CN114230780B

CN114230780B - Vegetable oil-based polymer, composition and preparation method thereof

Info

Publication number: CN114230780B
Application number: CN202111648534.1A
Authority: CN
Inventors: 秦敦忠; 王磊
Original assignee: Jiangsu Sinvo Chemical Technology Co ltd
Current assignee: Jiangsu Sinvo Chemical Technology Co ltd
Priority date: 2021-12-30
Filing date: 2021-12-30
Publication date: 2023-08-18
Anticipated expiration: 2041-12-30
Also published as: CN114230780A

Abstract

The invention discloses a plant oil-based polymer, a composition and a preparation method thereof, wherein the polymer is a polymer with five-membered heterocycle contained in active primary amine modified plant oil, and electron donating N-H units and quaternary aminated tertiary amine on polyethylene polyamine groups in the plant oil-based polymer can be firmly adsorbed on the surface of a target under the action of factors such as hydrogen bond, electrostatic force and the like, thereby being beneficial to improving the deposition amount of liquid medicine on the target, reducing the liquid medicine loss and avoiding the harm of environmental pollution.

Description

Vegetable oil-based polymer, composition and preparation method thereof

Technical Field

The invention belongs to the field of pesticide assistants, and in particular relates to a plant oil-based polymer, a composition and a preparation method thereof.

Background

The fertilizer and the pesticide are indispensable input products in agricultural production, and the agricultural auxiliary agent can improve the utilization rate of the pesticide and the fertilizer, so that the agricultural yield and the income of farmers are increased. However, as the living and consumption demands of the public are continuously improved, people pay more attention to safety, health and environmental protection, and higher requirements on the use of agricultural auxiliary agents are also provided. The world agrochemicals report data show that under the sowing of the 'green plant protection' concept, the global agricultural auxiliary sales market maintains a 7% composite growth rate throughout the year. With the implementation of 'zero growth of chemical fertilizer and pesticide decrement', china is eagerly calling for more efficient, more environment-friendly, more green and safer plant protection technology so as to reduce the usage amount of chemical fertilizer and pesticide and promote economic benefits of farmers.

The dispersible oil suspending agent is one or more solid pesticide active ingredients which are insoluble in oil solvents and are dispersed in a non-aqueous medium, and a highly dispersed and stable suspension liquid preparation is formed by virtue of an emulsifying dispersant and a viscosity regulator, so that the dispersible oil suspending agent has good dispersibility, stable performance, good adhesiveness and remarkable effect in target synergism, and is a novel pesticide preparation with great influence. Meanwhile, the oil is used as a dispersion medium, so that the pollution to the environment can be reduced, the permeability and the systemic property of the effective components are obviously improved, and the drug effect is further obviously improved.

However, dispersible oil suspending agents have the following problems: 1. the processing difficulty is high, and the stability is poor; the main reason is that the types of selectable processing aids are few, and the matching degree requirement among the components of the system is high; 2. the oil is used as a carrier, the specific gravity difference is large, and a thickening agent is needed to be added to adjust the viscosity of the preparation so as to delay the sedimentation rate of solid particles and reduce the storage oil precipitation of the preparation. The common thickening agents comprise white carbon black, organic bentonite and attapulgite, but the white carbon black is high in price, the attapulgite is not ideal in thickening effect, and cationic organic bentonite can be combined with an anionic auxiliary agent in an emulsifier dispersing agent to accelerate sedimentation and breaking of solid particles, so that the stability of the preparation is damaged, and the problems limit industrial application. Based on the above, in the patent application document of application number 201811391792.4, nicosulfan atrazine oil suspending agent using methyl oleate as a dispersion medium and a preparation method thereof are disclosed, but 10-15% NP series nonylphenol polyoxyethylene ether phosphate is used therein, the environment friendliness is poor, aquatic organisms are poisoned by accumulation in water, and the suspending agent has been gradually forbidden. In application number 200580007232.9, an oil-based suspension concentrate with a cyclic ketoenols is disclosed, but alkyl polyoxyethylene ethers and derivatives thereof are also used, which can be potentially harmful to the environment and to food products. Therefore, developing a safe, environment-friendly, efficient and renewable green auxiliary agent is a problem to be solved at present.

At present, vegetable oil-based auxiliary agents are synergistic auxiliary agents with highest development and utilization rate, particularly maleic anhydride vegetable oil, and can be used for preparing a plurality of oil-based materials, such as epoxy resin, polyester resin (containing alkyd resin), polyamide resin, photo-curing materials and the like, so as to be used in various aspects of coating, paint, adhesive, plasticizer and the like. The main component of the vegetable oil-based auxiliary agent is vegetable oil and derivatives thereof, but other emulsifying agents are difficult to emulsify due to the nature of the vegetable oil, so that the vegetable oil-based auxiliary agent is poor in stability and compatibility and easy to separate out, and the development of the vegetable oil-based auxiliary agent is limited to a certain extent.

In US2013210630A1, a self-emulsifying oil is disclosed, which is mainly applied to the field of pesticides, and this patent discloses a high temperature method and a method for preparing maleic anhydride modified vegetable oil by adding a catalyst. Wherein, the time for esterifying the maleic anhydride modified vegetable oil by ethanol and the like is up to 2 days, thereby reducing the production efficiency, improving the production cost and avoiding the commercial production. In the patent application document of WO2016153913A1, a maleated natural oil derivative for agriculture is disclosed, and although the drug effect can be improved, nonylphenol polyether monoamine is used in the preparation process, nonylphenol polyether and the derivative thereof bring potential harm to human bodies, natural environment and food, and limit the application thereof.

Disclosure of Invention

The main component of the vegetable oil-based auxiliary agent is vegetable oil and derivatives thereof, and is a green auxiliary agent with highest development and utilization rate at present. However, because of the nature of vegetable oil, it is difficult to be emulsified by other emulsifying agents, so that when the vegetable oil is used in pesticides such as dispersion oil suspending agents, the stability and compatibility are poor, and the vegetable oil is easy to separate out, which limits the development and use effect of vegetable oil-based auxiliary agents to a certain extent. Based on this, the present invention:

1. problems to be solved

The invention aims to provide a plant oil-based polymer which is renewable, easy to biodegrade, emulsifying and good in dispersibility and a composition thereof;

the second purpose of the invention is to provide a preparation method of the vegetable oil-based polymer and the composition thereof, which has short production process time consumption and can control cost.

2. Technical proposal

In order to solve the above problems, the present invention provides a method for preparing a vegetable oil-based polymer, comprising the steps of:

(1) Preparing maleated vegetable oil: maleic anhydride reacts with vegetable oil at high temperature to obtain maleated vegetable oil; the maleic anhydride accounts for 5-20% of the total weight of the maleic anhydride and the vegetable oil;

(2) In the environment of vegetable oil, the active polymerization monomer is contacted and mixed with organic amine in a dropwise manner to carry out amination reaction;

wherein the active polymerization monomer is maleic anhydride vegetable oil;

the organic amine is one or more of alkylene amine, polyether amine and alkanolamide;

the vegetable oil accounts for 30-70% of the total weight of the vegetable oil, the active polymerization monomer and the organic amine;

the amount of the active polymerization monomer and the organic amine is calculated according to the mole number of anhydride and the mole number of primary amine groups, and the mole ratio of the anhydride to the primary amine groups is (1-2): 1, a step of;

(3) Carrying out quaternization reaction, and distilling and recovering a quaternization reagent during the quaternization reaction to obtain a quaternized vegetable oil-based polymer taking vegetable oil as a solvent;

the molar ratio of the addition amount of the organic amine to the quaternizing agent is 1: (1-2.2).

Further, in the step (1), maleic anhydride and vegetable oil react at 190-230 ℃ to obtain maleated vegetable oil;

when the content of the maleic anhydride is reduced to 1-2 percent (detection can be carried out by gas chromatography), the reaction is finished;

then, heating and vacuumizing to further remove the free maleic anhydride; the conditions of heating and vacuumizing are as follows: the temperature is 50-150 ℃, the vacuum degree is 0.02-0.098 MPa, the time is 0.5-1.5 hours, and the condensing device is used for recycling for standby.

Further, in the step (1), the vegetable oil is one or more of castor oil, soybean oil, olive oil, peanut oil, rapeseed oil, corn oil, sesame oil, cotton oil, rape oil, safflower oil, linseed oil, palm oil, grape seed oil, tarragon oil, pumpkin oil, core oil, borage seed oil, wood germ oil, almond oil, pistachio oil, almond oil, kunsland nut oil, avocado oil, sea buckthorn oil, hemp oil, hazelnut oil, evening primrose oil, rose oil, thistle oil, walnut oil, sunflower oil, jatropha seed oil and swill-cooked dirty oil.

Further, in step (1), the maleated vegetable oil formula includes, but is not limited to, formulas (1), (2) and (3):

further, in the step (2), the specific contact mode between the active polymerization monomer and the organic amine is any one of the following modes:

firstly, mixing an active polymerization monomer and vegetable oil in a contact way, and then, adding the organic amine in a dropwise manner;

the temperature in the dropping process is 60-95 ℃, and the dropping time is 0.5-3 hours;

vacuum degassing and amination are carried out after the dripping is finished, the temperature is 120-160 ℃ and the time is 2-7 hours;

or firstly, contacting and mixing the organic amine with vegetable oil, and then, adding the active polymerization monomer in a dropwise manner;

and (3) after the dripping is finished, vacuum degassing and amination are carried out, the temperature is 120-160 ℃, and the time is 2-7 hours.

Further, in the step (2), the alkanolamine includes one or both of monoethanolamine and monoisopropanolamine;

the alkylene amine comprises one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dimethylaminopropylamine, aminopropylmorpholine and aminoethylpiperazine; preferably tetraethylenepentamine;

the polyetheramine comprises one or more of monofunctional polyetheramine (polyether monoamine structure), difunctional polyetheramine (polyether diamine structure), trifunctional polyetheramine (polyether triamine structure), tetrafunctional polyetheramine (polyether tetramine structure) and polyfunctional polyetheramine; wherein,,

the polyether monoamine has a structural general formula (4) as follows:

wherein R is a C1-C57 straight or branched alkyl group, phenyl group, unsaturated hydrocarbon chain, polymeric glyceryl group, sucrose group or sorbitan group; r is R ₁ ，R ₂ ，R ₃ Represent H, CH independently of each other ₃ Or CH (CH) ₂ CH ₃ ；n ₁ ，n ₂ ，n ₃ Independently of each other, an integer of 0 to 35; the sum of n1, n2 and n3 is not less than 2, and n is an integer of 1-8.

The polyether diamine has a general formula (5) as follows:

wherein R is ₄ ，R ₅ ，R ₆ Represent H, CH independently of each other ₃ Or CH (CH) ₂ CH ₃ The method comprises the steps of carrying out a first treatment on the surface of the n4, n5, n6 independently of each other represent an integer from 0 to 35; the sum of n4, n5, n6 is not less than 2.

The polyether triamine has a general formula (6) as follows:

wherein R is ₇ ，R ₈ ，R ₉ ，R ₁₀ Represent H, CH independently of each other ₃ Or CH (CH) ₂ CH ₃ The method comprises the steps of carrying out a first treatment on the surface of the n7, n8, n9, n11 independently of one another represent an integer from 1 to 100; n10 is an integer of 0 or 1.

The polyether tetramine has a general formula of (7):

wherein R is ₁₁ Represents H,CH ₃ Or CH (CH) ₂ CH ₃ ；R ₁₂ Represents a C1-C5 alkyl group; n12 independently of one another represents an integer from 20 to 55.

Further, in the step (2), the active polymerization monomer contains a product of the following structural general formula (8) and/or (9) after an amination reaction:

wherein R is ₁₃ Represents an alkylene amine residue or a polyetheramine residue;

wherein R is ₁₄ An alkylene amine residue or a polyetheramine residue;

further, in the step (2), after the dripping is completed, vacuum degassing amination is performed, and specific conditions are as follows: the temperature is 120-160 ℃, the time is 2-7 h, and the vacuum degree is-0.098-0 MPa; preferably, the specific conditions are as follows: the temperature is 135-155 ℃ and the time is 5-6 h.

Further, in the step (3), after the vacuum degassing amination reaction is completed, the reaction is carried out with a quaternizing agent, and the quaternizing agent is distilled and recovered during the reaction period, so that the quaternized vegetable oil-based polymer taking vegetable oil as a solvent is obtained;

The quaternization reaction temperature is 60-90 ℃ and the reaction time is 1-3 h.

Further, in the step (3), the quaternizing agent is one or more of chlorides such as dichloroethane, dichloropropane, dichlorobutane, dichloropentane, dichlorohexane, dibromoethane, dibromopropane, dibromobutane, dibromopentane, dibromohexane, chloromethane, chloroethane, chloropropane, tertiary butyl chloride, and benzyl chloride; preferably one or a combination of two of methyl chloride and dichloroethane.

Further, the preparation method of any one of the above, wherein the product obtained by the preparation method comprises quaternized vegetable oil-based polymer represented by the following general formula (10) and/or (11):

R ₁₅ is a quaternizing agent residue, X ^- Represents an anion in combination with a cation, said anion being chloride (Cl) ^- ) Or bromide (Br) ^- )；

Wherein R is ₁₄ Represents an alkylene amine residue or a polyetheramine residue;

R ₁₅ is a quaternizing agent residue;

X ^- represents an anion in combination with a cation, said anion being chloride (Cl) ^- ) Or bromide (Br) ^- )。

The composition containing any one of the quaternized vegetable oil-based polymers comprises the following components in parts by weight: 40-70 parts of quaternized vegetable oil-based polymer taking vegetable oil as solvent and 30-60 parts of composite additive; preferably, the formulation of the composition is: 55-68 parts of quaternized vegetable oil-based polymer taking vegetable oil as solvent and 30-45 parts of composite additive.

Further, the compound additive is formed by compounding a nonionic surfactant and fatty acid ester substances according to the mass ratio of (10-25) (45-80), wherein the general formula (12) of the nonionic surfactant is as follows:

wherein R is ₁₆ Is C1-C20 straight chain or branched alkyl, or sorbitol residue, or sucrose residue, or glycerolA residue, or a phenyl group having other substituents on the phenyl ring, or an unsaturated hydrocarbon chain, or H; r is R ₁₇ ，R ₁₈ ，R ₁₉ Represent H, CH independently of each other ₃ Or CH ₂ CH ₃ M1, m2, m3 independently of one another represent an integer from 0 to 30 and the sum of m1, m2 and m3 is greater than 0;

the fatty acid ester substances comprise one or more of trimethylolpropane fatty acid ester, propylene glycol fatty acid ester, pentaerythritol fatty acid ester, polyethylene glycol fatty acid monoester, polyethylene glycol fatty acid diester, fatty acid polyoxyethylene ether fatty acid ester, polyglycerol fatty acid ester, sorbitan fatty acid, sucrose fatty acid ester and general formula (9); wherein the general formula (13) is:

wherein R is ₂₀ Is a C1-C57 straight or branched alkyl group, an unsaturated hydrocarbon chain, an alkyl diamine residue, an amino alcohol residue, a carboxylic acid amide residue, an amino carboxylic acid residue, a polyglycerol residue, a sucrose residue, a sorbitol residue, or a sorbitan residue; r is R ₂₁ ，R ₂₂ ，R ₂₃ Represent H, CH independently of each other ₃ Or CH (CH) ₂ CH ₃ The method comprises the steps of carrying out a first treatment on the surface of the m4, m5, m6 independently of one another represent an integer from 0 to 30, m7 being an integer from 1 to 10; z is a poly 12-hydroxystearic acid residue, the residual acid number is typically less than 70mgKOH/g and preferably ranges from 30 to 56mgKOH/g, or a C1-C18 straight alkyl group or an unsaturated hydrocarbon chain.

A method of preparing a composition comprising a quaternized vegetable oil-based polymer comprising the steps of:

(1) Preparing a quaternized vegetable oil-based polymer with vegetable oil as a solvent;

(2) Mixing the quaternized vegetable oil-based polymer taking vegetable oil as a solvent with a composite additive at 60-70 ℃ and stirring to obtain the composition;

wherein, the quaternary vegetable oil-based polymer taking vegetable oil as solvent is 40 to 70 parts by weight; 30-60 parts of composite auxiliary agent; preferably, the formulation of the composition is: 55-68 parts of quaternized vegetable oil-based polymer taking vegetable oil as solvent and 30-45 parts of composite additive.

Advantageous effects

1) The preparation method of the vegetable oil-based polymer provided by the invention comprises the steps of preparing maleic anhydride vegetable oil active polymerization monomer by utilizing the olefine reaction of natural vegetable oil and maleic anhydride, then dripping one or a mixture of alkylene amine and polyether amine to perform amination reaction on the maleic anhydride vegetable oil to prepare the vegetable oil polymer, and then reacting with a quaternizing reagent to obtain the quaternized vegetable oil-based polymer, so that the time consumption is short and the production efficiency is high.

2) The vegetable oil-based polymer provided by the invention is a polymer containing five-membered heterocyclic rings of active primary amine modified vegetable oil, and electron donating N-H units and quaternary aminated tertiary amine on the polyethylene polyamine groups contained in the polymer can be firmly adsorbed on the surface of a target under the action of factors such as hydrogen bonds, electrostatic force and the like, so that the polymer is beneficial to improving the deposition amount of liquid medicine matched with the polymer in use on the target when used as an auxiliary agent, reducing the liquid medicine loss and avoiding the harm of environmental pollution;

3) The composition containing the vegetable oil-based polymer provided by the invention takes vegetable oil as a solvent, is similar to main components of the plant leaf surface, has good compatibility and strong affinity, and further enhances the retention and conduction of liquid medicine; the compatibility of different substances and raw medicines among the preparations is improved due to the inclusion of the oxyalkylated chain and the five-membered heterocycle, so that the physical stability among mixed medicines can be improved; meanwhile, the oil-soluble fatty acid is contained, so that the evaporation capacity of fog drops is reduced, and the utilization rate of the effective components of the pesticide can be improved;

meanwhile, the composition containing the vegetable oil-based polymer also has good adhesion, thickening and self-emulsifying properties, has the same charge as that of cationic organic soil in an oil suspension system, can slow down the sedimentation trend of accelerated particles caused by using an anionic auxiliary agent when being added into the oil suspension system, has better compatibility with vegetable oil, is easy to emulsify in water, can be independently used as an emulsifier, and can replace or reduce the application of other types of emulsifiers such as NP and OP polyether and derivatives thereof in the pesticide field of the oil suspension system. The composition can well emulsify vegetable oil, the obtained emulsion can be stored stably for a long time, the emulsifying property is excellent, the vegetable oil has natural high adhesive force, the waxy layers on the surfaces of targets and target crops can be dissolved, the permeability of a medicine on the targets or target plants is improved, and meanwhile, the introduction of amino and the quaternization of tertiary amine improve the pesticide effect of the composition in the aspect of sterilization, so that the composition has a certain synergistic effect.

Detailed Description

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

In the present invention, the specific conditions are not specified in the examples, and the process is carried out under conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.

The term "about" as used herein is used to provide the flexibility and inaccuracy associated with a given term, metric or value. The degree of flexibility of a particular variable can be readily determined by one skilled in the art.

As described herein, the vegetable oil iodine number (g iodine per 100g oil) described herein is: 120-137, preferably 125-130.

As described herein, maleic anhydride, abbreviated as MA, is also known as desiccated malic anhydride, maleic anhydride.

Example 1

860g of refined rapeseed oil and 45.28g of maleic anhydride are added into a four-necked flask to be mixed and stirred for 30min, nitrogen is introduced to protect, the temperature is raised to the set temperature of 205 ℃ (the actual temperature can have floating change of +/-5 ℃ in the reaction process) for 7h, the maleic anhydride content is detected to be 1-2% by meteorological chromatography, and the reaction is finished, so that the maleated soybean oil is obtained. Unreacted maleic anhydride is removed by a heating and vacuumizing method, the heating and vacuumizing set temperature is 112 ℃ (the actual temperature can have floating change of +/-3 ℃ in the reaction process), the vacuum degree is 0.05-0.065Mpa, the time is 0.6h, and a condensing device is utilized for recycling for standby, so that the active polymerization monomer 1A is obtained.

Example 1-1

3.1g of ethylenediamine and 103.1g of rapeseed oil are added into a four-necked flask, 100g of maleated rapeseed oil is added dropwise, the dropwise adding temperature is 77 ℃ (the actual temperature can have floating change of +/-3 ℃ in the process), and the dropwise adding time is 30 minutes. After the dripping is finished, vacuum degassing is carried out, the set temperature of the vacuum degassing is 152 ℃ (the actual temperature can have floating change of +/-3 ℃ in the reaction process), the degassing and amination time is 6 hours, and when the amine value is 28mgKOH/g, the vegetable oil-based polymer with the effective content of 50% is obtained; 3.87g of chloromethane is introduced under 72 ℃ (the actual temperature can have floating change of +/-3 ℃ in the process), and the reaction time is 2.5 hours; and distilling to recover chloromethane to obtain the quaternized vegetable oil-based polymer 1B taking vegetable oil as a solvent.

Examples 1 to 2

40g of the obtained 50% quaternized vegetable oil-based polymer, 60g of the composite emulsifier and stirring for 30min under the condition of the set temperature of 63 ℃ (the actual temperature possibly varies within 62-65 ℃), so as to obtain a vegetable oil-based polymer composition 1C.

Comparative example 1

This comparative example is substantially identical to example 1, except that the cis and vegetable oils are present in an amount of 3% by weight, based on the total weight of the cis and vegetable oils, to give the living polymeric monomer 1a.

Comparative examples 1 to 1

This comparative example was substantially the same as in example 1-1, and finally a vegetable oil-based polymer 1b having an effective content of 50% was obtained.

Comparative examples 1 to 2

This comparative example was substantially the same as in examples 1-2 to obtain a vegetable oil-based polymer composition 1c.

Example 2

Adding 920g of refined soybean oil and 80g of maleic anhydride into a four-neck flask, mixing, stirring for 30min, introducing nitrogen for protection, heating to a set temperature of 207 ℃ (the actual temperature can have floating change of +/-3 ℃ in the reaction process) for reacting for 6.5 hours, detecting that the maleic anhydride content is 1-2% by using a meteorological chromatograph, and obtaining the maleated soybean oil after the reaction is finished. Unreacted maleic anhydride is removed by a heating and vacuumizing method, the heating and vacuumizing temperature is 112 ℃, the vacuum degree is 0.065-0.07Mpa, the time is 1h, and a condensing device is utilized for recycling for standby, so that the active polymerized monomer 2A is obtained.

Example 2-1

8.4g of diethylenetriamine and 108.4g of soybean oil are added into a four-necked flask, 100g of maleated soybean oil is added dropwise, the set temperature during the dropwise addition is 78 ℃ (the actual temperature can have floating change of +/-2 ℃), and the dropwise addition time is 30 minutes. After the dripping is finished, vacuum degassing is carried out, the set temperature of the vacuum degassing is 152 ℃ (the actual temperature can have floating change of +/-3 ℃ in the reaction process), the degassing and amination time is 6.5 hours, after 50% vegetable oil-based polymer is obtained when the amine value is 42mgKOH/g, 6.17g chloromethane is introduced under 78 ℃ (the actual temperature can have floating change of +/-3 ℃ in the process), and the reaction time is 3 hours; recovering chloromethane by distillation to obtain quaternized vegetable oil-based polymer 2B

Example 2-2

40g of the obtained about 50% quaternized vegetable oil-based polymer, 60g of the composite emulsifier, and stirring for 30min under the condition of a set temperature of 63 ℃ (the actual temperature possibly has floating change of +/-5 ℃ in the reaction process) to obtain a vegetable oil-based polymer composition 2C.

Example 3

450g of refined cottonseed oil and 50g of maleic anhydride are added into a four-neck flask to be mixed and stirred for 30min, nitrogen is introduced to protect, the temperature is raised to be set to 198 ℃ (the actual temperature can have floating change of +/-2 ℃ in the reaction process) and the reaction is carried out for 8 hours, the maleic anhydride content is detected to be 1-2% by adopting a meteorological chromatograph, and the reaction is finished, so that the maleated soybean oil is obtained. Unreacted maleic anhydride is removed by a heating and vacuumizing method, the set temperature of heating and vacuumizing is 107 ℃ (the actual temperature can have floating change of +/-3 ℃ in the reaction process), the vacuum degree is 0.053-0.06Mpa, the time is 1.5 hours, and a condensing device is used for recycling for standby, so that the active polymerized monomer 3A is obtained.

Example 3-1

14.8g of triethylene tetramine and 114.8g of soybean oil are added into a four-necked flask, 100g of maleated cottonseed oil is added dropwise, the dropwise adding temperature is 77 ℃ (the actual temperature can have floating change of +/-3 ℃ in the process), and the dropwise adding time is 30 minutes. After the dripping is finished, vacuum degassing is carried out, the set temperature of the vacuum degassing is 152 ℃ (the actual temperature can have floating change of +/-3 ℃ in the reaction process), the degassing and amination time is 6.8 hours, after 50% vegetable oil-based polymer is obtained when the amine value is 74mgKOH/g, 7.67g chloromethane is introduced under 72 ℃ (the actual temperature can have floating change of +/-3 ℃ in the process), and the reaction time is 2.5 hours; and distilling to recover methyl chloride to obtain the quaternized vegetable oil-based polymer 3B.

Example 3-2

30g of the obtained about 50% quaternized vegetable oil-based polymer, 70g of the composite emulsifier and stirring for 30min under the condition of set temperature 65 ℃ (the actual temperature possibly has floating change of +/-5 ℃ in the reaction process) to obtain a vegetable oil-based polymer composition 3C.

Example 4

460g of refined soybean oil and 40g of maleic anhydride are added into a four-neck flask to be mixed and stirred for 30min, nitrogen is introduced to protect, the temperature is raised to set temperature 206 ℃ (the actual temperature can have floating change of +/-4 ℃ in the reaction process) for reaction for 6.8 hours, the maleic anhydride content is detected to be 1-2% by meteorological chromatography, and the reaction is finished, so that the maleated soybean oil is obtained. Unreacted maleic anhydride is removed by a heating and vacuumizing method, the heating and vacuumizing set temperature is 82 ℃ (the actual temperature can have floating change of +/-3 ℃ in the reaction process), the vacuum degree is 0.07-0.075MPa, the time is 0.5 hours, and a condensing device is used for recycling for standby, so that the active polymerized monomer 4A is obtained.

Example 4-1

15.4g of tetraethylenepentamine and 115.4g of soybean oil are added into a four-necked flask, 100g of maleated soybean oil is added dropwise, the dropping temperature is 79 ℃ (the actual temperature can have floating change of +/-3 ℃ in the process), and the dropping time is 30 minutes. After the dripping is finished, vacuum degassing is carried out, the set temperature of the vacuum degassing is 152 ℃ (the actual temperature can have floating change of +/-3 ℃ in the reaction process), the degassing and amination time is 6.6 hours, after 50% vegetable oil-based polymer is obtained when the amine value is 79.2mgKOH/g, 11.97g dichloroethane is introduced under 78 ℃ (the actual temperature can have floating change of +/-3 ℃ in the process), and the reaction time is 2.8 hours; and distilling to recover chloromethane to obtain quaternized vegetable oil-based polymerized 4B.

Example 4-2

50g of the obtained about 50% quaternized vegetable oil-based polymer, 50g of the composite emulsifier and stirring for 30min under the condition of set temperature 65 ℃ (the actual temperature possibly has floating change of +/-5 ℃ in the reaction process) to obtain the vegetable oil-based polymer composition 4C.

Comparative example 2

This comparative example is substantially identical to example 4, except that the cis-cis and vegetable oils are present in an amount of 23% by weight, based on the total weight of the oils, to give the living polymeric monomer 2a.

Comparative example 2-1 this comparative example was substantially the same as in example 4-1, and finally a vegetable oil-based polymer 2b having an effective content of 50% was obtained.

Comparative examples 2 to 2

This comparative example was substantially the same as in example 4-2 to obtain a vegetable oil-based polymer composition 2c.

Example 5

460g of refined soybean oil and 40g of maleic anhydride are added into a four-neck flask to be mixed and stirred for 30min, nitrogen is introduced to protect, the temperature is raised to a set temperature of 198 ℃ (the actual temperature can have floating change of +/-2 ℃ in the reaction process) and the reaction is carried out for 8.5 hours, the maleic anhydride content is detected to be 1-2% by adopting a meteorological chromatograph, and the reaction is finished, so that the maleated soybean oil is obtained. Unreacted maleic anhydride is removed by a heating and vacuumizing method, the heating and vacuumizing set temperature is 88 ℃ (the actual temperature can have floating change of +/-3 ℃ in the reaction process), the vacuum degree is 0.08-0.095MPa, the time is 0.7 hour, and a condensing device is used for recycling for standby, so that the active polymerized monomer 5A is obtained.

Example 5-1

100g of the maleated soybean oil and 115.4g of soybean oil are added into a four-necked flask, 15.4g of tetraethylenepentamine is added dropwise, the dropwise adding temperature is 78 ℃ (the actual temperature can have floating change of +/-3 ℃ in the process), and the dropwise adding time is 30 minutes. After the dripping is finished, vacuum degassing is carried out, the set temperature of the vacuum degassing is 152 ℃ (the actual temperature can have floating change of +/-3 ℃ in the reaction process), the degassing and amination time is 6.8 hours, after 50% vegetable oil-based polymer is obtained when the amine value is 70mgKOH/g, 11.97g dichloroethane is introduced under 80 ℃ (the actual temperature can have floating change of +/-2 ℃ in the process), and the reaction time is 3 hours; and distilling to recover methyl chloride to obtain the quaternized vegetable oil-based polymer 5B.

Example 5-2

50g of the obtained about 50% quaternized vegetable oil-based polymer, 50g of the composite emulsifier and stirring for 30min under the condition of set temperature 65 ℃ (the actual temperature possibly has floating change of +/-5 ℃ in the reaction process) to obtain a vegetable oil-based polymer composition 5℃.

Example 6

Adding 950g of refined soybean oil and 50g of maleic anhydride into a four-necked flask, mixing, stirring for 30min, introducing nitrogen for protection, heating to a set temperature of 205 ℃ (the actual temperature can have floating change of +/-2 ℃ in the reaction process) for reaction for 6 hours, detecting that the maleic anhydride content is 1-2% by using a meteorological chromatograph, and obtaining the maleated soybean oil after the reaction is finished. Unreacted maleic anhydride is removed by a heating and vacuumizing method, the heating and vacuumizing set temperature is 112 ℃ (the actual temperature can have floating change of +/-3 ℃ in the reaction process), the vacuum degree is 0.055-0.06MPa, the time is 1 hour, and a condensing device is used for recycling for standby, so that the active polymerized monomer 6A is obtained.

Example 6-1

100g of the maleated soybean oil and 104.8g of soybean oil are added into a four-necked flask, 4.8g of tetraethylenepentamine is added dropwise, the dropwise adding temperature is 77 ℃ (the actual temperature can have floating change of +/-3 ℃ in the process), and the dropwise adding time is 30 minutes. After the dripping is finished, vacuum degassing is carried out, the set temperature of the vacuum degassing is 152 ℃ (the actual temperature can have floating change of +/-3 ℃ in the reaction process), the degassing and amination time is 2-7 hours, after the effective content of the vegetable oil-based polymer is 50 percent when the amine value is 20mgKOH/g, 1.92g of chloromethane is introduced under 80 ℃ (the actual temperature can have floating change of +/-2 ℃ in the process), and the reaction time is 2.8 hours; recovering chloromethane by distillation to obtain quaternized vegetable oil-based polymerized 6B

Example 6-2

70g of the obtained about 50% quaternized vegetable oil-based polymer, 30g of the composite emulsifier and stirring for 30min under the condition of set temperature 65 ℃ (the actual temperature possibly has floating change of +/-5 ℃ in the reaction process) to obtain a vegetable oil-based polymer composition 6C.

Example 7

Adding 920g of refined rapeseed oil and 80g of maleic anhydride into a four-necked flask, mixing, stirring for 30min, introducing nitrogen for protection, heating to a set temperature of 198 ℃ (the actual temperature can have floating change of +/-3 ℃ in the reaction process) for 6 hours, detecting that the maleic anhydride content is 1-2% by using a meteorological chromatograph, and obtaining the maleated soybean oil after the reaction is finished. Unreacted maleic anhydride is removed by a heating and vacuumizing method, the heating and vacuumizing set temperature is 88 ℃ (the actual temperature can have floating change of +/-3 ℃ in the reaction process), the vacuum degree is 0.068-0.072MPa, the time is 0.7 hours, and a condensing device is used for recycling for standby, so that the active polymerized monomer 7A is obtained.

Example 7-1

100g of maleated rapeseed oil and 140.8g of soybean oil are added into a four-necked flask, 40.8g of polyoxyethylene ether diamine (M=500) is added dropwise, the dropwise adding temperature is 78 ℃ (the actual temperature can have floating change of +/-3 ℃ in the process), and the dropwise adding time is 30 minutes. After the dripping is finished, vacuum degassing is carried out, the set temperature of the vacuum degassing is 152 ℃ (the actual temperature can have floating change of +/-3 ℃ in the reaction process), the degassing and amination time is 6.6 hours, when the amine value is 16.2mgKOH/g, after the vegetable oil-based polymer with the effective content of 50% is finally obtained, 4.2g of chloromethane is introduced under 82 ℃ (the actual temperature can have floating change of +/-3 ℃ in the process), and the reaction time is 3 hours; and distilling to recover chloromethane to obtain quaternized vegetable oil-based polymer 7B.

Example 7-2

35g of the obtained about 50% quaternized vegetable oil-based polymer, 65g of the composite emulsifier, and stirring for 30min under the condition of a set temperature of 65 ℃ (the actual temperature possibly has floating change of +/-5 ℃ in the reaction process) to obtain a vegetable oil-based polymer composition 7C.

Example 8

880g of refined rapeseed oil and 120g of maleic anhydride are added into a four-neck flask to be mixed and stirred for 30min, nitrogen is introduced to protect, the temperature is raised to 207 ℃ (the actual temperature can have floating change of +/-3 ℃ in the reaction process) for reaction for 5.5 hours, the maleic anhydride content is detected to be 1-2% by meteorological chromatography, and the reaction is finished, so that the maleated soybean oil is obtained. Unreacted maleic anhydride is removed by a heating and vacuumizing method, the set temperature of heating and vacuumizing is 107 ℃ (the actual temperature can have floating change of +/-3 ℃ in the reaction process), the vacuum degree is 0.066-0.071MPa, the time is 0.8 hours, and a condensing device is used for recycling for standby, so that the active polymerization monomer 8A is obtained.

Example 8-1

100g of the maleated rapeseed oil and 191.8g of palm oil are added into a four-necked flask, 73.46g of polyether diamine ED-600 (M=600) is added dropwise, the dropping temperature is 77 ℃ (the actual temperature can have floating change of +/-3 ℃ in the process), and the dropping time is 30 minutes. After the dripping is finished, vacuum degassing is carried out, the set temperature of the vacuum degassing is 152 ℃ (the actual temperature can have floating change of +/-3 ℃ in the reaction process), the degassing and amination time is 6.8 hours, 7.72g of chloromethane is introduced under 87 ℃ (the actual temperature can have floating change of +/-3 ℃ in the process) after the effective content of 50% of vegetable oil-based polymer is obtained when the amine value is 1.2mgKOH/g, and the reaction time is 2.75 hours; recovering chloromethane by distillation to obtain quaternized vegetable oil-based polymerized 8B

Example 8-2

70g of the obtained about 50% quaternized vegetable oil-based polymer, 30g of the composite emulsifier and stirring for 30min under the condition of set temperature 65 ℃ (the actual temperature possibly has floating change of +/-5 ℃ in the reaction process) to obtain the vegetable oil-based polymer composition 8C.

Comparative example 3

This comparative example is substantially the same as example 8, except that the maleic anhydride is 15% of the total weight of the vegetable oil.

Comparative example 3-1

This comparative example is substantially identical to example 8, except that, when polyether diamine ED-600 (m=600) is added dropwise, the addition temperature is 40 ℃. Finally, the vegetable oil-based polymer 3b with the effective content of 50% is obtained.

Comparative example 3-2

This comparative example was identical to example 8-2, resulting in vegetable oil-based polymer composition 3c.

Example 9

Adding 800g of refined soybean oil and 200g of maleic anhydride into a four-neck flask, mixing, stirring for 30min, introducing nitrogen for protection, heating to a set temperature of 212 ℃ (the actual temperature can have floating change of +/-3 ℃ in the reaction process) for reacting for 5.8 hours, detecting that the maleic anhydride content is 1-2% by using a meteorological chromatograph, and obtaining the maleated soybean oil after the reaction is finished. Unreacted maleic anhydride is removed by a heating and vacuumizing method, the heating and vacuumizing set temperature is 112 ℃ (the actual temperature can have floating change of +/-3 ℃ in the reaction process), the vacuum degree is 0.083-0.089MPa, the time is 1.5 hours, and a condensing device is used for recycling for standby, so that the active polymerized monomer 9A is obtained.

Example 9-1

100g of the maleated soybean oil and 183g of soybean oil are added into a four-necked flask, 183g of polyether diamine ED-900 (M=900) is added dropwise, the dropwise adding temperature is 78 ℃ (the actual temperature can have floating change of +/-3 ℃ in the process), and the dropwise adding time is 30 minutes. After the dripping is finished, vacuum degassing is carried out, the set temperature of the vacuum degassing is 152 ℃ (the actual temperature can have floating change of +/-3 ℃ in the reaction process), the degassing and amination time is 6.9 hours, when the amine value is 3.1mgKOH/g, the vegetable oil-based polymer with the effective content of 50% is obtained, 15.4g of chloromethane is introduced under 72 ℃ (the actual temperature can have floating change of +/-3 ℃ in the process), and the reaction time is 2.6 hours; recovering chloromethane by distillation to obtain quaternized vegetable oil-based polymer 9B

Example 9-2

70g of the obtained about 50% quaternized vegetable oil-based polymer, 30g of composite emulsifier and stirring for 30min at the temperature of 60-70 ℃ to obtain a vegetable oil-based polymer composition 9C.

Example 10

Adding 850g of refined soybean oil and 150g of maleic anhydride into a four-neck flask, mixing, stirring for 30min, introducing nitrogen for protection, heating to a set temperature of 208 ℃ (the actual temperature can have floating change of +/-3 ℃ in the reaction process) for reacting for 5 hours, detecting that the maleic anhydride content is 1-2% by using a meteorological chromatograph, and obtaining the maleated soybean oil after the reaction is finished. Unreacted maleic anhydride is removed by a heating and vacuumizing method, the heating and vacuumizing set temperature is 82 ℃ (the actual temperature can have floating change of +/-3 ℃ in the reaction process), the vacuum degree is 0.08-0.085MPa, the time is 0.8 hour, and a condensing device is used for recycling for standby, so that the active polymerized monomer 10A is obtained.

Example 10-1

100g of the maleated soybean oil and 406g of soybean oil are added into a four-necked flask, 306g of methyl-terminated polyether monoamine JAM-2070 (M=2000 and EO/PO=70/30) is added dropwise, the dropwise adding temperature is 77 ℃ (the actual temperature can have floating change of +/-3 ℃ in the process), and the dropwise adding time is 30 minutes. After the dripping is finished, vacuum degassing is carried out, the set temperature of the vacuum degassing is 152 ℃ (the actual temperature can have floating change of +/-3 ℃ in the reaction process), the degassing and amination time is 6 hours, when the amine value is 1.0mgKOH/g, the vegetable oil-based polymer with the effective content of 50% is obtained, 11.58g of chloromethane is introduced under 80 ℃ (the actual temperature can have floating change of +/-2 ℃ in the process), and the reaction time is 2.7 hours; recovering chloromethane by distillation to obtain quaternized vegetable oil-based polymer 10B

Example 10-2

70g of the obtained about 50% quaternized vegetable oil-based polymer, 30g of the composite emulsifier and stirring for 30min under the condition of set temperature 65 ℃ (the actual temperature possibly has floating change of +/-5 ℃ in the reaction process) to obtain the vegetable oil-based polymer composition 10C.

Comparative example 4

This comparative example was identical to example 10, and living polymerization monomer 4a was obtained.

Comparative example 4-1

100g of the maleated soybean oil and 406g of soybean oil are added into a four-necked flask, 306g of methyl-terminated polyether monoamine JAM-2070 (M=2000 and EO/PO=70/30) is added dropwise, the dropwise adding temperature is 40 ℃, and the dropwise adding time is 30min. After the dripping is finished, stirring for 2 hours at 40 ℃ to finally obtain the vegetable oil-based polymer 4b with the effective content of 50%.

Comparative example 4-2

This comparative example was identical to example 10-2, resulting in vegetable oil-based polymer composition 4c.

Comparative example 5

This comparative example was identical to example 10, and living polymerization monomer 5a was obtained.

Comparative example 5-1

This comparative example is substantially the same as example 10-1 except that the methyl capped polyether monoamine JAM-2070 (m=2000, eo/po=70/30) is replaced with methoxy polyether (m=2000, eo/po=70/30), resulting in a final effective content of 50% vegetable oil based polymer 5b.

Comparative example 5-2

This comparative example was identical to example 10-2, resulting in vegetable oil-based polymer composition 5c.

Verification experiment 1

The performance of the auxiliary compositions prepared from the compositions 1C to 10C in the above-described embodiments (1-3) to (10-3) of the present invention was characterized by experiments: the equilibrium surface tension, contact angle, viscosity and water-entry-dispersibility tank mix stability, retention amount, rainwash resistance, water-entry-dispersibility, formulation addition, and field control effects of compositions 1C to 10C in examples (1-3) to (10-3) of the present invention were measured, respectively.

1. Contact angle

The assistant compositions prepared by the compositions 1C to 10C in the examples (1-3) to (10-3) of the present invention were diluted into 0.2 mass% aqueous assistant solutions, and then contact angles were measured, respectively, and the results are shown in Table 1 below.

2. Viscosity of the mixture

The viscosity of the auxiliary compositions prepared from compositions 1C to 10C in examples (1-3) to (10-3) of the present invention was measured by a spindle, and the viscosity of the pure sample was measured on a TA ARG2 rheometer of TA Instruments, and the results are shown in Table 1 below.

3. Balancing surface tension

The compositions 1℃ to 10C and the compositions 1 to 5 of the comparative auxiliaries 1 to 5 of the present invention obtained in examples (1-3) to (10-3) were diluted to 1% by mass of an aqueous solution of the auxiliaries, and then measured at 25.0deg.C.+ -. 0.1deg.C using a Kruss model K10ST tensiometer equipped with a Wilhelmy plate, and the results are shown in Table 1 below.

TABLE 1

As is apparent from the data in Table 1, the compositions 1C to 10C in the examples (1-3) to (10-3) of the present invention:

1. the preparation has a lower contact angle, is beneficial to the spreading of the preparation on the target, can avoid the loss caused by the smaller contact angle, and is beneficial to the retention of the preparation on the target;

2. the emulsion is easy to form uniform and stable emulsion in cold water, and the compatibility and stability among preparations are improved by combining vegetable oil base (hydrophobicity), hydrophilic alkylene amine and compatible nonionic chain segments;

3. the auxiliary compositions prepared from compositions 1C-10C exhibit high viscosity and good rheological performance.

However, in comparative example 1, since the amount of maleic anhydride is 3% and less than the preferable amount range of 5 to 20%, the introduced hydrophilic group and amine group are insufficient, and thus, in comparative example 1, it is difficult to disperse oily substances in water, and oil slivers are generated;

comparative example 2 has a high viscosity and is difficult to disperse in water because the amount of maleic anhydride is 23% and exceeds the range of 5-20% of maleic anhydride, and compared with example 4, more tetraethylenepentamine is required to be added to form a single vegetable oil-based five-membered heterocyclic polymer with maleic anhydride modified vegetable oil, and more tetraethylenepentamine can form cross-linking with maleic anhydride modified vegetable oil during the reaction, resulting in an increase in viscosity and difficulty in dispersing in water.

Comparative examples 3 and 4, in which polyether diamine ED-600 and JAM-2070 (m=2000 and eo/po=70/30) were respectively dropped at a reaction temperature of 40 ℃, were dehydrated by vacuum amination without increasing the temperature, and were only capable of forming-CO-NH-bonds, thus five-membered nitrogen-containing heterocycles were not formed, and the corresponding pH was higher than in example 8.

Comparative example 5 the substitution of methyl capped polyether monoamine JAM-2070 (m=2000, eo/po=70/30) with methoxy polyether (m=2000, eo/po=70/30) only results in monoester compounds, which are less salt tolerant than nitrogen-containing adjuvants, and are detrimental to the increase of deposition and hold-up. Thus, none of the compositions of comparative examples 1c, 2c, 3c, 4c, 5c is advantageous for application.

Verification experiment 2

The compositions 1C to 10C in examples (1-3) to (10-3), the compositions 1C to 5C in comparative examples 1 to 5, and the conventional anionic (calcium dodecylbenzenesulfonate) -containing vegetable oil emulsifier A were subjected to comparative experiments.

TABLE 2 stability data for vegetable oils of different types (24 h, 348 ppm,30 ℃ C.)

TABLE 3 stability data at different amounts (24 h, 348 ppm,30 ℃ C.)

Note that:

(1) compatibility: the composition 1C-10C, C-5C and the vegetable oil emulsifier A are mixed with vegetable oil according to the mass ratio of 20:80 respectively, the mixture is cooled to room temperature for observing transparency, and the grade is clear and transparent, slightly muddy and turbid;

(2) Emulsion stability: the emulsified vegetable oil emulsifier composition or other vegetable oil auxiliary agent and vegetable oil are uniformly mixed according to the mass ratio of 15-25:75-85 at 50 ℃, cooled to room temperature, diluted by 20 times with 342ppm of standard hard water, placed at 30 ℃ for 24 hours, observed to separate layers and get out of oil, and 2ml of oil is unqualified.

From the data in tables 2 and 3, it is possible to:

1. the compatibility of the obtained composition 1C-10C and the vegetable oil emulsifier A with several vegetable oils is good, the prepared oil phase is clear, and the emulsion stability is qualified; the compatibility of the compositions 1 c-5 c with vegetable oil is slightly poor, the prepared oil phase has a blurred appearance, and the emulsion stability is poor after long-term layering.

2. When the dosage of the composition 1C-10C is 15%, more than 2ml of floating oil is commonly present in the oil phase diluted 20 times; when the dosage is 20%, the oil phase can be basically ensured to be only 0.5-1ml of floating oil, and the oil phase can be considered as qualified; whereas at 25% the examples showed little oil slick, the oil phases formulated with compositions 1 c-5 c showed less oil slick. As can be seen, the compositions 1C to 10C in examples (1-3) to (10-3) of the present invention are significantly advantageous in comparison with the compositions 1C to 5C in comparative examples 1 to 5.

Verification experiment 3

Comparative experiments were carried out by experiments on compositions 3C to 5C of examples (3-3) to (5-3) and on the conventional organic soil SK-04 containing the anionic (12-alkylbenzene sulfonate calcium) vegetable oil emulsifier A as a thickener.

The data in Table 4 are compared as follows (24 h, 348 ppm,30 ℃ C.)

Note that:

(1) compatibility: the composition 1C-10C, C-5C and the vegetable oil emulsifier A obtained by the invention are respectively mixed with vegetable oil according to the mass ratio of 20:80, organic soil SK-04 with different contents is added, the mixture is uniformly mixed at 50 ℃, and the mixture is cooled to room temperature to detect viscosity and appearance;

(2) emulsion stability: the composition 1C-10C, C-5C and the vegetable oil emulsifier A are respectively mixed with different contents of SK-04 and vegetable oil according to the mass ratio of 15-25:75-85, cooled to room temperature under the condition of 50 ℃, diluted by 342ppm of standard hard water for 20 times, and placed at 30 ℃ for 24 hours to observe layering and oil separation. 2ml of the oil is disqualified.

From the data of table 4 it is surprisingly possible to:

1. the composition of the invention has good compatibility with soybean oil, clear formulated oil phase, obvious enhancement effect and qualified emulsion stability, and the thickening effect of the traditional vegetable oil emulsifier A added with the same content of organic soil SK-04 is far lower than that of the composition of the invention of the embodiment 3-5.

2. Meanwhile, because the traditional vegetable oil emulsifier A contains an anionic auxiliary agent, the addition of the cationic thickener SK-04 accelerates particle sedimentation, is unfavorable for preparation stability, and can cause phenomena of bottom formation, oil separation and the like in the preparation, and the compositions of the examples 3-5 and the quaternized organic soil thickener have the same charge to slow down particle sedimentation speed and improve the stability of the preparation.

Verification experiment 4 (liquid medicine tank stability experiment)

Medicament: 100g/L OF bispyribac-sodium dispersible oil suspending agent (OF), 48% OF acetochlor atrazine Suspension Emulsion (SE), 10% OF quizalofop-p-ethyl aqueous Emulsion (EW), 250g/L OF pyraclostrobin suspending agent (SC), 80% OF mancozeb Wettable Powder (WP) and 25g/L OF deltamethrin Emulsifiable Concentrate (EC);

the testing method comprises the following steps: the compositions 1C to 10C and the compositions 1C to 3C of the comparative example assistants 1 to 3C in the examples (1-3) to (10-3) of the present invention were diluted according to the dilution factors shown in Table 2, respectively, and prepared into tank-mixed liquid medicines with the medicines; the barreled mixed liquor is placed in a 100ml pointed-bottomed measuring cylinder with a plug, and is kept stand for 1h to observe whether the phenomenon of floating paste precipitation exists, and the phenomenon of floating paste precipitation is marked as qualified, otherwise, the phenomenon of floating paste precipitation is not qualified, and the result is shown in the following table 5.

TABLE 5 liquid medicine tank stability test data (1 time hard water 342 ppm)

From the data in table 5 it is evident that:

the auxiliary agent compositions prepared in the embodiments 2-10 OF the invention have good compatibility with 100g/L bispyribac-sodium dispersible oil suspending agent (OF), 48% acetochlor-atrazine Suspension Emulsion (SE), 10% quizalofop-p-ethyl aqueous Emulsion (EW), 250g/L pyraclostrobin suspending agent (SC) and 25g/L deltamethrin emulsifiable oil (EC), and the compatibility and the universality OF comparative examples 1c, 2c, 3c, 4c and 5c are not good.

Verification experiment 5 (Effect of Synthesis aid composition on the Hold-Up amount of liquid medicine)

Medicament: 100g/L bispyribac-sodium OF;

the testing method comprises the following steps: the compositions 1C to 10C in examples (1-3) to (10-3) and the compositions of comparative examples 1 to 3 were diluted 400X, 300X and 200X, respectively, and the preparations were diluted 1500X. The secondary dilution method can be adopted, 10 times of auxiliary agent diluent is firstly prepared, then 150 times of medicament diluent is prepared, after full stirring, three parts of mixed liquid are prepared, and 3 times of clear water, 2 times of clear water and 1 time of clear water are respectively added, and the mixed liquid is uniformly stirred. Then, a culture dish with phi 30mm is placed on a ten-thousandth balance, and after zeroing, a puncher with phi 16mm is adopted to intercept about 2cm ² The method comprises the steps of weighing and recording the mass of round plant leaves, clamping the leaves with pointed tweezers, dipping the prepared liquid medicine to be measured, repeatedly soaking for 10s, suspending and standing for 10s, and placing the plant leaves in a culture dish to weigh the mass of the liquid medicine held by the leaves. The measurement was repeated 10 times, and the difference in the remaining amounts of the medicinal liquids was obtained by averaging the results, and the results are shown in Table 6 below.

TABLE 6 data on the effect of Synthesis aid composition on the retention of medicinal liquid

From the experimental results in table 6 above, it is evident that: the compositions 1C to 10C in the examples (1-3) to (10-3) prepared by the invention are beneficial to the increase of the preparation retention compared with the compositions of the traditional vegetable oil emulsifier and the comparative example auxiliary agents 1 to 5; the retention of the preparation obtained by adding the auxiliary agent composition prepared by the invention is larger than that of the liquid medicine diluted by clear water.

Verification experiment 6 (rain wash resistance)

Medicament: 250g/L pyraclostrobin SC

The testing method comprises the following steps: the compositions 1C to 10C in examples (1-3) to (10-3) and the comparative examples 1 to 3 were diluted 500X and the medicines were diluted 3000X. The secondary dilution method can be adopted, 50 times of auxiliary agent diluent is firstly prepared, then 300 times of medicament diluent is prepared, the two are prepared into mixed solution after being fully stirred, and then 9 times of clear water is added, and the mixed solution is uniformly stirred. Then, uniformly spraying potted luffa seedlings by adopting a potter spray tower, 1h after the spraying, adopting a 1mm aperture shower head, respectively simulating rainfall for 30min, 60min and 120min for the potted luffa seedlings after the spraying, adopting a 5-point sampling method to cut equivalent plant stems and leaves after the rainfall simulation, and analyzing the pesticide residue of the weed plants by utilizing a pesticide residue detector. The effect of the auxiliary on the rain wash resistance of the agent can be obtained, and the results are shown in the following table 7.

Table 7 rain wash resistance test data

From the data in Table 7 above, it is evident that: the compositions 1C-10C and the compositions 1-5 of the comparative example assistants 1-3 in the embodiments (1-3) - (10-3) of the invention can obviously improve the pesticide residue of the weed plants after simulated rainfall by barrel mixing with the chemicals, which shows that the synthesized assistants of the invention have the effect of improving the rainwash resistance of the chemicals and can effectively reduce the influence of rainfall on the pesticide effect after application.

Verification experiment 7 (field anti-efficiency experiment)

(1) Control object 1: barnyard grass; test crop: rice; medicament: 100g/L bispyribac-sodium OF;

the testing method comprises the following steps: in the 3-4 leaf stage of rice, the 2-3 leaf stage of barnyard grass is investigated in the field, and the test is carried out on the land with about 3000 plants per square meter. The synthesized auxiliary agent was diluted 500X and the drug was diluted 1000X. The secondary dilution method can be adopted, 50 times of auxiliary agent diluent is firstly prepared, then 100 times of medicament diluent is prepared, the two are prepared into mixed solution after being fully stirred, and then 9 times of clear water is added, and the mixed solution is uniformly stirred. An electric knapsack sprayer is adopted, the model is 20FT, the volume is 15L, a 110-degree fan-shaped spray head is used, the spraying pressure is 0.25 MPa-0.3 MPa, random area blocks are uniformly sprayed, an additive-free group and a clear water control group are arranged, and the number of weed plants and the fresh weight are respectively investigated after the medicine is applied for 14d and 28 d. The control data of whether the auxiliary agent has synergistic effect on the pesticide can be obtained, and the results are shown in the following table 8.

Table 8 field control experiment data one

(2) Control object 2: downy mildew; test crop: cucumber; medicament: 250g/L pyraclostrobin SC;

the testing method comprises the following steps: in the middle and later period of cucumber growth, a control test can be carried out. The synthesized auxiliary was diluted 500X and the reagent was diluted 3000X. The secondary dilution method can be adopted, 50 times of auxiliary agent diluent is firstly prepared, then 300 times of medicament diluent is prepared, the two are prepared into mixed solution after being fully stirred, and then 9 times of clear water is added, and the mixed solution is uniformly stirred. An electric knapsack sprayer is adopted, the model is 20FT, the volume is 15L, a conical nozzle is adopted, the spraying pressure is 0.3 MPa-0.35 MPa, random area blocks are uniformly sprayed, an additive group and a clear water control group are not added, secondary expansion and renaturation are carried out on the pathogen of artificially stored Qiongqiao mould (Pseudoperonospora cubensis (Berk. Et Curt.) Roscov.) 1d after the medicine is adopted, the inoculum with the spore concentration of 8.0X106/L is prepared, and full-field spraying inoculation is carried out. And observing disease indexes of the blank control area and the medicament treatment area after the spores are inoculated for 7d and 14d, so as to obtain control data of whether the auxiliary agent has a synergistic effect on the pesticide or not, and the results are shown in Table 9.

Table 9 field control experiment data two

(3) Control object 3: aphids; test crop: corn; medicament: 25g/L deltamethrin EC;

the testing method comprises the following steps: the test was performed on plots with approximately 200 heads/leaf of the insect population under corn seedling stage investigation. The synthesized auxiliary was diluted 500X and the reagent was diluted 1500X. The secondary dilution method can be adopted, 50 times of auxiliary agent diluent is firstly prepared, then 150 times of medicament diluent is prepared, the two are prepared into mixed solution after being fully stirred, and then 9 times of clear water is added, and the mixed solution is uniformly stirred. An electric knapsack sprayer is adopted, the model is 20FT, the volume is 15L, a conical nozzle and the spraying pressure are 0.25 MPa-0.3 MPa, random area blocks are uniformly sprayed, an additive group and a clear water control group are arranged, and the number of insect mouths is respectively investigated after 1d, 7d and 14d of the medicine. The control data of whether the auxiliary agent has synergistic effect on the pesticide can be obtained, and the results are shown in table 10.

Table 10 field control experiment data three

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From the data in tables 8 to 10 above, it is apparent that: the prepared auxiliary agent and the medicament barrel can obviously improve the control effect of herbicide, bactericide and insecticide, and the synergistic effect is higher than that of the auxiliary agent sold in the market.

More specifically, although exemplary embodiments of the present invention have been described herein, the present invention is not limited to these embodiments, but includes any and all embodiments that have been modified, omitted, e.g., combined, adapted, and/or substituted between the various embodiments, as would be recognized by those skilled in the art in light of the foregoing detailed description. The limitations in the claims are to be interpreted broadly based on the language employed in the claims and not limited to examples described in the foregoing detailed description or during the prosecution of the application, which examples are to be construed as non-exclusive. Any steps recited in any method or process claims may be executed in any order and are not limited to the order presented in the claims. The scope of the invention should, therefore, be determined only by the appended claims and their legal equivalents, rather than by the descriptions and examples given above.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, definitions, will control. Where a mass, concentration, temperature, time, or other value or parameter is expressed as a range, preferred range, or as a range bounded by a list of upper and lower preferred values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, a range of 1-50 should be understood to include any number, combination of numbers, or subranges of numbers selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50, as well as all fractional values between the integers described above, such as 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, and 1.9. Regarding sub-ranges, specifically considered are "nested sub-ranges" that extend from any end point within the range. For example, the nested subranges of exemplary ranges 1-50 can include 1-10, 1-20, 1-30, and 1-40 in one direction, or 50-40, 50-30, 50-20, and 50-10 in another direction.

Claims

1. A method for preparing a vegetable oil-based polymer, comprising the steps of:

(1) Preparing maleated vegetable oil: carrying out olefine reaction on maleic anhydride and vegetable oil at high temperature to obtain maleated vegetable oil; the maleic anhydride accounts for 5-20% of the total weight of the maleic anhydride and the vegetable oil;

wherein,,

the active polymerization monomer is the maleic anhydride vegetable oil prepared in the step (1);

the organic amine is one or more of alkylene amine and polyether amine;

the plant oil accounts for 30-70% of the total weight of the plant oil, the active polymerization monomer and the organic amine;

(3) Carrying out quaternization reaction with a quaternizing agent to obtain a quaternized vegetable oil-based polymer taking vegetable oil as a solvent;

the molar ratio of the addition amount of the quaternizing agent to the organic amine is (1-2.2): 1.

2. The method for producing a vegetable oil-based polymer according to claim 1, characterized in that: in the step (1), maleic anhydride and vegetable oil react at 190-230 ℃ to obtain maleated vegetable oil;

when the content of the maleic anhydride is reduced to 1-2%, ending the reaction;

then, heating and vacuumizing treatment is carried out; the conditions of heating and vacuumizing are as follows: the temperature is 50-150 ℃, the vacuum degree is 0.02-0.098 MPa, and the time is 0.5-1.5 hours.

3. The method for producing a vegetable oil-based polymer according to claim 1, characterized in that: in the step (2), the specific contact mode of the active polymerization monomer and the organic amine is any one of the following:

the temperature in the dripping process is 60-95 ℃, and the dripping time is 0.5-3 hours;

after the dripping is finished, vacuum degassing and amination are carried out, the temperature is 120-160 ℃, and the time is 2-7 hours;

And (3) after the dripping is finished, carrying out vacuum degassing amination, wherein the temperature is 120-160 ℃ and the time is 2-7 hours.

4. A method of preparing a vegetable oil-based polymer according to claim 3, wherein: in the step (3), the quaternary ammonium agent is distilled and recovered during the reaction with the quaternary ammonium agent, and the quaternary ammonium vegetable oil-based polymer taking vegetable oil as a solvent is obtained;

5. The method for producing a vegetable oil-based polymer according to claim 1, characterized in that: in the step (2), the active polymerization monomer contains the product of the following structural general formulas (8) and/or (9) after amination reaction:

（8）

（9）

wherein R is ₁₄ An alkylene amine residue or a polyetheramine residue.

6. The method for producing a vegetable oil-based polymer according to any one of claims 1 to 5, characterized in that: the prepared product comprises quaternized vegetable oil-based polymer represented by the following general formula (10) and/or (11):

（10）

R ₁₅ is a quaternizing agent residue, X ^- Represents an anion in combination with a cation, said anion being chloride or bromide;

（11）

R ₁₅ is a quaternizing agent residue;

X ^- represents an anion in combination with a cation, which is chloride or bromide.

7. A composition comprising the quaternized vegetable oil-based polymer of any one of the preceding claims, characterized in that: the composition comprises the following components in parts by weight: 40-70 parts of quaternized vegetable oil-based polymer taking vegetable oil as a solvent and 30-60 parts of composite additive;

the quaternized vegetable oil-based polymer with vegetable oil as solvent, which is prepared by the method of any one of claims 1 to 6.

8. The quaternized vegetable oil-based polymer composition of claim 7 wherein: the composite additive is formed by compounding a nonionic surfactant and fatty acid ester substances according to the mass ratio of (10-25) (45-80), wherein the nonionic surfactant has the following general formula (12):

（12）

wherein R is ₁₆ Is C1-C20 straight chain or branched chain alkyl, or sorbitol residue, or sucrose residue, or glycerin residue, or phenyl with other substituent groups on benzene ring, or unsaturated hydrocarbon chain, or H; r is R ₁₇ ，R ₁₈ ，R ₁₉ Represent H, CH independently of each other ₃ Or CH ₂ CH ₃ M1, m2, m3 independently represent an integer of 0 to 30 and the sum of m1, m2 and m3 is greater than 0.

9. The quaternized vegetable oil-based polymer composition of claim 8, wherein: the fatty acid ester substance comprises one or more of trimethylolpropane fatty acid ester, propylene glycol fatty acid ester, pentaerythritol fatty acid ester, polyethylene glycol fatty acid monoester, polyethylene glycol fatty acid diester, polyglycerol fatty acid ester, sorbitan fatty acid ester and sucrose fatty acid ester.

10. A process for preparing a composition comprising a quaternized vegetable oil-based polymer as defined in any one of claims 7 to 9, characterized in that:

(1) Preparing a quaternized vegetable oil-based polymer with vegetable oil as a solvent, which is prepared by the method of any one of claims 1 to 6;

(2) And mixing the quaternized vegetable oil-based polymer taking vegetable oil as a solvent with a composite additive at the temperature of 60-70 ℃ and stirring to obtain the composition.