CN111269349A - Polycarboxylic acid polymer emulsifier and preparation method thereof - Google Patents
Polycarboxylic acid polymer emulsifier and preparation method thereof Download PDFInfo
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- CN111269349A CN111269349A CN202010076427.5A CN202010076427A CN111269349A CN 111269349 A CN111269349 A CN 111269349A CN 202010076427 A CN202010076427 A CN 202010076427A CN 111269349 A CN111269349 A CN 111269349A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
- A01N43/68—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms with two or three nitrogen atoms directly attached to ring carbon atoms
- A01N43/70—Diamino—1,3,5—triazines with only one oxygen, sulfur or halogen atom or only one cyano, thiocyano (—SCN), cyanato (—OCN) or azido (—N3) group directly attached to a ring carbon atom
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
Abstract
The invention relates to a polycarboxylic acid polymer emulsifier and a preparation method thereof, belonging to the technical field of polymer material preparation. The polycarboxylic acid polymer emulsifier is prepared from the following components in parts by weight: 10-70 parts of acrylic monomers, 5-50 parts of acrylate monomers, 20-100 parts of alcohols, 10-40 parts of initiators, 1-40 parts of alkali and 50-200 parts of water; the molar mass ratio of the acrylic monomer to the acrylate monomer is 1-6: 1-5. The HLB value of the emulsifier is adjusted by controlling the adding proportion of the acrylic monomer and the acrylic monomer, so that the emulsifier is simple and convenient, and has excellent performance; and the prepared emulsion has good stability.
Description
Technical Field
The invention relates to the technical field of preparation of high polymer materials, and particularly provides a polycarboxylic acid high polymer emulsifier and a preparation method thereof.
Background
An emulsifier is a substance used to prepare an emulsion and impart it with a minimum degree of stability, and is an essential component. Common emulsifiers are small molecular emulsifiers, mainly including nonionic emulsifiers such as alkylphenol ethoxylates and fatty alcohol-polyoxyethylene ethers, and anionic emulsifiers such as alkylbenzene sulfonates. The polymer emulsifier generally refers to a polymer compound having a surface active function with a relative molecular mass of more than several thousands. The polymer surfactant compounds can be classified into natural polymer surfactants, natural modified (or semi-synthetic) polymer surfactants, and chemical synthetic polymer surfactants according to their sources. The natural polymer surfactant exists in animal and plant bodies, plays a very important role in the life process, and is an amphiphilic polymer compound prepared by separating and refining animals and plants; the modified high molecular surfactant comprises modified starch, cellulose, protein, chitosan and the like, and is obtained by processing natural substances serving as main raw materials; the synthetic polymer surfactant refers to a hydrophilic monomer homopolymerization or copolymerization with a hydrophobic monomer, or is prepared by chemically modifying some common polymers, and the types of the synthetic polymer surfactants are various, and generally include polymerization types (such as polyacrylates) and condensation types (such as polyamine). The polymer emulsifier is a novel emulsifier developed in 20 years, and is mainly developed by foreign and international companies, such as enterprises in Noyu, Ciba and the like. The production cycle is long, the cost is high, and the method is mainly applied to industries with high product price, such as the cosmetic industry. Due to cost constraints, it is rarely used in the pesticide industry.
When the micromolecule surfactant is used as an emulsifier, the micromolecule surfactant is adsorbed on an oil/water interface as a third phase, and stable emulsion is obtained by reducing interfacial tension and preventing dispersed phase droplets from aggregating. However, surfactant emulsifying systems are metastable and are thermodynamically unstable. The adsorption of the surfactant on the oil/water interface is a dynamic equilibrium, and under certain conditions, the adsorption and desorption can be fast, so that the phenomenon that surfactant molecules migrate to a body phase can occur, the long-term stability of the emulsion is poor, and the migration of small molecules can cause many negative problems. The macromolecular emulsifier has a large molecular weight and long oleophylic chains, can well wrap the oil phase, and can enhance the stability.
In order to overcome the defect that the conventional emulsifier is unstable in emulsion polymerization, researchers at home and abroad develop a plurality of novel emulsifier varieties, and one effective way is to use a polymerizable emulsifier in emulsion polymerization. Compared with the conventional emulsifier, the high molecular emulsifier comprises a reactive functional group besides a hydrophilic and lipophilic group, and the reactive functional group can participate in the reaction; the emulsifier plays a role of a conventional emulsifier, and can be bonded to the surface of a polymer particle in a covalent bond mode to form a part of a polymer, so that the emulsifier is prevented from being desorbed from the polymer particle or migrating in the latex film, and hydrophilic groups on the surface of the latex film are greatly reduced, thereby improving the stability of the emulsion and improving the performance of the latex film.
Disclosure of Invention
The invention provides a polypropylenecarboxylic acid polymer emulsifier and a preparation method thereof, aiming at solving the problems that a small molecule emulsifier in the prior art is insufficient in use and the existing polymer emulsifier is less in variety and is applied to the field of pesticides.
In order to solve the technical problems, the invention provides the following technical scheme:
on the one hand, the invention provides a polycarboxylic acid polymer emulsifier which is prepared from the following components in parts by weight: 10-70 parts of acrylic monomers, 5-50 parts of acrylate monomers, 20-100 parts of alcohols, 10-40 parts of initiators, 1-40 parts of alkali and 50-200 parts of water;
the molar mass ratio of the acrylic monomer to the acrylate monomer is 1-6: 1-5.
Preferably, the polycarboxylic acid type polymer emulsifier is prepared from the following components in parts by weight: 10-20 parts of acrylic monomer, 15-20 parts of acrylate monomer, 50 parts of alcohol, 20-30 parts of initiator, 1-40 parts of alkali and 100 parts of water.
Preferably, the polycarboxylic acid type polymer emulsifier is prepared from the following components in parts by weight: 20 parts of acrylic monomers, 15 parts of acrylate monomers, 50 parts of alcohols, 30 parts of initiators, 1-40 parts of alkali and 100 parts of water.
Further, the weight average relative molecular weight of the polymeric emulsifier is 10000-50000.
Preferably, the acrylic monomer is acrylic acid and/or methacrylic acid;
the acrylate monomer is one or two of acrylate with carbon number of 5-18 alcohol and methacrylate with carbon number of 5-18 alcohol.
Preferably, the alcohol is one or two of propanol and isopropanol.
Preferably, the alkali is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ammonia water and ethanolamine;
preferably, the initiator is a persulfate.
Preferably, the dosage of the polycarboxylic acid polymer emulsifier is 1-20 wt%.
On the other hand, the invention also provides a preparation method of the polycarboxylic acid polymer emulsifier, which comprises the following steps:
step 1: adding deionized water and alcohols into a reaction kettle, uniformly stirring, and heating to 65-90 ℃;
step 2: simultaneously dripping acrylic monomers, acrylic ester monomers and an initiator solution into the solution, finishing dripping within 0.5-2.5 hours, and reacting for 1-6 hours under the condition of heat preservation;
and step 3: and (3) stirring the solution obtained in the step (2), cooling to room temperature, adjusting the pH to 6.0-8.0 by using alkali, and discharging to obtain the catalyst.
On the other hand, the invention also provides an application of the polycarboxylic acid high-molecular emulsifier in preparation of an atrazine suspending agent.
Compared with the prior art, the invention has the following beneficial effects:
1. the acrylic monomer used in the invention is hydrophilic, the acrylic monomer is lipophilic, the HLB value of the emulsifier can be adjusted by controlling the adding proportion of the acrylic monomer and the acrylic monomer, the method is simple and convenient, and the emulsifier is endowed with excellent performance;
2. the invention does not use extra micromolecular emulsifier, not only has emulsification effect, but also the prepared emulsion has good stability.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, the following detailed description is given with reference to specific embodiments.
Unless otherwise specified, the reagents and the like used in the present invention are commercially available products.
The invention provides a polycarboxylic acid polymer emulsifier and a preparation method thereof, and specific examples are as follows.
Example 1
The polycarboxylic acid polymer emulsifier and the preparation method thereof are as follows: adding 100 parts of water and 50 parts of isopropanol into a reaction kettle, and heating while stirring; when the temperature of the solution in the reaction kettle is raised to 70 ℃, 10 parts of acrylic acid, 15 parts of isooctyl acrylate and 30 parts of initiator ammonium persulfate solution are dripped, the dripping is finished within 1 hour, and then the reaction is carried out for 2 hours under heat preservation; and (3) after the heat preservation reaction is finished, stirring and cooling to room temperature, and adjusting the pH to 7.2 by using a sodium hydroxide solution to obtain the polymer emulsifier.
The weight average relative molecular weight of the polymeric emulsifier was 38800 by GPC.
Example 2
The polycarboxylic acid polymer emulsifier and the preparation method thereof are as follows: adding 100 parts of water and 50 parts of isopropanol into a reaction kettle, and heating while stirring; when the temperature of the solution in the reaction kettle is raised to 80 ℃, 15 parts of acrylic acid, 20 parts of isooctyl acrylate and 30 parts of initiator ammonium persulfate solution are dripped, the dripping is finished within 1 hour, and then the reaction is carried out for 2 hours under heat preservation; and (3) after the heat preservation reaction is finished, stirring and cooling to room temperature, and adjusting the pH to 7.2 by using a sodium hydroxide solution to obtain the polymer emulsifier.
The weight average relative molecular weight of the polymeric emulsifier is 40600 by GPC.
Example 3
The polycarboxylic acid polymer emulsifier and the preparation method thereof are as follows: adding 100 parts of water and 50 parts of isopropanol into a reaction kettle, and heating while stirring; when the temperature of the solution in the reaction kettle is raised to 85 ℃, 15 parts of acrylic acid, 20 parts of isooctyl acrylate and 30 parts of initiator ammonium persulfate solution are dripped, the dripping is finished within 1.5 hours, and then the reaction is carried out for 2 hours under heat preservation; and (3) after the heat preservation reaction is finished, stirring and cooling to room temperature, and adjusting the pH to 7.2 by using a sodium hydroxide solution to obtain the polymer emulsifier.
The weight average relative molecular weight of the polymeric emulsifier is 41500 by GPC.
Example 4
The polycarboxylic acid polymer emulsifier and the preparation method thereof are as follows: adding 100 parts of water and 50 parts of isopropanol into a reaction kettle, and heating while stirring; when the temperature of the solution in the reaction kettle is raised to 80 ℃, 20 parts of acrylic acid, 15 parts of isooctyl acrylate and 30 parts of initiator ammonium persulfate solution are dripped, the dripping is finished within 0.5 hour, and then the reaction is carried out for 2 hours under heat preservation; and (3) after the heat preservation reaction is finished, stirring and cooling to room temperature, and adjusting the pH to 7.2 by using a sodium hydroxide solution to obtain the polymer emulsifier.
The weight average relative molecular weight of the polymeric emulsifier is 42600 by GPC detection.
Example 5
The polycarboxylic acid polymer emulsifier and the preparation method thereof are as follows: adding 100 parts of water and 50 parts of isopropanol into a reaction kettle, and heating while stirring; when the temperature of the solution in the reaction kettle is raised to 70 ℃, 10 parts of acrylic acid, 20 parts of isooctyl acrylate and 30 parts of initiator ammonium persulfate solution are dripped, the dripping is finished within 1.5 hours, and then the reaction is carried out for 2 hours under heat preservation; and (3) after the heat preservation reaction is finished, stirring and cooling to room temperature, and adjusting the pH to 7.2 by using a sodium hydroxide solution to obtain the polymer emulsifier.
The weight average relative molecular weight of the high molecular emulsifier is 39800 by GPC.
Example 6
The polycarboxylic acid polymer emulsifier and the preparation method thereof are as follows: adding 200 parts of water and 20 parts of propanol into a reaction kettle, and heating while stirring; when the temperature of the solution in the reaction kettle rises to 90 ℃, dropwise adding 30 parts of methacrylic acid, 5 parts of amyl methacrylate and 10 parts of initiator ammonium persulfate solution, finishing dropwise adding within 0.5 hour, and then carrying out heat preservation reaction for 6 hours; and (3) after the heat preservation reaction is finished, stirring and cooling to room temperature, and adjusting the pH to 8 by using a sodium hydroxide solution to obtain the polymer emulsifier.
The weight average relative molecular weight of the polymer emulsifier is 10400 by GPC.
Example 7
The polycarboxylic acid polymer emulsifier and the preparation method thereof are as follows: adding 50 parts of water and 100 parts of isopropanol into a reaction kettle, and heating while stirring; when the temperature of the solution in the reaction kettle is increased to 65 ℃, 70 parts of acrylic acid, 50 parts of octadecyl acrylate and 40 parts of initiator ammonium persulfate solution are dropwise added, the dropwise addition is finished within 2.5 hours, and the reaction is carried out for 4 hours under heat preservation; and (3) after the heat preservation reaction is finished, stirring and cooling to room temperature, and adjusting the pH to 6 by using a sodium hydroxide solution to obtain the polymer emulsifier.
The weight average relative molecular weight of the polymeric emulsifier is 49560 by GPC.
To further illustrate the beneficial effects of the polycarboxylic acid emulsifier of the present invention, the following comparative examples were constructed for reasons of space only, using example 4 as an example.
Comparative example 1
The alcohol was omitted and the remaining conditions were the same as in example 4.
Comparative example 2
The alcohol was replaced with an equivalent amount of allyloxyphenoxypropanol polyoxyethylene ether and the remaining conditions were the same as in example 4.
Comparative example 3
The alcohol was replaced with an equivalent amount of ammonium allyloxyphenoxypropanol polyoxyethylene ether sulfate and the remaining conditions were the same as in example 4.
Comparative example 4
The amount of isooctyl acrylate was adjusted to 4 parts, and the other conditions were the same as in example 4.
Comparative example 5
The amount of acrylic acid was adjusted to 8 parts, and the other conditions were the same as in example 4.
Comparative example 6
The isooctyl acrylate was replaced with methyl acrylate, and the other conditions were the same as in example 4.
Comparative example 7
The isooctyl acrylate was replaced with behenyl acrylate and the remaining conditions were the same as in example 4.
The emulsifiers prepared in the above examples 1 to 7 and comparative examples 1 to 7 were subjected to an emulsification performance test, which was specifically as follows.
1. Emulsion stability
The polymeric emulsifier prepared in example 4 was added to water in a certain proportion of oil to make a 40% emulsion, which was sheared with shear emulsifier for 5min, allowed to stand for 30min, and the emulsion stability was observed, the results are shown in table 1.
TABLE 1 emulsion stability
As can be seen from Table 1, when the amount of the polymeric emulsifier added in the present invention reaches 1%, the properties of the emulsion prepared are stable.
2. The emulsifying properties of the polymeric emulsifiers prepared in examples 1 to 7 and the emulsifiers prepared in comparative examples 1 to 8 were examined.
(1) Evaluation of emulsifier stability
Adding 50mL of the emulsifier into a centrifugal tube of a desktop centrifuge (TDZ5-WS), centrifuging for 30min at the speed of 3000r/min, wherein if no layering and no precipitation exist, the stability is good, and otherwise, the stability is poor;
(2) evaluation of emulsion stability
Mixing the emulsifier 5%, fatty acid methyl ester 40% and water 55% at a certain proportion, and shearing with shearing emulsifier for 5min to obtain emulsion. The emulsion stability test is carried out according to the stability of the pesticide emulsion GB/T1603-2001 and diluted by 100 times; the emulsion was tested for D [ V, 50] particle size using a Mastorsizer2000 laser particle sizer. The relevant properties are shown in Table 2.
TABLE 2
As can be seen from Table 2, the polymeric emulsifier prepared by the present invention has no delamination phenomenon under high speed centrifugation condition and good stability. The emulsifier is used in emulsifying fatty acid methyl ester and has high emulsion stability and small D V, 50 particle size.
3. Enhanced emulsion high temperature stability tests were conducted on the polymeric emulsifiers prepared in examples 1-7 above and the emulsifiers prepared in comparative examples 1-7.
Mixing the emulsifier 1%, OP-102%, fatty acid methyl ester 40% and water 57% in proportion, and shearing with shearing emulsifier for 5 min. The sample is put into an ampoule bottle and sealed, and then placed in an incubator at 54 ℃ for 24h, and the change is observed. The D [ V, 50] particle size of the emulsion before and after heat storage was measured using a Mastorsizer2000 laser particle sizer.
And (4) comparison treatment: proportionally mixing OP-103%, fatty acid methyl ester 40% and water 57%, and shearing with shearing emulsifier for 5 min. The sample is put into an ampoule bottle and sealed, and then placed in an incubator at 54 ℃ for 24h, and the change is observed. The D [ V, 50] particle size of the emulsion before and after heat storage was measured using a Mastorsizer2000 laser particle sizer.
Before and after the control treatment and heat storage, the D [ V, 50] particle sizes were 1.0 μm and 25.4 μm, respectively, and the color became dark. The test results of examples 1 to 7 and comparative examples 1 to 8 are shown in Table 3.
TABLE 3
The results show that the high-molecular emulsifier prepared by the invention has small change before and after thermal storage, and the high-temperature stability of the emulsion can be improved, and the defect that the low-molecular emulsifier cannot resist high temperature is reduced
4. The emulsifiers of examples 1 to 7 and comparative examples 1 to 8 were applied to a 24% atrazine suspending agent, the amount of the emulsifier added was 5 wt%, and the performance tests are shown in table 4 below.
TABLE 4
As can be seen from table 4, when the acrylic monomer and the acrylic monomer are controlled within a certain ratio range, the obtained emulsifier can greatly improve the stability of the pesticide suspension concentrate, and can effectively reduce the decomposition rate of the pesticide.
In summary, the acrylic monomer used in the present invention is hydrophilic, the acrylic monomer is lipophilic, the HLB value of the emulsifier can be adjusted by controlling the addition ratio of the acrylic monomer and the acrylic monomer, which is simple and convenient, and imparts excellent performance to the emulsifier.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The polycarboxylic acid polymer emulsifier is characterized by being prepared from the following components in parts by weight: 10-70 parts of acrylic monomers, 5-50 parts of acrylate monomers, 20-100 parts of alcohols, 10-40 parts of initiators, 1-40 parts of alkali and 50-200 parts of water;
the molar mass ratio of the acrylic monomer to the acrylate monomer is 1-6: 1-5.
2. The polycarboxylic acid type polymeric emulsifier according to claim 1, which is prepared from the following components in parts by weight: 10-20 parts of acrylic monomer, 15-20 parts of acrylate monomer, 50 parts of alcohol, 20-30 parts of initiator, 1-40 parts of alkali and 100 parts of water.
3. The polycarboxylic acid type polymeric emulsifier according to claim 1, which is prepared from the following components in parts by weight: 20 parts of acrylic monomers, 15 parts of acrylate monomers, 50 parts of alcohols, 30 parts of initiators, 1-40 parts of alkali and 100 parts of water.
4. The polycarboxylic acid type polymeric emulsifier according to any one of claims 1 to 3, wherein the polymeric emulsifier has a weight average relative molecular weight of 10000-50000.
5. The polycarboxylic acid type polymeric emulsifier of claim 4, wherein the acrylic monomer is acrylic acid and/or methacrylic acid;
the acrylate monomer is one or two of acrylate with carbon number of 5-18 alcohol and methacrylate with carbon number of 5-18 alcohol.
6. The polycarboxylic acid polymer emulsifier of claim 4, wherein the alcohol is one or both of propanol and isopropanol.
7. The polycarboxylic acid polymer emulsifier of claim 4, wherein the alkali is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ammonia water and ethanolamine; the initiator is persulfate.
8. The polycarboxylic acid polymer emulsifier according to claim 4, wherein the amount of the polycarboxylic acid polymer emulsifier is 1 to 20 wt%.
9. The method for preparing a polycarboxylic acid type polymeric emulsifier according to any one of claims 1 to 8, comprising the steps of:
step 1: adding deionized water and alcohols into a reaction kettle, uniformly stirring, and heating to 65-90 ℃;
step 2: simultaneously dripping acrylic monomers, acrylic ester monomers and an initiator solution into the solution, finishing dripping within 0.5-2.5 hours, and reacting for 1-6 hours under the condition of heat preservation;
and step 3: and (3) stirring the solution obtained in the step (2), cooling to room temperature, adjusting the pH to 6.0-8.0 by using alkali, and discharging to obtain the catalyst.
10. The use of the polycarboxylic acid polymeric emulsifier of any one of claims 1 to 8 for preparing atrazine suspending agent.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115403692A (en) * | 2022-06-14 | 2022-11-29 | 上海启璇化工科技有限公司 | Powdery polycarboxylate polymer dispersant, and preparation method and application thereof |
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