CN115067324B - High-molecular polycarboxylate dispersant and preparation method thereof - Google Patents
High-molecular polycarboxylate dispersant and preparation method thereof Download PDFInfo
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- CN115067324B CN115067324B CN202110912989.3A CN202110912989A CN115067324B CN 115067324 B CN115067324 B CN 115067324B CN 202110912989 A CN202110912989 A CN 202110912989A CN 115067324 B CN115067324 B CN 115067324B
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- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 41
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000003999 initiator Substances 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 20
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 10
- -1 polyethylene Polymers 0.000 claims description 38
- 229920001610 polycaprolactone Polymers 0.000 claims description 27
- 239000004632 polycaprolactone Substances 0.000 claims description 27
- 239000004698 Polyethylene Substances 0.000 claims description 24
- 229920000573 polyethylene Polymers 0.000 claims description 24
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 9
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 3
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims description 2
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims 1
- 239000000575 pesticide Substances 0.000 abstract description 21
- 239000002245 particle Substances 0.000 abstract description 13
- 239000006185 dispersion Substances 0.000 abstract description 5
- 230000000361 pesticidal effect Effects 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229940051841 polyoxyethylene ether Drugs 0.000 description 11
- 229920000056 polyoxyethylene ether Polymers 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 10
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- GLGNXYJARSMNGJ-VKTIVEEGSA-N (1s,2s,3r,4r)-3-[[5-chloro-2-[(1-ethyl-6-methoxy-2-oxo-4,5-dihydro-3h-1-benzazepin-7-yl)amino]pyrimidin-4-yl]amino]bicyclo[2.2.1]hept-5-ene-2-carboxamide Chemical compound CCN1C(=O)CCCC2=C(OC)C(NC=3N=C(C(=CN=3)Cl)N[C@H]3[C@H]([C@@]4([H])C[C@@]3(C=C4)[H])C(N)=O)=CC=C21 GLGNXYJARSMNGJ-VKTIVEEGSA-N 0.000 description 3
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 3
- 229940125758 compound 15 Drugs 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 150000003926 acrylamides Chemical class 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005338 heat storage Methods 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 150000003254 radicals Chemical group 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229940104256 sodium taurate Drugs 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000004562 water dispersible granule Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Wood Science & Technology (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention belongs to the technical field related to pesticide auxiliary agents, and particularly relates to a high-molecular polycarboxylate dispersant and a preparation method thereof. A high molecular polycarboxylate dispersant is prepared from the following raw materials: reaction monomers, polyethylene glycol copolymer and initiator. The high molecular polycarboxylate prepared by the invention can control the adsorption of the high molecular polycarboxylate on the surfaces of pesticide particles, avoid adsorption competition of other particles among molecules, ensure the stability of the prepared high molecular polycarboxylate dispersing agent, ensure the dispersion performance of the raw pesticide in the preparation when the high molecular polycarboxylate dispersing agent is used in pesticides, ensure the exertion of pesticide effect, avoid repeated use of the pesticides and reduce unnecessary environmental pollution.
Description
Technical Field
The invention belongs to the technical field related to A01N25/00, and particularly relates to a high molecular polycarboxylate dispersant and a preparation method thereof.
Background
With the development of society and the progress of technology, researchers have been increasingly researching in the pesticide field, and researchers hope to reduce the use amount of pesticides and reduce the harm to the applicators and the environment while improving the pesticide effect.
However, the research on pesticides is not only reflected in the development and use of raw materials, the correct selection of auxiliary agents is also an important factor for determining the efficacy of the pesticides, and the Chinese patent publication No. CN109180875A discloses a high-molecular polycarboxylate dispersant, and in the disclosed patent, itaconic acid, sodium bisulfite, N-sunflower alcohol, trisstyrylphenol polyoxyethylene ether, dialkyl polyoxyethylene ether methacrylate, N-oleoyl-N-methyl sodium taurate, deionized water and an initiator are used as raw materials to synthesize the high-molecular polycarboxylate dispersant through emulsion polymerization. However, the type of initiator used in the disclosed patent is not completely safe and environmentally friendly, and there may be misuse of the initiator during use which may cause some damage to the soil during specific use.
With the progress of technology, although the polycarboxylate dispersants are increasingly used in pesticides, functional groups such as sulfonic acid groups, carboxyl groups and the like contained in the polycarboxylate dispersants have better dispersibility on pesticide particles. However, the polycarboxylate dispersants on the market have unstable dispersing effect on different pesticides in the preparation, poor storage effect and the problem of the current stage, and the preparation of a widely applied dispersing agent with excellent dispersing effect and high storage stability becomes an important task.
Disclosure of Invention
In order to solve the above problems, a first aspect of the present invention provides a polymeric polycarboxylate dispersant, which is prepared from the following raw materials: reaction monomers, polyethylene glycol copolymer, initiator and hexadecyl trimethyl ammonium chloride.
In some preferred embodiments, the reactive monomer is selected from one or more of acrylic acid, acrylic acid ester compounds, acrylamide compounds and allyl polyoxyethylene ether.
In some preferred embodiments, the acrylic compound is hydroxypropyl acrylate and/or butyl acrylate.
In some preferred embodiments, the molar ratio of hydroxypropyl acrylate to butyl acrylate is 1: (0.1-1).
Further preferably, the molar ratio of the hydroxypropyl acrylate to the butyl acrylate is 1:0.3.
in some preferred embodiments, the polyethylene glycol copolymer is selected from at least one of polyethylene glycol-polycaprolactone copolymer, polyethylene glycol-polylactic acid-glycolic acid copolymer, polyethylene glycol-polytrimethylene carbonate copolymer, methoxypolyethylene glycol-polycaprolactone copolymer.
In some preferred embodiments, the weight ratio of polyethylene glycol copolymer to cetyltrimethylammonium chloride is (0.2-0.5): 1.
in some preferred embodiments, the polyethylene glycol copolymer has a weight average molecular weight of 3200 to 9600.
In some preferred embodiments, the polyethylene glycol copolymer has a weight average molecular weight of 3200 to 7200.
In some preferred embodiments, the polyethylene glycol copolymer has a weight average molecular weight of 4800 to 7200.
In some preferred embodiments, the polyethylene glycol-based copolymer is selected from methoxy polyethylene glycol-polycaprolactone copolymers.
Methoxy polyethylene glycol-polycaprolactone copolymer
Methoxy polyethylene glycol-polycaprolactone (mPEG-PCL) is a block copolymer, one end of which is a hydrophilic chain segment-methoxy polyethylene glycol, and one end of which is an oleophilic chain segment-polycaprolactone.
In some preferred embodiments, the methoxypolyethylene glycol-polycaprolactone copolymer has a weight average molecular weight of 4800 to 7200.
Methoxy polyethylene glycol-polycaprolactone copolymer, model mPEG-PCL0204, available from Wuhan Haishan technology Co., ltd.
In some preferred embodiments, the preparation raw materials comprise, in parts by weight: 80-150 parts of reaction monomer, 0.5-5 parts of polyethylene glycol copolymer, 0.01-0.5 part of initiator and 1-15 parts of hexadecyl trimethyl ammonium chloride.
In some preferred embodiments, the reactive monomer comprises: acrylic acid, acrylic ester compounds, acrylamide compounds and allyl polyoxyethylene ether.
In some preferred embodiments, the acrylamide-based compound is N, N-dimethylacrylamide.
In some preferred embodiments, the reactive monomer comprises, in weight percent: 30-50% of acrylic acid, 10-20% of acrylic ester compound, 5-10% of acrylamide compound and the balance of allyl polyoxyethylene ether to 100%.
In some preferred embodiments, the weight ratio of methoxypolyethylene glycol-polycaprolactone copolymer to cetyltrimethylammonium chloride is (0.2-0.5): 1.
through a great deal of creative experimental research, the applicant discovers that the polycarboxylate dispersing agent prepared by selecting methoxy polyethylene glycol-polycaprolactone copolymer and cetyl trimethyl ammonium chloride can ensure that the obtained dispersing agent has a good dispersing effect in pesticide use. Applicant speculates that there may be reasons: the addition of the methoxy polyethylene glycol-polycaprolactone copolymer can influence the molecular chain segment of high molecular polycarboxylate formed by the synergistic effect of the reaction monomer and the initiator, the weight average molecular weight of the methoxy polyethylene glycol-polycaprolactone copolymer is 4800-7200, and the weight ratio of the methoxy polyethylene glycol-polycaprolactone copolymer to the hexadecyl trimethyl ammonium chloride is controlled to be (0.2-0.5): 1, the prepared high polymer polycarboxylate particles have proper steric hindrance effect, so that van der Waals acting force among the particles can be reduced, the surface energy of the particles is reduced, and the dispersion performance of the particles is stable; in the experimental process, the applicant finds that when the ratio of the selected methoxy polyethylene glycol-polycaprolactone copolymer is lower than the range of the application, the competition between free ammonium cations, carboxylate anions and other active groups in the system can be enhanced, the high molecular polycarboxylate adsorbed on the surface of the high molecular polycarboxylate pesticide preparation is reduced, and the dispersion performance is reduced.
On the other hand, the applicant finds that when the weight average molecular weight of the selected methoxy polyethylene glycol-polycaprolactone copolymer is too small, the steric barrier effect generated by a solvated chain is not obvious, so that the steric effect among particles cannot reach an equilibrium state, and flocculation and precipitation among particles are caused, and the pesticide effect of the pesticide is affected; when the weight average molecular weight of the methoxypolyethylene glycol-polycaprolactone copolymer is too large, the inter-entanglement between solvated chains is enhanced, the inter-particle aggregation is enhanced, and inter-particle aggregation may occur.
In some preferred embodiments, the initiator is a free radical initiator.
The second aspect of the invention provides a method for preparing a polymeric polycarboxylate dispersant, comprising the steps of:
s01: adding the reaction monomer into a reaction kettle, mixing, and stirring for 30-60 minutes;
s02: adding polyethylene glycol copolymer, hexadecyl trimethyl ammonium chloride and initiator in the step S01, controlling the stirring speed to be 1000-1500rpm, after reacting for 10-20 minutes, turning off stirring, heating to 50-60 ℃, reacting for 1-3 hours, and cooling to 25-30 ℃ to obtain a mixture A;
s03: adjusting ApH value of the mixture, and spray drying.
It should be noted that the reagent for adjusting the pH value in the application selects 1M sodium hydroxide aqueous solution.
The beneficial effects are that: the high molecular polycarboxylate prepared by the invention can control the adsorption of the high molecular polycarboxylate on the surfaces of pesticide particles, avoid adsorption competition of other particles among molecules, ensure the stability of the prepared high molecular polycarboxylate dispersing agent, ensure the dispersion performance of the raw pesticide in the preparation when the high molecular polycarboxylate dispersing agent is used in pesticides, ensure the exertion of pesticide effect, avoid repeated use of the pesticides and reduce unnecessary environmental pollution.
Detailed Description
Examples
Example 1
The high-molecular polycarboxylate dispersant comprises the following preparation raw materials in parts by weight: 80 parts of reaction monomer, 0.5 part of methoxy polyethylene glycol-polycaprolactone copolymer, 1.25 parts of cetyl trimethyl ammonium chloride and 0.05 part of initiator.
The weight average molecular weight of the methoxy polyethylene glycol-polycaprolactone copolymer is 4800-7200.
The reaction monomer comprises the following components in percentage by weight: acrylic acid 35%, acrylic ester compound 15%, N-dimethylacrylamide 12%, and allyl polyoxyethylene ether with the balance being 100%.
The acrylic ester compound is hydroxypropyl acrylate and butyl acrylate, and the molar ratio is 1:0.3.
the allyl polyoxyethylene ether has a hydroxyl value of 53-59mgKOH/g and a model APEG-1000, and is purchased from the company of Chen Tai blue sky fine chemical Co., ltd; methoxy polyethylene glycol-polycaprolactone copolymer, model mPEG-PCL0204, available from Wuhan Haishan technology Co., ltd.
The initiator is selected from ammonium persulfate.
A preparation method of a high molecular polycarboxylate dispersant comprises the following steps:
s01: adding the reaction monomer into a reaction kettle, mixing, and stirring for 30 minutes;
s02: adding polyethylene glycol copolymer, hexadecyl trimethyl ammonium chloride and an initiator in the step S01, controlling the stirring speed to be 1200rpm, after reacting for 10 minutes, turning off stirring, heating to 50 ℃, and cooling to 25 ℃ after reacting for 2 hours to obtain a mixture A;
s03: adjusting the pH value of the mixture A to 6.8 by using sodium hydroxide aqueous solution, and spray drying to obtain the product.
Example 2
The high-molecular polycarboxylate dispersant comprises the following preparation raw materials in parts by weight: 150 parts of reaction monomer, 5 parts of methoxy polyethylene glycol-polycaprolactone copolymer, 12.5 parts of cetyl trimethyl ammonium chloride and 0.5 part of initiator.
The weight average molecular weight of the methoxy polyethylene glycol-polycaprolactone copolymer is 4800-7200.
The reaction monomer comprises the following components in percentage by weight: acrylic acid 35%, acrylic ester compound 15%, N-dimethylacrylamide 12%, and allyl polyoxyethylene ether with the balance being 100%.
The acrylic ester compound is hydroxypropyl acrylate and butyl acrylate, and the molar ratio is 1:0.3.
the allyl polyoxyethylene ether has a hydroxyl value of 53-59mgKOH/g and a model APEG-1000, and is purchased from the company of Chen Tai blue sky fine chemical Co., ltd; methoxy polyethylene glycol-polycaprolactone copolymer, model mPEG-PCL0204, available from Wuhan Haishan technology Co., ltd.
The initiator is selected from potassium persulfate.
A preparation method of a high molecular polycarboxylate dispersant comprises the following steps:
s01: adding the reaction monomer into a reaction kettle, mixing, and stirring for 30 minutes;
s02: adding polyethylene glycol copolymer, hexadecyl trimethyl ammonium chloride and an initiator in the step S01, controlling the stirring speed to be 1200rpm, after reacting for 10 minutes, turning off stirring, heating to 50 ℃, and cooling to 25 ℃ after reacting for 2 hours to obtain a mixture A;
s03: adjusting the pH value of the mixture A to 6.8 by using sodium hydroxide aqueous solution, and spray drying to obtain the product.
Example 3
The high-molecular polycarboxylate dispersant comprises the following preparation raw materials in parts by weight: 120 parts of reaction monomer, 2 parts of methoxy polyethylene glycol-polycaprolactone copolymer, 5 parts of cetyl trimethyl ammonium chloride and 0.2 part of initiator.
The weight average molecular weight of the methoxy polyethylene glycol-polycaprolactone copolymer is 4800-7200.
The reaction monomer comprises the following components in percentage by weight: acrylic acid 35%, acrylic ester compound 15%, N-dimethylacrylamide 12%, and allyl polyoxyethylene ether with the balance being 100%.
The acrylic ester compound is hydroxypropyl acrylate and butyl acrylate, and the molar ratio is 1:0.3.
the allyl polyoxyethylene ether has a hydroxyl value of 53-59mgKOH/g and a model APEG-1000, and is purchased from the company of Chen Tai blue sky fine chemical Co., ltd; methoxy polyethylene glycol-polycaprolactone copolymer, model mPEG-PCL0204, available from Wuhan Haishan technology Co., ltd.
The initiator is selected from potassium persulfate.
A preparation method of a high molecular polycarboxylate dispersant comprises the following steps:
s01: adding the reaction monomer into a reaction kettle, mixing, and stirring for 30 minutes;
s02: adding polyethylene glycol copolymer, hexadecyl trimethyl ammonium chloride and an initiator in the step S01, controlling the stirring speed to be 1200rpm, after reacting for 10 minutes, turning off stirring, heating to 50 ℃, and cooling to 25 ℃ after reacting for 2 hours to obtain a mixture A;
s03: adjusting the pH value of the mixture A to 6.8 by using sodium hydroxide aqueous solution, and spray drying to obtain the product.
Example 4
A polymeric polycarboxylate dispersant, the specific embodiment of which is the same as in example 3, is different from example 3 in that the reactive monomer does not contain acrylic acid, and the weight percentage of the acrylic ester compound is 55%.
Example 5
A polymeric polycarboxylate dispersant, the specific embodiment of which is the same as in example 3, is different from example 3 in that the acrylic ester compound is butyl acrylate.
Example 6
A polymeric polycarboxylate dispersant was prepared in the same manner as in example 3, except that 10 parts by weight of cetyltrimethylammonium chloride was used as the dispersant in example 3.
Example 7
A high molecular polycarboxylate dispersant, the specific embodiment of which is the same as that of example 3, is different from example 3 in that the weight average molecular weight of methoxy polyethylene glycol-polycaprolactone copolymer is 12000-18000, and the model mPEG-PCL0510 is purchased from the Wuhan Haishan technology Co.
Performance test:
the high molecular polycarboxylate dispersant prepared in examples 1-7 of the application is used for preparing atrazine water dispersible granules, wherein the mass fraction of atrazine is 90%, the mass fraction of the dispersant is 5%, and the balance is supplemented by corn starch to 100%.
The dispersibility, suspension rate and heat storage stability of the atrazine obtained are tested, and the test results are counted in the following table:
dispersibility: test methods refer to GB/T32775-2016.
Suspension ratio: the test method refers to GB/T14825-2006, and the suspension rate calculation formula refers to R=m 1 -m 2 /m 1 X 10/9 x 100 where m 1 The mass of the effective components in the sample for preparing the suspension is expressed in g; m is m 2 The unit is g for the mass of the active ingredients left at the bottom of the measuring cylinder; and 10/9 is a conversion coefficient.
Thermal storage stability: according to the test method, according to GB/T19136-2003, the effective component decomposition rate after the test is specified to be less than or equal to 5%, the suspension rate accords with the index and is marked as qualified, otherwise, the effective component decomposition rate is not qualified.
| Experiment | Dispersibility of | Suspension rate/% | Thermal storage stability |
| Example 1 | No precipitate | 96.32 | Qualified product |
| Example 2 | No precipitate | 96.56 | Qualified product |
| Example 3 | No precipitate | 97.23 | Qualified product |
| Example 4 | Precipitation occurs | 91.24 | Failure to pass |
| Example 5 | Precipitation occurs | 93.52 | Failure to pass |
| Example 6 | More precipitate | 89.32 | Failure to pass |
| Example 7 | More precipitate | 90.12 | Failure to pass |
The high-molecular polycarboxylate dispersant prepared by the application has good dispersion effect and high heat storage stability, ensures the pesticide effect of the pesticide, avoids repeated pesticide spraying and protects the environment.
Claims (4)
1. The high molecular polycarboxylate dispersant is characterized in that the preparation raw materials comprise: reaction monomers, polyethylene glycol copolymer, initiator and hexadecyl trimethyl ammonium chloride;
the polyethylene glycol copolymer is polyethylene glycol-polycaprolactone copolymer;
the weight ratio of the polyethylene glycol copolymer to the hexadecyl trimethyl ammonium chloride is (0.2-0.5): 1, a step of;
the reaction monomer is selected from acrylic ester compounds;
the acrylic ester compounds are hydroxypropyl acrylate and butyl acrylate;
the molar ratio of the hydroxypropyl acrylate to the butyl acrylate is 1: (0.1-1);
the weight average molecular weight of the polyethylene glycol copolymer is 3200-9600.
2. The polymeric polycarboxylate dispersant of claim 1, wherein the acrylamide compound is N, N-dimethylacrylamide.
3. The polymeric polycarboxylate dispersant of claim 1, wherein the preparation raw materials include, in parts by weight: 80-150 parts of reaction monomer, 0.5-5 parts of polyethylene glycol copolymer, 0.01-0.5 part of initiator and 1-15 parts of hexadecyl trimethyl ammonium chloride.
4. A process for the preparation of a polymeric polycarboxylate dispersant as claimed in any one of claims 1 to 3, comprising the steps of:
s01: adding the reaction monomer into a reaction kettle, mixing, and stirring for 30-60 minutes;
s02: adding polyethylene glycol copolymer, hexadecyl trimethyl ammonium chloride and initiator in the step S01, controlling the stirring speed to be 1000-1500rpm, after reacting for 10-20 minutes, turning off stirring, heating to 50-60 ℃, reacting for 1-3 hours, and cooling to 25-30 ℃ to obtain a mixture A;
s03: adjusting the pH value of the mixture A, and spray drying to obtain the final product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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Citations (5)
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|---|---|---|---|---|
| CN103450407A (en) * | 2013-08-15 | 2013-12-18 | 吉林大学 | Allyl polyoxyethylene ether modified polycarboxylate pesticide dispersing agent and preparation method thereof |
| CN103563895A (en) * | 2013-11-15 | 2014-02-12 | 石家庄博佳特化工有限公司 | Dispersing agent for pesticide emulsion in water, and preparation method and application of dispersing agent |
| CN103910832A (en) * | 2014-04-22 | 2014-07-09 | 南京太化化工有限公司 | Polycarboxylate pesticide dispersing agent and preparation method thereof |
| CN110054736A (en) * | 2019-04-11 | 2019-07-26 | 上海是大高分子材料有限公司 | A kind of polycarboxylate salt dispersant and preparation method thereof |
| CN111972407A (en) * | 2020-07-31 | 2020-11-24 | 常州润源新材料科技有限责任公司 | Pesticide suspension dispersant and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103450407A (en) * | 2013-08-15 | 2013-12-18 | 吉林大学 | Allyl polyoxyethylene ether modified polycarboxylate pesticide dispersing agent and preparation method thereof |
| CN103563895A (en) * | 2013-11-15 | 2014-02-12 | 石家庄博佳特化工有限公司 | Dispersing agent for pesticide emulsion in water, and preparation method and application of dispersing agent |
| CN103910832A (en) * | 2014-04-22 | 2014-07-09 | 南京太化化工有限公司 | Polycarboxylate pesticide dispersing agent and preparation method thereof |
| CN110054736A (en) * | 2019-04-11 | 2019-07-26 | 上海是大高分子材料有限公司 | A kind of polycarboxylate salt dispersant and preparation method thereof |
| CN111972407A (en) * | 2020-07-31 | 2020-11-24 | 常州润源新材料科技有限责任公司 | Pesticide suspension dispersant and preparation method thereof |
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