A high-load pesticide oil suspension dispersant and its preparation method and application

Abstract

The invention discloses a high-load pesticide oil suspension dispersant and a preparation method and application thereof, belonging to the technical field of pesticides. The dispersant is obtained by graft copolymerization of unsaturated monomers and is a "comb-shaped" polyacrylate cationic structure. The molecular skeleton is composed of a main chain and a side chain, and the main side chain contains active groups including dimethylene, long-chain alkyl, EO / PO block, ester group and nitrogen-containing cations. Through these active groups, on the one hand, the lipophilic water ratio is adjusted to make it easy to dissolve in the oily dispersed phase; on the other hand, through electrostatic repulsion, dispersion force, steric hindrance generated by its own macromolecular structure and tighter inclusion of cations and original drugs, the adsorption amount is larger, so that the viscosity of the preparation system is lower, and a better dispersion stability effect is achieved. The various dispersants prepared in the present invention can effectively solve the problems of high viscosity, difficult discharging, poor stability over time, and no fluidity during the sand milling process of the high-load pesticide oil suspension through multiple performance evaluations.

Description

Technical Field

[0001] The invention belongs to the technical field of pesticides, and in particular relates to a high-load pesticide oil suspension dispersant and a preparation method and application thereof. Background Art

[0002] Oil-based suspension concentrate (OD) is an important pesticide formulation. It forms a highly dispersed, highly suspended, and flowable stable liquid-solid system by using surfactants and other additives to form the solid active ingredients of pesticides that are insoluble in oil in a non-aqueous medium. It has many advantages such as stabilizing the active ingredients of pesticides, improving the efficacy, and facilitating mechanized fertilization. It plays an important role in modern agricultural production. With the demand for more efficient, environmentally friendly, and economical pesticide formulations in agricultural production, high-load (active ingredient solid content greater than 25%) pesticide oil suspensions provide stronger efficacy while reducing the volume and weight of the formulation, effectively reducing packaging and transportation costs; the problem after high loading is that although the addition of emulsifiers and other additives in the formulation plays a certain role in dispersion, the actual material sand milling process still has problems such as high viscosity, difficult discharge, poor stability over time, and no fluidity.

[0003] Dispersants are key additives in pesticide oil suspensions. They 1) adsorb on the surface of solid particles to reduce the interfacial tension between liquid and liquid or solid and liquid, making the surface of condensed solid particles easy to wet; 2) form an adsorption layer on the surface of solid particles to increase the charge on the surface of solid particles and increase the reaction force between particles that forms steric hindrance; 3) form a bilayer structure on the surface of solid particles. The polar end of the outer dispersant has a strong affinity with water, which increases the degree of wetting of solid particles by water. The solid particles are kept away from each other due to electrostatic repulsion, thereby dispersing the active ingredients of pesticides, preventing particle aggregation, and forming a more stable oil suspension system.

[0004] Existing dispersants still have some defects in dispersing high-load pesticide oil suspensions. For example, the oil suspension adjuvant disclosed in CN115104603A includes isomeric alcohol ether sulfates or a mixture of isomeric alcohol ether sulfates and isomeric alcohol ethers, and salicylic acid or a mixture of salicylic acid and isomeric alcohol ethers, which aims to solve the problems of poor emulsification effect, increased viscosity, easy oil precipitation, stratification and paste formation during storage at room temperature, etc. in the process of preparing high-content oil suspensions. However, this type of small molecule non-aqueous carrier dispersant has almost no dispersing effect on high-load pesticide oil suspensions; for example, CN103109804A discloses a comb-like structured graft copolymer, in which the main chain is "anchored" on the pesticide particles through the main chain group, and the side chain introduces higher fatty acids and their higher fatty alcohol polyoxyethylene ethers or higher fatty acids and their esters with good compatibility with vegetable oils, so that they can be extended in the vegetable oil and form a huge three-dimensional structure on the particle surface. The body adsorption structure produces a steric hindrance effect, thereby dispersing and stabilizing the pesticide particles. However, this type of comb-like polymer dispersant has a weak adsorption force on pesticide particles. Although the molecular weight is greater than that of conventional emulsifiers, the steric hindrance is still small, and it is difficult to obtain long-term storage stability; for example, CN118812762A discloses a comb-like structure dispersant, whose molecular structure includes a central skeleton and a multi-arm comb-like structure extending from the skeleton, which can effectively entangle and stabilize the active ingredients of the pesticide, prevent agglomeration, and promote uniform dispersion in the oil phase, but there are certain defects in its preparation process: its monoesterification reaction is carried out at 70-90°C, the water generated during the reaction cannot evaporate, which will make it difficult to fully esterify, and the number of repeating units in the obtained dispersant is greater than or equal to 5 and less than or equal to 50, resulting in a smaller steric hindrance of the comb-like dispersant, and the solubility of the comb-like dispersant in non-aqueous carriers is not specified.

[0005] In view of the above reasons, a new dispersant suitable for high-loaded pesticide oil suspension is in urgent need of development. It not only needs to have stronger dispersing ability to effectively reduce the aggregation between pesticide particles, so that the high-loaded pesticide active ingredients are evenly dispersed in the oil phase to form a stable suspension system; it also needs to have good compatibility with the carrier to adapt to different environments and conditions, thereby solving the problems of high viscosity, difficult discharging, poor stability over time, and no fluidity during the sand grinding process of high-loaded pesticide oil suspension. Summary of the invention

[0006] 1. Problem to be solved

[0007] In view of one of the problems existing in the above-mentioned prior art, the present invention provides a high-load pesticide oil suspension dispersant and its preparation method and application, which is a polyacrylate superdispersant. The dispersant is a "comb-shaped" polyacrylate cationic structure, which is obtained by copolymerizing vinyl derivatives, acrylate derivatives and alkylamino polyethers with acrylates or maleic anhydride esters or acrylic amide derivatives as raw materials, and then oxidizing and cationizing. Through the main side chain including dimethylene, long-chain alkyl, EO / PO block, ester group and nitrogen-containing cationic active groups and its own macromolecular structure characteristics, the viscosity of the formulation system is reduced, and the effect of stable dispersion is achieved, which solves the problems of high viscosity, difficult discharging, poor stability over time, and no fluidity during the sand milling process of the high-load pesticide oil suspension.

[0008] 2. Technical solution

[0009] In order to solve the above problems, the technical solution adopted by the present invention is as follows:

[0010] The present invention provides a high-load pesticide oil suspension dispersant, which comprises the following three types of structural units:

[0011] The general formula of the structural unit of type A is

[0012] The general formula of the B-type structural unit is

[0013] The general formula of the C-type structural unit is

[0014] in:

[0015] R1 is C5~C 20 Alkyl, benzene ring or Any one of, n1, n2 is any integer from 0 to 20;

[0016] R2 is C1~C 20 Any one of alkyl, R3 is any one of -H, -CH3, X is any one of nitrogen, oxygen;

[0017] R4 is -H, R5 and R6 are -H, any one of a linear or branched, saturated or unsaturated alkyl group having 1 to 20 carbon atoms, Y is any one of nitrogen and oxygen, and n3, n4 and n5 are any integers from 0 to 10.

[0018] Furthermore, in the above dispersant, R1 is Wherein: n1 is any integer from 0 to 3; n2 is any integer from 7 to 10.

[0019] Furthermore, in the above dispersant, n1 is 1, n2 is 9; or n1 is 2, n2 is 8; or n1 is 3, n2 is 7.

[0020] Furthermore, in the above dispersant, X is oxygen.

[0021] Furthermore, in the above dispersant, Y is oxygen.

[0022] Furthermore, in the above dispersant, n3, n4, and n5 are any integers from 0 to 5.

[0023] Furthermore, in the above dispersant, n3, n4, and n5 are 0; or n3 is 0, n4 is 0, and n5 is 5; or n3 is 0, n4 is 0, and n5 is 4; or n3 is 0, n4 is 0, and n5 is 2.

[0024] Furthermore, in the above dispersant, n1 is 1, n2 is 9, and n3, n4, and n5 are 0.

[0025] Furthermore, in the above dispersant, n1 is 2, n2 is 8, and n3, n4, and n5 are 0.

[0026] Furthermore, in the above dispersant, n1 is 3, n2 is 7, and n3, n4, and n5 are 0.

[0027] Furthermore, in the above dispersant, n1 is 1, n2 is 9, n3 is 0, n4 is 0, and n5 is 5.

[0028] Furthermore, in the above dispersant, n1 is 1, n2 is 9, n3 is 0, n4 is 0, and n5 is 4.

[0029] Furthermore, in the above dispersant, n1 is 1, n2 is 9, n3 is 0, n4 is 0, and n5 is 2.

[0030] Furthermore, in the above dispersant, the mass ratio of A, B and C structural units is (2-8): (2-8): (1-4).

[0031] Furthermore, the above-mentioned high-load pesticide oil suspension dispersant is composed of A, B and C structural units, and the dispersant structural formula is:

[0032]

[0033]

[0034]

[0035] or

[0036]

[0037] The present invention also provides a method for preparing the above-mentioned high-load pesticide oil suspension dispersant. The preparation method uses the above-mentioned A, B and C structural units, and carries out 1) graft polymerization reaction: adding reaction monomer A, reaction monomer C and chain transfer agent to butanone solution, stirring and heating to reflux at 70-100° C. to obtain a mixed solution; adding reaction monomer B and butanone solution containing initiator to the mixed solution at the same time, and the dropping time is 2-5 hours; 2) after the above-mentioned dropping is completed, continuing to keep warm and reflux at 60-90° C. for 3-5 hours; 3) introducing chloroform at 70-85° C. to carry out quaternization reaction on the tertiary amine groups in the above-mentioned reaction monomers, and obtaining a high-load pesticide oil suspension dispersant. After the reaction is completed, the above-mentioned monomer A, monomer B and monomer C constitute the A, B and C structural units of the dispersant.

[0038] Furthermore, the reactive monomer A is any one of styrene and alkoxy compounds of allyl alcohol.

[0039] Furthermore, the above-mentioned reaction monomer A is an allyl alcohol alkoxy compound, and its general structural formula is R1 is n1 is 1, n2 is 9; or n1 is 2, n2 is 8; or n1 is 3, n2 is 7.

[0040] Furthermore, the above-mentioned reactive monomer B is any one of methyl acrylate, methyl methacrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, isomeric dodecyl acrylate, isomeric tridecyl acrylate, tetradecyl acrylate, eicosyl acrylate or oleyl acrylate.

[0041] Furthermore, the reactive monomer B is any one of methyl acrylate, butyl acrylate, octyl acrylate, isomeric dodecyl acrylate or eicosyl acrylate.

[0042] Furthermore, the above-mentioned reactive monomer C is an alkylamino polyether and an acrylate or maleic anhydride ester or an acrylic amide derivative.

[0043] Furthermore, the above-mentioned reactive monomer C is ethoxylated methylamino polyether ester of acrylic acid, having the structural formula R4 is -H, Y is oxygen, n3, n4, and n5 are 0; or n3 is 0, n4 is 0, and n5 is 5; or n3 is 0, n4 is 0, and n5 is 4; or n3 is 0, n4 is 0, and n5 is 2.

[0044] Furthermore, the mass ratio of the above-mentioned reaction monomers A, B, and C is (2-8): (2-8): (1-4).

[0045] Furthermore, the mass ratio of the above-mentioned reaction monomers A, B, and C is 3:2:5.

[0046] Furthermore, the chain transfer agent is any one or more of dicarboxymethyl trithiocarbonate, dibenzyl trithiocarbonate, dicarboxyisopropyl trithiocarbonate, 3-mercaptopropionic acid, thioglycolic acid, mercaptoethanol, isopropanol, dodecyl mercaptan or octanol.

[0047] Furthermore, the chain transfer agent is 3-mercaptopropionic acid.

[0048] Furthermore, the amount of the chain transfer agent is 0.5-5% of the sum of the mass of the reactive monomer A, reactive monomer B and reactive monomer C.

[0049] Furthermore, the initiator is any one or more of benzoyl oxide, tert-butyl benzoyl peroxide, methyl ethyl ketone peroxide, dodecyl peroxide, diisopropyl peroxydicarbonate, bis(4-tert-butylcyclohexyl) peroxydicarbonate, azobisisobutyronitrile or azobisisoheptanenitrile.

[0050] Furthermore, the initiator is any one of benzoyl oxide, azobisisoheptanenitrile, azobisisobutyronitrile, methyl ethyl ketone peroxide, dodecyl peroxide, diisopropyl peroxydicarbonate or bis(4-tert-butylcyclohexyl) peroxydicarbonate.

[0051] Furthermore, the amount of the initiator is 1-5% of the total mass of the reactive monomer A, reactive monomer B and reactive monomer C.

[0052] The present invention also provides the use of the above-mentioned high-load pesticide oil suspension dispersant in the preparation of the high-load pesticide oil suspension.

[0053] The present invention also provides a high-load pesticide oil suspension, comprising the above-mentioned high-load pesticide oil suspension dispersant, which can be adsorbed on the surface of the original drug particles to generate charge repulsion or steric hindrance, prevent agglomeration between particles, and ensure the stability of the preparation during storage and use.

[0054] Furthermore, the above-mentioned high-load pesticide oil suspension also includes an emulsifier and a thickener.

[0055] 3. Beneficial effects

[0056] Compared with the prior art, the present invention has the following beneficial effects:

[0057] (1) The present invention provides a novel polyacrylate superdispersant, which is a "comb-shaped" polyacrylate cationic structure. The molecular skeleton is composed of a main chain and a side chain, wherein: the di-methylene and long-chain alkyl groups on the main side chains provide dispersion force and have good compatibility with the oily dispersed phase, can be extended in the liquid phase, and form a large three-dimensional adsorption structure on the surface of the preparation, generating a large steric hindrance; the EO / PO block in the side chain can further improve the compatibility of the dispersant with the oily dispersed phase by adjusting the lipophilic water property, and exert a better dispersing effect to stabilize the system; the nitrogen cation in the side chain can be close to the electronegative atoms such as nitrogen, oxygen or phosphorus in the pesticide original drug, so that the dispersant and the original drug are better adsorbed, and the adsorption amount is increased. At the same time, a positively charged adsorption layer is formed on the particle surface, and the stability of the dispersed system is further improved by electrostatic repulsion.

[0058] (2) When preparing the above-mentioned polyacrylate cationic dispersant, the preparation process is carried out in an oily system containing butanone, and the obtained product does not need to separate the solvent, and the product itself can be well dissolved in the oily dispersed phase. The entire preparation process is simple, easy to operate, and has a short production cycle, and is suitable for industrial-scale production.

[0059] (3) The high-load pesticide oil suspension dispersant obtained by the present invention using the above-mentioned preparation process has good performance in various performance tests such as viscosity, stability and effective suspension rate. In practical applications, it can effectively solve the problems of high viscosity, difficult discharge, poor stability after long-term placement, and lack of fluidity during the sand grinding process of the high-load pesticide oil suspension. It has good application prospects as a high-load pesticide oil suspension dispersant. DETAILED DESCRIPTION

[0060] The present application is further described below in conjunction with specific embodiments.

[0061] It should be noted that the terms such as "upper", "lower", "left", "right", "middle", etc. cited in this specification are only for the convenience of description and are not used to limit the scope of implementation. Changes or adjustments to their relative relationships should be regarded as the scope of implementation of this application without substantially changing the technical content.

[0062] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention belongs; the term "and / or" used herein includes any and all combinations of one or more of the associated listed items.

[0063] If the specific conditions are not specified in the examples, the experiments were carried out under conventional conditions or conditions recommended by the manufacturer. If the manufacturers of the reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0064] As used herein, the term "about" is used to provide flexibility and imprecision associated with a given term, measurement or value. The degree of flexibility for a particular variable can be easily determined by one skilled in the art.

[0065] As used herein, the term "at least one of" is intended to be synonymous with "one or more of." For example, "at least one of A, B, and C" expressly includes only A, only B, only C, and combinations of each thereof.

[0066] Concentration, amount and other numerical data can be presented in range format herein.It should be understood that such range format is only used for convenience and simplicity, and should be flexibly interpreted as not only including the numerical value clearly described as range limit, but also including all single numerical values ​​or sub-ranges contained in the range, just as each numerical value and sub-range are clearly described.For example, the numerical range of about 1 to about 4.5 should be interpreted as not only including the limit value of 1 to about 4.5 clearly described, but also including single numerals (such as 2,3,4) and sub-ranges (such as 1 to 3,2 to 4, etc.).The same principle is applicable to the scope of only narrating a numerical value, such as "less than about 4.5", which should be interpreted as including all the above-mentioned values ​​and ranges.In addition, no matter how the breadth of the described range or feature is, this explanation should be applicable.

[0067] Example 1

[0068] This embodiment provides a high-load pesticide oil suspension dispersant.

[0069] (1) The structural formula is as follows:

[0070]

[0071] (2) The preparation method is as follows:

[0072] The reaction monomer A used is an allyl alcohol alkoxy compound (n1=1, n2=9), the reaction monomer B is methyl acrylate, and the reaction monomer C is ethoxylated methylamino polyether acrylate (Y is an oxygen atom, n3=0, n4=0, n5=0, R5 and R6 are -CH3, and R4 is -H).

[0073] Take 30g of the above-mentioned reaction monomer A, 50g of reaction monomer C, 400g of butanone and 3g of 3-mercaptopropionic acid and add them into a reaction kettle, stir and heat to 75-80°C for insulation to obtain a mixed solution; within 2.5 hours, simultaneously add 20g of reaction monomer B, 3g of initiator benzoyl oxide and 35g of butanone mixed solution to the above-mentioned mixed solution, and heat it at 60-90°C for 4 hours; add 6g of methyl chloride at 70-80°C, and heat it at 75-80°C for 3.5-4 hours to obtain a cationic polycarboxylate solution of a nitrogen-containing structure with an effective content (ratio of output material to input material) of 20%.

[0074] Example 2

[0075] This embodiment provides a high-load pesticide oil suspension dispersant.

[0076] (1) The structural formula is as follows:

[0077]

[0078] (2) The preparation method is as follows:

[0079] The reactive monomer A used is the same as that in Example 1, the reactive monomer B is butyl acrylate, and the reactive monomer C is the same as that in Example 1.

[0080] Take the above reaction monomer A30g, reaction monomer C 50g, butanone 400g and 3g of 3-mercaptopropionic acid into a reaction kettle, stir and heat to 75-80°C for insulation to obtain a mixed solution; add 20g of reaction monomer B, 3g of initiator benzoyl oxide and 35g of butanone mixed solution dropwise to the above mixed solution within 2.5h, and keep the temperature at 60-90°C for reaction for 4h; add 6g of methyl chloride at 70-80°C, and keep the temperature at 75-80°C for 3.5-4h to obtain a cationic polycarboxylate solution with an effective content of 20% of a nitrogen-containing structure.

[0081] Example 3

[0082] This embodiment provides a high-load pesticide oil suspension dispersant.

[0083] (1) The structural formula is as follows:

[0084]

[0085] (2) The preparation method is as follows:

[0086] The reactive monomer A used is the same as that in Example 1, the reactive monomer B is octyl acrylate, and the reactive monomer C is the same as that in Example 1.

[0087] Take the above reaction monomer A30g, reaction monomer C 50g, butanone 400g and 3g of 3-mercaptopropionic acid into a reaction kettle, stir and heat to 75-80°C for insulation to obtain a mixed solution; add 20g of reaction monomer B, 3g of initiator benzoyl oxide and 35g of butanone mixed solution dropwise to the above mixed solution within 2.5h, and keep the temperature at 60-90°C for reaction for 4h; add 6g of methyl chloride at 70-80°C, and keep the temperature at 75-80°C for 3.5-4h to obtain a cationic polycarboxylate solution with an effective content of 20% of a nitrogen-containing structure.

[0088] Example 4

[0089] This embodiment provides a high-load pesticide oil suspension dispersant.

[0090] (1) The structural formula is as follows:

[0091]

[0092] (2) The preparation method is as follows:

[0093] The reaction monomers used are the same as those in Example 1, reaction monomer B is isomeric dodecyl acrylate, and reaction monomer C is the same as that in Example 1.

[0094] Take the above reaction monomer A30g, reaction monomer C 50g, butanone 400g and 3g of 3-mercaptopropionic acid into a reaction kettle, stir and heat to 75-80°C for insulation to obtain a mixed solution; add 20g of reaction monomer B, 3g of initiator benzoyl oxide and 35g of butanone mixed solution dropwise to the above mixed solution within 2.5h, and keep the temperature at 60-90°C for reaction for 4h; add 6g of methyl chloride at 70-80°C, and keep the temperature at 75-80°C for 3.5-4h to obtain a cationic polycarboxylate solution with an effective content of 20% of a nitrogen-containing structure.

[0095] Example 5

[0096] This embodiment provides a high-load pesticide oil suspension dispersant.

[0097] (1) The structural formula is as follows:

[0098]

[0099] (2) The preparation method is as follows:

[0100] The reactive monomer A used is the same as that in Example 1, the reactive monomer B is butyl acrylate, and the reactive monomer C is the same as that in Example 1.

[0101] Take the above reaction monomer A30g, reaction monomer C 50g, butanone 400g and 3g of 3-mercaptopropionic acid into a reaction kettle, stir and heat to 75-80°C for insulation to obtain a mixed solution; add reaction monomer B 20g, 3g initiator azobisisoheptanenitrile and 35g butanone mixed solution dropwise to the above mixed solution within 2.5h, and heat at 60-90°C for reaction for 4h; add methyl chloride 6g at 70-80°C, and heat at 75-80°C for 3.5-4h to obtain a cationic polycarboxylate solution with an effective content of 20% of nitrogen-containing structure.

[0102] Example 6

[0103] This embodiment provides a high-load pesticide oil suspension dispersant.

[0104] (1) The structural formula is as follows:

[0105]

[0106] (2) The preparation method is as follows:

[0107] The reaction monomer A used is an allyl alcohol alkoxy compound (n1=2, n2=8), the reaction monomer B is the same as in Example 1, and the reaction monomer C is the same as in Example 1.

[0108] Take the above reaction monomer A30g, reaction monomer C 50g, butanone 400g and 3g of 3-mercaptopropionic acid into a reaction kettle, stir and heat to 75-80°C for insulation to obtain a mixed solution; add reaction monomer B20g, 3g initiator azobisisobutyronitrile and 35g butanone mixed solution to the above solution at the same time within 2.5h, and keep the temperature at 60-90°C for reaction for 4h; add methyl chloride 6g at 70-80°C, and keep the temperature at 75-80°C for 3.5-4h to obtain a cationic polycarboxylate solution with an effective content of 20% of nitrogen-containing structure.

[0109] Example 7

[0110] This embodiment provides a high-load pesticide oil suspension dispersant.

[0111] (1) The structural formula is as follows:

[0112]

[0113] (2) The preparation method is as follows:

[0114] The reaction monomer A used is an allyl alcohol alkoxy compound (n1=3, n2=7), the reaction monomer B is the same as in Example 1, and the reaction monomer C is the same as in Example 1.

[0115] Take the above reaction monomer A30g, reaction monomer C50g, butanone400g and 3g of 3-mercaptopropionic acid into a reaction kettle, stir and heat to 75-80°C for insulation to obtain a mixed solution; add reaction monomer B20g, 3g initiator methyl ethyl ketone peroxide and 35g butanone mixed solution to the above mixed solution dropwise within 2.5h, and keep the temperature at 60-90°C for reaction for 4h; add methyl chloride 6g at 70-80°C, and keep the temperature at 75-80°C for 3.5-4h to obtain a cationic polycarboxylate solution with an effective content of 20% of a nitrogen-containing structure.

[0116] Example 8

[0117] This embodiment provides a high-load pesticide oil suspension dispersant.

[0118] (1) The structural formula is as follows:

[0119]

[0120] (2) The preparation method is as follows:

[0121] The reaction monomer A used is the same as in Example 1, the reaction monomer B is the same as in Example 1, and the reaction monomer C is an ethoxylated methylamino polyether ester of acrylic acid (Y is an oxygen atom, n3=0, n4=0, n5=5, R4, R5 are -H, R6 is -C 20 H 41 ).

[0122] Take the above reaction monomer A30g, reaction monomer C 50g, butanone 400g and 3g of 3-mercaptopropionic acid into a reaction kettle, stir and heat to 75-80°C for insulation to obtain a mixed solution; add reaction monomer B 20g, 3g initiator dodecyl peroxide and 35g butanone mixed solution dropwise to the above mixed solution within 2.5h, and heat at 60-90°C for reaction for 4h; add methyl chloride 6g at 70-80°C, and heat at 75-80°C for 3.5-4h to obtain a cationic polycarboxylate solution with an effective content of 20% of a nitrogen-containing structure.

[0123] Example 9

[0124] This embodiment provides a high-load pesticide oil suspension dispersant.

[0125] (1) The structural formula is as follows:

[0126]

[0127] (2) The preparation method is as follows:

[0128] The reaction monomer A used is the same as in Example 1, the reaction monomer B is the same as in Example 1, and the reaction monomer C is an ethoxylated methylamino polyether ester of acrylic acid (Y is an oxygen atom, n3=0, n4=0, n5=4, R4, R5 are -H, R6 is -C 18 H 37 ).

[0129] Take the above reaction monomer A30g, reaction monomer C 50g, butanone 400g and 3g of 3-mercaptopropionic acid into a reaction kettle, stir and heat to 75-80°C for insulation to obtain a mixed solution; add reaction monomer B 20g, 3g initiator diisopropyl peroxydicarbonate and 35g butanone mixed solution dropwise to the above mixed solution within 2.5h, and heat at 60-90°C for reaction for 4h; add methyl chloride 6g at 70-80°C, and heat at 75-80°C for 3.5-4h to obtain a cationic polycarboxylate solution with an effective content of 20% of a nitrogen-containing structure.

[0130] Example 10

[0131] This embodiment provides a high-load pesticide oil suspension dispersant.

[0132] (1) The structural formula is as follows:

[0133]

[0134] (2) The preparation method is as follows:

[0135] The reaction monomer A used is the same as in Example 1, the reaction monomer B is the same as in Example 1, and the reaction monomer C is an ethoxylated methylamino polyether ester of acrylic acid (Y is an oxygen atom, n3=0, n4=0, n5=2, R4, R5 are -H, R6 is -C 12 H 25 ).

[0136] Take the above reaction monomer A30g, reaction monomer C 50g, butanone 400g and 3g of 3-mercaptopropionic acid into a reaction kettle, stir and heat to 75-80°C for insulation to obtain a mixed solution; within 2.5 hours, simultaneously add reaction monomer B 20g, 3g initiator peroxydicarbonate bis (4-tert-butylcyclohexyl) ester and 35g of butanone mixed solution dropwise to the above mixed solution, and heat at 60-90°C for 4 hours; add methyl chloride 6g at 70-80°C, and heat at 75-80°C for 3.5-4 hours to obtain a cationic polycarboxylate solution with an effective content of 20% of a nitrogen-containing structure.

[0137] Embodiment 11

[0138] This example provides an evaluation of the application performance of a high-load pesticide oil suspension dispersant.

[0139] Application Case 1: 3% Nicosulfuron + 5% Mesotrione + 25% Atrazine OD

[0140] The recipe is as follows:

[0141]

[0142] Application Case 2: 3% Nicosulfuron + 6% Mesotrione + 30% Atrazine OD

[0143] The recipe is as follows:

[0144]

[0145] The preparation method of the above oil suspension formula is as follows: add the components in the table in sequence, mix them evenly, shear them evenly with a high-speed shearing machine, add 1.6-1.8 mm zirconium oxide beads and sand grind them for 60 minutes, filter the material, test the viscosity, divide it into 3 groups of samples, and conduct normal storage, hot storage and cold storage experiments respectively to observe the stability of the preparation.

[0146] The purchasing channels of each component are as follows: Nicosulfuron, atrazine: Shandong Binnong Technology Co., Ltd.; Mesotrione: Hebei Chengxin Group Co., Ltd.; Organic soil: Suzhou Guojian Huitou Mineral New Materials Co., Ltd.; Fumed silica: Jiangsu Haoneng Chemical Co., Ltd.; SP-OF3473E, SP-OF3462E: Jiangsu Qingyu Chemical Technology Co., Ltd.; Methyl oleate: Jiangsu Fengbei Biotechnology Co., Ltd.; Competitor additive 1: Star-shaped polycarboxylate dispersant; Competitor additive 2: Polyisobutylene succinimide dispersant.

[0147] The performance testing methods are as follows:

[0148] (1) Viscosity test: measured according to the Agricultural Industry Standard of the People's Republic of China "Guidelines for the Determination of Physical and Chemical Properties of Pesticides - Viscosity", NY / T 1860.21-2016 (MT 192);

[0149] (2) Room temperature stability: Determined according to the General Rules for Storage Stability Tests of Pesticides at Room Temperature, NY T 1427-2016, the agricultural industry standard of the People's Republic of China;

[0150] (3) Thermal storage stability: Determined according to the method in GB / T19136-2003, the national standard of the People's Republic of China, "Method for Determination of Thermal Storage Stability of Pesticides";

[0151] (4) Cold storage stability: Determined according to the method in GB / T19137-2003, the national standard of the People's Republic of China, "Determination of low temperature stability of pesticides";

[0152] (5) Determination of effective suspension rate: Determined according to the agricultural industry standard of the People's Republic of China "Method for Determination of Pesticide Suspension Rate", GB / T 14825-2006.

[0153] Result analysis:

[0154] Performance evaluation of different dispersants in 3% Nicosulfuron + 5% Mesotrione + 25% Atrazine OD:

[0155]

[0156] Performance evaluation of different dispersants in 3% Nicosulfuron + 6% Mesotrione + 30% Atrazine OD:

[0157]

[0158] It can be seen from the above results that the dispersant provided by the present invention has the effects of electrostatic repulsion, dispersion force, steric hindrance generated by its own macromolecular structure, tighter inclusion of cations and original drugs, and greater adsorption capacity. In practical applications, the suspension rates of the above-mentioned different high-loaded pesticide oil suspensions are mostly excellent, and some are good, and the suspension effects are better than those of competing adjuvants; for the viscosity of the high-loaded oil suspension, each dispersant group has a significant reduction compared with the competing adjuvant group; the storage stability at different temperatures of each dispersant group is also better than that of the competing adjuvant group, effectively solving the problems of high viscosity, difficult discharging, and poor stability and fluidity during the sand milling process of different high-loaded pesticide oil suspensions. On the whole, the dispersant in the present invention has good dispersibility and applicability, and has good prospects for use as a dispersant for other different high-loaded pesticide oil suspensions.

Claims

1. A high-load pesticide oil suspension dispersant, characterized in that: The dispersant comprises the following three types of structural units: The general formula of the structural unit of type A is The general formula of the B-type structural unit is The general formula of the C-type structural unit is in: R1 is C5~C 20 Alkyl, benzene ring or Any one of, n1, n2 is any integer from 0 to 20; R2 is C1~C 20 Any one of alkyl, R3 is any one of -H, -CH3, X is any one of nitrogen, oxygen; R4 is -H, R5 and R6 are -H, any one of a linear or branched, saturated or unsaturated alkyl group having 1 to 20 carbon atoms, Y is any one of nitrogen and oxygen, and n3, n4 and n5 are any integers from 0 to 10.

2. The dispersant according to claim 1, characterized in that The n1 is any integer from 0 to 3, n2 is any integer from 7 to 10, and n3, n4 and n5 are any integers from 0 to 5.

3. The dispersant according to claim 1, characterized in that The mass ratio of the A, B and C structural units is (2-8): (2-8): (1-4).

4. A method for preparing a high-load pesticide oil suspension dispersant according to any one of claims 1 to 3, characterized in that: It is prepared using monomers A, B and C corresponding to the A, B and C structural units, specifically including: 1) adding reaction monomer A, reaction monomer C and chain transfer agent to butanone solution, stirring at 70-100° C. and heating under reflux to obtain a mixed solution; simultaneously adding reaction monomer B and butanone solution containing initiator dropwise to the mixed solution for 2-5 hours; 2) After the addition is completed, continue to reflux at 60-90°C for 3-5 hours; 3) introducing methyl chloride at 70-85° C. to carry out quaternization reaction on the tertiary amine groups in the reaction monomer.

5. The preparation method according to claim 4, characterized in that: The reactive monomer A is any one of styrene and alkoxylate of allyl alcohol; and / or The reactive monomer B is any one of methyl acrylate, methyl methacrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, isomeric dodecyl acrylate, isomeric tridecyl acrylate, tetradecyl acrylate, eicosyl acrylate or oleyl acrylate; and / or The reactive monomer C is an alkylamino polyether and an acrylate or maleic anhydride ester or an acrylic acid amide derivative.

6. The preparation method according to claim 4 or 5, characterized in that: The mass ratio of the three reaction monomers A, B and C is (2-8): (2-8): (1-4).

7. The preparation method according to claim 6, characterized in that: The chain transfer agent is any one or more of dicarboxymethyl trithiocarbonate, dibenzyl trithiocarbonate, dicarboxyisopropyl trithiocarbonate, 3-mercaptopropionic acid, thioglycolic acid, mercaptoethanol, isopropanol, dodecyl mercaptan or octanol; and / or the initiator is any one or more of benzoyl oxide, tert-butyl benzoyl peroxide, methyl ethyl ketone peroxide, dodecyl peroxide, diisopropyl peroxydicarbonate, bis(4-tert-butylcyclohexyl) peroxydicarbonate, azobisisobutyronitrile or azobisisoheptonitrile.

8. The preparation method according to claim 7, characterized in that: The amount of the chain transfer agent is 0.5-5% of the total mass of the reaction monomer A, reaction monomer B and reaction monomer C; and / or the amount of the initiator is 1-5% of the total mass of the reaction monomer A, reaction monomer B and reaction monomer C.

9. Use of a high-loaded pesticide oil suspension dispersant according to any one of claims 1 to 3 in the preparation of a high-loaded pesticide oil suspension.

10. A high-load pesticide oil suspension, characterized in that: The oil suspension concentrate comprises a high-loaded pesticide oil suspension concentrate dispersant as described in any one of claims 1-3.

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