenediamine derivatives, and then the hydroxyethylethylenediamine derivatives are reacted with inorganic acids to obtain the alkanes base ester salt derivatives.
  • the general structural formula of the substance represented by the formula (2) is R 1 , R 2 , and R 3 in the formula (2) are the same as R 1 , R 2 , and R 3 in the formula (1).
  • the inorganic acid is one or more of hydrochloric acid, sulfuric acid and phosphoric acid.
  • Hydroxyethylethylenediamine derivatives react with hydrochloric acid, sulfuric acid and phosphoric acid to form salts with strong electronegativity and strong intermolecular charge adsorption, which can form a firm protective film on the surface of crops. Enhanced resistance to rain erosion.
  • the epoxy value of the epoxy esters is 1-5%, further 2-3%.
  • the epoxidation includes the following steps: reacting the substance represented by the formula (2) with hydrogen peroxide in the presence of formic acid and sulfuric acid.
  • the chemical reaction formula of described epoxidation reaction is:
  • the preparation of epoxy compounds mainly adopts halohydrin method and peracid oxidation method.
  • the halohydrin method generates a halohydrin from the raw material, and then reacts the halohydrin with a base to form an epoxy compound.
  • This method is complicated in process and difficult to handle by-products;
  • the peroxyacid oxidation method generates epoxy by reacting the raw material with peroxyacid.
  • the steps are simple, the peroxyacid is a strong oxidant with poor stability and easy explosion.
  • the present application uses hydrogen peroxide as an oxygen donor, sulfuric acid as a catalyst, and formic acid as an active carrier for the reaction, which has the advantages of simpler preparation process and easier control of the reaction process.
  • the mass ratio of the material represented by the formula (2), the formic acid, and the sulfuric acid is 100:(5-10):(0.2-0.8), further 100:(8-10) : (0.5 to 0.8).
  • the addition of sulfuric acid and formic acid not only has a stabilizing effect on hydrogen peroxide, but also promotes the epoxidation reaction. However, the addition of sulfuric acid and formic acid is not as large as possible. Too much sulfuric acid and formic acid will promote the ring-opening reaction of epoxy bonds. Therefore, it is necessary to control the addition amount of sulfuric acid and formic acid in an appropriate range.
  • the added amount of the hydrogen peroxide is 10 to 15 times the mass of the formic acid.
  • the mass concentration of the hydrogen peroxide is 30-50%, further 35-45%, and further 40-45%.
  • the temperature for controlling the epoxidation reaction is 40-70°C, further 50-70°C, still further 60-70°C, and still further 65-70°C.
  • the lower the reaction temperature the lower the reaction rate of the epoxidation reaction, and the lower the epoxy value of the prepared epoxide.
  • the reaction temperature is lower than 40°C, the epoxy value of the prepared epoxide is lower than 1%; the reaction
  • the increase of temperature can increase the reaction rate, when the reaction temperature is higher than 70°C, the epoxide will undergo a ring-opening reaction, which will increase the by-products in the product, thereby reducing the epoxy value of the obtained epoxide.
  • the epoxy ester is reacted with the hydroxyethylethylenediamine in the presence of zinc oxide.
  • zinc oxide is used as a catalyst, and the reaction formula of the reaction between the epoxy esters and the hydroxyethyl ethylene diamine is:
  • the pressure during the reaction is controlled to be 0.1-0.6 MPa.
  • the temperature of the reaction process is controlled to be 110-130°C, further 120-130°C.
  • the mass ratio of the epoxy esters, the hydroxyethyl ethylene diamine, and the zinc oxide is 100: (70-80): (0.5-1.0), further 100: (70 ⁇ 75): (0.5 ⁇ 0.8).
  • the invention utilizes the highly active amine group of hydroxyethylethylenediamine, reacts it with epoxy ester substances, and synthesizes the hydroxyethylethylenediamine derivative with long-chain alkyl ester side chain by ring-opening addition, Since hydroxyethylethylenediamine has multiple active sites, if it is directly reacted, there will be many by-products.
  • the present invention can effectively suppress the generation of by-products by controlling the pressure, temperature and the feeding amount of the reaction raw materials.
  • the mass ratio of the hydroxyethylethylenediamine derivative to the inorganic acid is 1:(1.5-5), preferably 1:(2-3.5), more preferably 1:(2-3.5) 1: (2 to 3).
  • the reaction formula of the reaction of the hydroxyethylethylenediamine derivative and the inorganic acid is:
  • the mass concentration of the inorganic acid is 15-40%, further 15-35%.
  • the reaction temperature of the hydroxyethylethylenediamine and the inorganic acid is controlled to be 40-60°C, further 50-60°C.
  • the substances represented by the formula (2) include methyl oleate, methyl soybean oil, methyl rapeseed oil, ethyl oleate, ethyl soybean oil, and ethyl rapeseed oil , one or more of isopropyl oleate, isopropyl soybean oil, isopropyl rapeseed oil, butyl oleate, butyl soybean oil, and butyl rapeseed oil.
  • the raw materials of the above-mentioned methyl oleate, soybean oil methyl ester, rapeseed oil methyl ester, etc. are derived from natural vegetable oil, and the synthetic alkyl ester base salt derivatives have good fat solubility and can effectively penetrate the waxy layer of plant leaves. , When used in conjunction with drugs, it can increase the effect of the drug, shorten the action time of the drug, and is easy to degrade, has low toxicity, and is environmentally friendly.
  • the third aspect of the present invention provides the above-mentioned alkyl ester base salt derivative and/or the alkyl ester base salt derivative obtained by the above-mentioned preparation method as a synergist in glyphosate Applications.
  • synergists will be added during the processing and use of glyphosate formulations.
  • the commonly used synergists are tallow amine synergists, but tallow amine synergists have stimulating effects on humans and animals and are highly toxic to aquatic organisms.
  • alternative products such as alkyl glycosides and polysiloxane synergists, appear one after another, the synergistic effect is generally poor.
  • the alkyl ester base salt derivative in the present invention is used as a synergist and mixed with glyphosate aqueous solution, which can effectively resist the structural decomposition caused by ions in the glyphosate high-salt system, has strong stability, and can effectively increase the medicinal solution.
  • the alkyl ester base salt derivative Adhesion, expansion and permeability on the surface of plant leaves, so that the liquid medicine can be firmly adsorbed on the surface of crops, and the alkyl ester base salt derivatives form a good oil film on the plant surface through its long-chain alkyl and ester groups, which is waterproof
  • the alkyl ester base salt derivative has osmotic conduction effect, which can be transmitted to the whole plant and roots through the stems and leaves of the plant, so as to ensure that the active ingredients can smoothly enter the plant and be quickly transmitted to the target site to hinder the progress of the plant biological process. , play a role in weeding.
  • the volume-to-mass ratio of the alkyl ester base salt derivative to the glyphosate is (3-9) ml:20 g.
  • the present invention has the following advantages compared with the prior art: the alkyl ester salt derivatives in the present invention have good hydrophilic and lipophilic properties, can reduce the surface tension of the aqueous solution, and can dissociate at the same time. Positive charge, strong adsorption, not easy to decompose.
  • Fig. 1 is the hydrogen spectrogram of the alkyl ester base salt derivative in embodiment 1;
  • FIG. 2 is a carbon nuclear magnetic spectrum of the alkyl ester salt derivative in Example 1.
  • the present invention will be further described below in conjunction with the examples. However, the present invention is not limited to the following examples.
  • the implementation conditions adopted in the embodiment can be further adjusted according to the different requirements of specific use, and the unremarked implementation conditions are the conventional conditions in the industry.
  • the technical features involved in the various embodiments of the present invention can be combined with each other as long as they do not conflict with each other.
  • the parts described in the present invention refer to parts by mass, and the “multiple types" in the present invention refer to two or more kinds.
  • the structural formula of the main product in the product of this example is: See Figure 1 and Figure 2 for the relevant spectrum. It is a brown-yellow to brown-red paste at room temperature (25°C) with a density of 0.937 g/cm 3 .
  • the structural formula of the main product in the product of this example is: At room temperature (25°C), it is a brownish yellow to brownish red paste with a density of 0.952 g/cm 3 .
  • the structural formula of the main product in the product of this example is: At room temperature (25°C), it is a brownish yellow to brownish red paste with a density of 0.929 g/cm 3 .
  • the related products in the embodiment of the present invention are matched with glyphosate isopropylamine saline, and the results after 14 days of prevention and control of abalone are shown in Table 2 below.
  • the test method and the determination of the control effect are based on the Agricultural Industry Standard of the People's Republic of China NY/T 1155.4-2006 "Agricultural Industry Standard NY/T 1155.4-2006

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Abstract

本发明提供一种烷基酯基盐衍生物，烷基酯基盐衍生物的结构通式如式(1)所示，其中，R1为(CH2)7、(CH2)10、(CH2) 11中的任一种，R2为CH3、CH3CH2、CH(CH3)2、CH3(CH2)3中的任一种，R3为CH3(CH2)7、CH3(CH2)4、CH3(CH2)5中的任一种，Xn-为盐酸根、硫酸根、磷酸二氢根中的任一种。本发明中的烷基酯基盐衍生物具有很好的亲水亲油性，可降低水溶液的表面张力，同时能够解离出正电荷，吸附性强，不易分解。

Description

一种烷基酯基盐衍生物、其制备方法和应用 技术领域
本发明属于农药助剂技术领域，本发明具体涉及一种烷基酯基盐衍生物、其制备方法和应用。
背景技术
行业内草甘膦作为市场占比最大的除草剂产品，市场规模大，生产厂家多，但制剂一般为水剂，其增效剂一般使用烷基糖苷、牛脂胺、聚硅氧烷类及其复配。但存在牛脂胺有一定危害，聚硅氧烷类不稳定易分解，烷基糖苷的效果达不到客户的使用要求的缺点。
在草甘膦的高盐体系下，一般的阴离子和非离子增效剂对草甘膦的增效甚微，开发合适的增效剂用于草甘膦的增效市场，前景广大。
发明内容
本发明所要解决的第一个技术问题是提供一种既能亲水又能亲油、不易分解、吸附作用强的烷基酯基盐衍生物。
本发明所要解决的第二个技术问题是提供一种上述烷基酯基盐衍生物的制备方法。
本发明所要解决的第三个技术问题是提供一种上述烷基酯基盐衍生物在草甘膦除草剂中的应用，以提高除草剂的除草效果。
为达到上述目的，本发明采用的技术方案是：
本发明的第一方面，提供一种烷基酯基盐衍生物，所述烷基酯基盐衍生物的结构通式如式(1)所示：
Figure PCTCN2021114507-appb-000001
其中，所述R 1为(CH 2) 7、(CH 2) 10、(CH 2) 11中的任一种，所述R 2为CH 3、CH 3CH 2、CH(CH 3) 2、CH 3(CH 2) 3中的任一种，所述R 3为CH 3(CH 2) 7、CH 3(CH 2) 4、CH 3(CH 2) 5中的任一种，所述X n-为盐酸根、硫酸根、磷酸二氢根中的任一种。
本发明的烷基酯基盐衍生物中铵离子的存在能够有效抵抗高盐体系中离子引起的结构分解，结构稳定性好、水溶性佳；同时其具有长链烷基酯基结构，有够与油类、酯类物质相融合，脂溶性佳，例如当其作用于作物时，可以有效渗透植物叶面蜡质层，从而作用于植物内 部。
优选地，所述烷基酯基盐衍生物为如下结构式所示物质中的一种或多种：
Figure PCTCN2021114507-appb-000002
Figure PCTCN2021114507-appb-000003
Figure PCTCN2021114507-appb-000004
Figure PCTCN2021114507-appb-000005
本发明的第二方面，提供一种如上所述的烷基酯基盐衍生物的制备方法，包括对结构通式如式(2)所示物质进行环氧化反应得到环氧酯类物质，然后使所述环氧酯类物质与羟乙基乙二胺进行反应制得羟乙基乙二胺衍生物，再使所述羟乙基乙二胺衍生物与无机酸反应制得所述烷基酯基盐衍生物。
优选地，所述式(2)所示物质的结构通式为
Figure PCTCN2021114507-appb-000006
所述式(2)中的R 1、R 2、R 3与所述式(1)中的R 1、R 2、R 3相同。
优选地，所述无机酸为盐酸、硫酸、磷酸中的一种或多种。羟乙基乙二胺衍生物与盐酸、硫酸、磷酸反应生成的盐电负性强，分子间的电荷吸附作用强，能够在作物的表面形成牢固的保护膜，与制剂配合使用时，使得制剂的抗雨水冲刷能力增强。
优选地，所述环氧酯类物质的环氧值为1～5％，进一步为2～3％。
根据一些具体且优选的实施方式，所述环氧化包括如下步骤：使所述式(2)所示物质在甲酸和硫酸的存在下，与双氧水进行反应。其中，所述环氧化反应的化学反应式为：
Figure PCTCN2021114507-appb-000007
环氧化合物的制备主要采用卤醇法以及过酸氧化法。卤醇法通过将原料生成卤代醇，再将卤代醇与碱反应生成环氧化合物，此方法工艺繁琐、副产物难处理；过氧酸氧化法通过将原料与过氧酸反应生成环氧化合物，虽然步骤简便，但过氧酸为强氧化剂，稳定性差、易爆炸。本申请通过采用双氧水作为供氧体，硫酸作为催化剂，甲酸作为活性载体进行反应，具有制备过程更加简单、反应过程易于控制的优点。
进一步优选地，所述式(2)所示物质、所述甲酸、所述硫酸的投料质量比为100：(5～10)：(0.2～0.8)，更进一步为100：(8～10)：(0.5～0.8)。硫酸与甲酸的加入不仅对双氧水起到稳定作用，还会促进环氧化反应的进行，但硫酸与甲酸的加入量并非越大越好，硫酸、甲酸过多会促使环氧键发生开环反应，因此，需要将硫酸、甲酸的加入量控制在合适的范围。
进一步优选地，所述双氧水的添加量为所述甲酸质量的10～15倍。
进一步优选地，所述双氧水的质量浓度为30～50％，更进一步为35～45％，再进一步为40～45％。
优选地，控制所述环氧化反应的温度为40～70℃，进一步为50～70℃，更进一步为60～70℃，再进一步为65～70℃。反应温度越低环氧化反应反应速率越低，制得的环氧化物的环氧值越低，当反应温度低于40℃，制得的环氧化物的环氧值低于1％；反应温度升高虽然能够提高反应速率，而当反应温度高于70℃时，环氧化物会发生开环反应，使产物中的副产物增加，从而使得到的环氧化物的环氧值降低。
根据一些具体且优选的实施方式，所述环氧酯类物质与所述羟乙基乙二胺在氧化锌的存在下进行反应。其中，氧化锌作为催化剂，所述环氧酯类物质与所述羟乙基乙二胺反应的反应式为：
Figure PCTCN2021114507-appb-000008
进一步优选地，控制反应过程中的压力为0.1～0.6MPa。
进一步优选地，控制反应过程的温度为110～130℃，更进一步为120～130℃。
进一步优选地，所述环氧酯类物质、所述羟乙基乙二胺、所述氧化锌的投料质量比100：(70～80)：(0.5～1.0)，更进一步为100：(70～75)：(0.5～0.8)。本发明利用羟乙基乙二胺的高活性胺基，通过将其与环氧酯类物质反应，开环加成合成具有长链烷基酯基侧链的羟乙基乙二胺衍生物，由于羟乙基乙二胺具有多个活性位点，若是直接反应生成的产物副产物多。本发明通过压力、温度以及反应原料的投料量的控制能够有效抑制副产物的生成。
根据一些具体且优选的实施方式，所述羟乙基乙二胺衍生物与所述无机酸的投料质量比为1：(1.5～5)，优选为1：(2～3.5)，进一步优选为1：(2～3)。其中，所述羟乙基乙二胺衍生物与所述无机酸反应的反应式为：
Figure PCTCN2021114507-appb-000009
通过将无机酸过量，能够有效抑制副产物的生成，但由于羟乙基乙二胺衍生物上具有多 个反应位点，如果无机酸过量太多的话会使无机酸继续与产物反应生成副产物，通过将羟乙基乙二胺衍生物与无机酸的投料质量比控制在1：(1.5～5)能够有效抑制副产物的形成。
优选地，所述无机酸的质量浓度为15～40％，进一步为15～35％。
优选地，控制所述羟乙基乙二胺与所述无机酸的反应温度为40～60℃，进一步为50～60℃。
根据一些具体且优选的实施方式，所述式(2)所示物质包括油酸甲酯、大豆油甲酯、菜籽油甲酯、油酸乙酯、大豆油乙酯、菜籽油乙酯、油酸异丙酯、大豆油异丙酯、菜籽油异丙酯、油酸丁酯、大豆油丁酯、菜籽油丁酯中的一种或多种。
上述油酸甲酯、大豆油甲酯、菜籽油甲酯等的原料来源于天然植物油，用其作为反应物合成烷基酯基盐衍生物脂溶性好，能够有效渗透植物叶面蜡质层，与药物配合使用时，能够增加药物作用效果，缩短药物作用时间，并且易降解，毒性低，绿色环保。
本发明的第三个方面，提供一种如上所述的烷基酯基盐衍生物和/或如上所述的制备方法制得的烷基酯基盐衍生物作为增效剂在草甘膦中的应用。
为了提高草甘磷的除草效果，降低其使用剂量和成本，会在草甘磷制剂的加工和使用过程中加入增效剂。目前常使用的增效剂为牛脂胺类增效剂，但牛脂胺类增效剂对人畜有刺激作用且对水生生物毒性较高。虽然陆续出现替代产品，如烷基糖苷、聚硅氧烷类增效剂，但普遍增效效果较差。本发明中的烷基酯基盐衍生物作为增效剂与草甘膦水剂混合使用，能够有效抵抗草甘膦高盐体系中离子引起的结构分解，稳定性强，同时能够有效增加药液在植物叶片表面上粘着、扩展和渗透性，使药液在作物表面牢固吸附，烷基酯基盐衍生物通过其长链烷基、酯基基团在植物表面形成良好的油膜，起到防水作用；同时该烷基酯基盐衍生物有渗透传导作用，可经过植株茎叶进行传导至全株和根部，保证有效成分能顺利地进入植物体内快速传导到靶标部位以阻碍植物生物过程的进行，起到除草作用。
优选地，所述烷基酯基盐衍生物与所述草甘膦的体积质量比为(3～9)ml：20g。
由于上述技术方案运用，本发明与现有技术相比具有下列优点：本发明中的烷基酯基盐衍生物具有很好的亲水亲油性，可降低水溶液的表面张力，同时能够解离出正电荷，吸附性强，不易分解。
附图说明
图1为实施例1中的烷基酯基盐衍生物的氢谱图；
图2为实施例1中的烷基酯基盐衍生物的核磁碳谱图。
具体实施方式
下面结合实施例对本发明作进一步描述。但本发明并不限于以下实施例。实施例中采用 的实施条件可以根据具体使用的不同要求做进一步调整，未注明的实施条件为本行业中的常规条件。本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
在没有特别说明的情况下，本发明中所述的份数指质量份数，本发明中的“多种”指2种或2种以上。
实施例1
1.将油酸甲酯、甲酸、硫酸按质量比100：8：0.5投入反应釜，搅拌均匀，升温至70℃，匀速加入甲酸质量10倍的40％质量含量的双氧水，在1～2h内滴加完成，然后继续反应3h，蒸馏得到环氧值为2％的环氧油酸甲酯。
2.将环氧油酸甲酯、羟乙基乙二胺、氧化锌按质量比100：75：0.8投入压力反应釜，升温至120℃，恒温反应1h，等压力归零后，倒入蒸馏瓶中，负压0.4-0.5MPa，温度210-230℃进行蒸馏，所得馏分即为羟乙基乙二胺衍生物。
3.将羟乙基乙二胺衍生物100份加入到反应釜中加热至50℃，将15％质量浓度盐酸300份分次加入，完全加入后恒温搅拌反应1.5小时即得烷基酯基盐衍生物(产品1)。
本实施例产物中主要产品的结构式为
Figure PCTCN2021114507-appb-000010
相关谱图详见图1和图2，室温(25℃)情况下为棕黄色至棕红色膏状物，密度0.937g/cm 3。
实施例2
1.将油酸甲酯、甲酸、硫酸按质量比100：10：0.8投入反应釜，搅拌均匀，升温至65℃，匀速加入甲酸质量15倍的40％质量含量的双氧水，在1～2h内滴加完成，然后继续反应3h，蒸馏得到环氧值为2.3％的环氧油酸甲酯。
2.将环氧油酸甲酯、羟乙基乙二胺、氧化锌按质量比100：70：0.5投入压力反应釜，升温至120℃，恒温反应1.5h，等压力归零后，倒入蒸馏瓶中，负压0.4-0.5MPa，温度210-230℃进行蒸馏，所得馏分即为羟乙基乙二胺衍生物。
3.将羟乙基乙二胺衍生物100份加入到反应釜中加热至50℃，将35％质量浓度磷酸200份分次加入，完全加入后恒温搅拌反应2小时即得烷基酯基盐衍生物(产品2)。
本实施例产物中主要产品的结构式为
Figure PCTCN2021114507-appb-000011
室温(25℃)情况下为棕黄色至棕红色膏状物，密度0.952g/cm 3。
实施例3
1.将油酸甲酯、甲酸、硫酸按质量比100：10：0.8投入反应釜，搅拌均匀，升温至65℃，匀速加入甲酸质量15倍的40％质量含量的双氧水，在1～2h内滴加完成，然后继续反应3h，蒸馏得到环氧值为2.3％的环氧油酸甲酯。
2.将环氧油酸甲酯、羟乙基乙二胺、氧化锌按质量比100：70：0.5投入压力反应釜，升温至120℃，恒温反应1.5h，等压力归零后，倒入蒸馏瓶中，负压0.4-0.5MPa，温度210-230℃进行蒸馏，所得馏分即为羟乙基乙二胺衍生物。
3.将羟乙基乙二胺衍生物100份加入到反应釜中加热至50℃，将35％质量浓度盐酸200份分次加入，完全加入后恒温搅拌反应1小时即得烷基酯基盐衍生物(产品3)。
本实施例产物中主要产品的结构式为
Figure PCTCN2021114507-appb-000012
室温(25℃)情况下为棕黄色至棕红色膏状物，密度0.929g/cm 3。
将上述实施例中制得的产品分别添加至去离子水中配制成烷基酯基盐衍生物的质量浓度在10％至80％之间的溶液，观察烷基酯基盐衍生物在水中的溶解性，具体结果见表1，从表1可以看出烷基酯基盐衍生物与去离子水互溶，水溶性佳。
表1
Figure PCTCN2021114507-appb-000013
本发明实施例中的相关产品搭配草甘膦异丙胺盐水剂，防治苘麻14天后的结果如下表2所示。测试方法以及防治效果的测定依据中华人民共和国农业行业标准NY/T 1155.4-2006《农
药室内生物测定试验准则除草剂第4部分：活性测定试验茎叶喷雾法》进行。
表2
Figure PCTCN2021114507-appb-000014
以上对本发明做了详尽的描述，其目的在于让熟悉此领域技术的人士能够了解本发明的内容并加以实施，并不能以此限制本发明的保护范围，凡根据本发明的精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围内。

Claims (13)

  1. 一种烷基酯基盐衍生物，其特征在于：所述烷基酯基盐衍生物的结构通式如式(1)所示：
    Figure PCTCN2021114507-appb-100001
    其中，所述R 1为(CH 2) 7、(CH 2) 10、(CH 2) 11中的任一种，所述R 2为CH 3、CH 3CH 2、CH(CH 3) 2、CH 3(CH 2) 3中的任一种，所述R 3为CH 3(CH 2) 7、CH 3(CH 2) 4、CH 3(CH 2) 5中的任一种，所述X n-为盐酸根、硫酸根、磷酸二氢根中的任一种。
  2. 根据权利要求1所述的烷基酯基盐衍生物，其特征在于：所述烷基酯基盐衍生物为如下结构式所示物质中的一种或多种：
    Figure PCTCN2021114507-appb-100002
    Figure PCTCN2021114507-appb-100003
    Figure PCTCN2021114507-appb-100004
    Figure PCTCN2021114507-appb-100005
  3. 一种如权利要求1或2所述的烷基酯基盐衍生物的制备方法，其特征在于：对结构通式如式(2)所示物质进行环氧化反应得到环氧酯类物质，然后使所述环氧酯类物质与羟乙基乙二胺进行反应制得羟乙基乙二胺衍生物，再使所述羟乙基乙二胺衍生物与无机酸反应制得所述烷基酯基盐衍生物；其中，所述式(2)所示物质的结构通式为
    Figure PCTCN2021114507-appb-100006
    所述式(2)中的R 1、R 2、R 3与所述式(1)中的R 1、R 2、R 3相同，所述无机酸为盐酸、硫酸、磷酸中的一种或多种。
  4. 根据权利要求3所述的烷基酯基盐衍生物的制备方法，其特征在于：所述环氧化反应包括如下步骤：使所述式(2)所示物质在甲酸和硫酸的存在下，与双氧水进行反应，其中，所述式(2)所示物质、所述甲酸、所述硫酸的投料质量比为100：(5～10)：(0.2～0.8)；所述双氧水的添加质量为所述甲酸质量的10～15倍，所述双氧水的质量浓度为30～50％；控制所述环氧化反应的温度为40～70℃。
  5. 根据权利要求3所述的烷基酯基盐衍生物的制备方法，其特征在于：所述环氧酯类物质的环氧值为1～5％。
  6. 根据权利要求3所述的烷基酯基盐衍生物的制备方法，其特征在于：所述环氧酯类物质与所述羟乙基乙二胺在氧化锌的存在下进行反应，并且控制反应过程中的压力为0.1～0.6MPa、温度为110～130℃；其中，所述环氧酯类物质、所述羟乙基乙二胺、所述氧化锌的投料质量比100：(70～80)：(0.5～1.0)。
  7. 根据权利要求3所述的烷基酯基盐衍生物的制备方法，其特征在于：所述羟乙基乙二胺衍生物与所述无机酸的投料质量比为1：(1.5～5)，控制反应温度为40～60℃。
  8. 根据权利要求7所述的烷基酯基盐衍生物的制备方法，其特征在于：所述无机酸的质量浓度为15～40％。
  9. 根据权利要求7所述的烷基酯基盐衍生物的制备方法，其特征在于：控制反应时间为1.5～2h。
  10. 根据权利要求3或4所述的烷基酯基盐衍生物的制备方法，其特征在于：所述式(2)所示物质包括油酸甲酯、大豆油甲酯、菜籽油甲酯、油酸乙酯、大豆油乙酯、菜籽油乙酯、油酸异丙酯、大豆油异丙酯、菜籽油异丙酯、油酸丁酯、大豆油丁酯、菜籽油丁酯中的一种或多种。
  11. 根据权利要求3所述的烷基酯基盐衍生物的制备方法，其特征在于：所述制备方法包括如下步骤：
    (1)使所述式(2)所示物质在甲酸和硫酸的存在下与双氧水进行反应得到环氧酯类物质，其中，所述式(2)所示物质、所述甲酸、所述硫酸的投料质量比为100：(5～10)：(0.2～0.8)，所述双氧水的添加质量为所述甲酸质量的10～15倍，所述双氧水的质量浓度为30～50％，控制所述环氧化反应的温度为40～70℃；
    (2)使所述环氧酯类物质与所述羟乙基乙二胺在氧化锌的存在下进行反应制得羟乙基乙二胺衍生物，其中，所述环氧酯类物质、所述羟乙基乙二胺、所述氧化锌的投料质量比100：(70～80)：(0.5～1.0)，控制反应过程中的压力为0.1～0.6MPa、温度为110～130℃；
    (3)使所述羟乙基乙二胺衍生物与所述无机酸反应制得所述烷基酯基盐衍生物，其中，所述无机酸为盐酸、硫酸、磷酸中的一种或多种，所述无机酸的质量浓度为15～40％，所述羟乙基乙二胺衍生物与所述无机酸的投料质量比为1：(1.5～5)，控制反应温度为40～60℃、反应时间为1.5～2h。
  12. 如权利要求1或2所述的烷基酯基盐衍生物和/或如权利要求3至11中任一项所述的制备方法制得的烷基酯基盐衍生物作为增效剂在草甘膦除草剂中的应用。
  13. 根据权利要求12所述的应用，其特征在于：所述烷基酯基盐衍生物与所述草甘膦的体积质量比为(3～9)ml：20g。
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