CN115067324A - High-molecular polycarboxylate dispersant and preparation method thereof - Google Patents
High-molecular polycarboxylate dispersant and preparation method thereof Download PDFInfo
- Publication number
- CN115067324A CN115067324A CN202110912989.3A CN202110912989A CN115067324A CN 115067324 A CN115067324 A CN 115067324A CN 202110912989 A CN202110912989 A CN 202110912989A CN 115067324 A CN115067324 A CN 115067324A
- Authority
- CN
- China
- Prior art keywords
- polyethylene glycol
- polycarboxylate dispersant
- copolymer
- polymeric polycarboxylate
- pesticide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 47
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 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 9
- 238000000034 method Methods 0.000 claims abstract description 5
- -1 acrylate compound Chemical class 0.000 claims description 37
- 229920001610 polycaprolactone Polymers 0.000 claims description 28
- 239000004632 polycaprolactone Substances 0.000 claims description 28
- 239000004698 Polyethylene Substances 0.000 claims description 21
- 229920000573 polyethylene Polymers 0.000 claims description 21
- 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
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 12
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 12
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 12
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 5
- 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
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims description 5
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 4
- 150000003926 acrylamides Chemical class 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- 239000000575 pesticide Substances 0.000 abstract description 19
- 239000002245 particle Substances 0.000 abstract description 13
- 230000000361 pesticidal effect Effects 0.000 abstract description 6
- 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 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000000694 effects Effects 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 6
- 239000000725 suspension Substances 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- 238000005338 heat storage Methods 0.000 description 4
- 239000007864 aqueous solution Substances 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
- 238000005516 engineering process Methods 0.000 description 3
- 239000012847 fine chemical Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 2
- 239000003905 agrochemical Substances 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
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development 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
- 239000002244 precipitate Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- TVFWYUWNQVRQRG-UHFFFAOYSA-N 2,3,4-tris(2-phenylethenyl)phenol Chemical compound C=1C=CC=CC=1C=CC1=C(C=CC=2C=CC=CC=2)C(O)=CC=C1C=CC1=CC=CC=C1 TVFWYUWNQVRQRG-UHFFFAOYSA-N 0.000 description 1
- 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
- 229940126062 Compound A Drugs 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-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
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 230000004888 barrier function 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
- 239000008120 corn starch Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 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
- 229920001606 poly(lactic acid-co-glycolic acid) Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003254 radicals Chemical group 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution 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 dispersing agent and a preparation method thereof. A macromolecular polycarboxylate dispersant is prepared by the following raw materials: reaction monomer, polyethylene glycol copolymer and initiator. The macromolecular polycarboxylate prepared by the method can control the adsorption of the macromolecular polycarboxylate on the surface of pesticide particles, avoids the adsorption competition of other particles among molecules, ensures the stability of the prepared macromolecular polycarboxylate dispersing agent, ensures the dispersing performance of the original pesticide in the preparation when the macromolecular polycarboxylate dispersing agent is used in the pesticide, ensures the exertion of the pesticide effect, avoids the repeated use of the pesticide and reduces unnecessary environmental pollution.
Description
Technical Field
The invention belongs to the related technical field of A01N25/00, and particularly relates to a high-molecular polycarboxylate dispersing agent and a preparation method thereof.
Background
With the development of society and the progress of technology, researchers have been increasing the research in the field of pesticides, and the researchers hope that the pesticide effect of the pesticides can be improved, the usage amount of the pesticides can be reduced, and the harm to the pesticide applicator and the environment can be reduced.
However, the research on the pesticide is not only reflected in the development and use of the original pesticide, and the correct selection of the auxiliary agent is also an important factor for determining the pesticide effect, and chinese patent publication No. CN109180875A discloses a polymeric polycarboxylate dispersant, in which a polymeric polycarboxylate dispersant is synthesized by emulsion polymerization reaction using itaconic acid, sodium bisulfite, N-decyl alcohol, tristyrylphenol polyoxyethylene ether, dialkyl polyoxyethylene ether methacrylate, N-oleoyl-N-methyltaurate, deionized water, and an initiator as raw materials. However, the type of initiator used in the published patent is not completely safe and environmentally friendly, and there may be some damage to the soil during the particular use due to improper use of the initiator during use.
With the progress of the technology, although the polycarboxylate-type dispersants are increasingly used in agricultural chemicals, functional groups such as sulfonic acid groups, carboxyl groups, and the like contained in the polycarboxylate-type dispersants have better dispersibility in agricultural chemical particles. However, the polycarboxylate dispersants on the market are unstable in dispersing effect of different pesticides in preparations, and poor in storage effect, and in order to solve the problems in the prior art, it is an important task to prepare a dispersant which is widely used, and has excellent dispersing effect and high storage stability.
Disclosure of Invention
In order to solve the above problems, a first aspect of the present invention provides a polymeric polycarboxylate dispersant prepared by using the following raw materials: reaction monomer, polyethylene glycol copolymer, initiator and hexadecyl trimethyl ammonium chloride.
In some preferred embodiments, the reactive monomer is one or more compounds selected from acrylic acid, acrylate compounds, acrylamide compounds, and allyl polyoxyethylene ether.
In some preferred embodiments, the acrylate 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 hydroxypropyl acrylate to butyl acrylate is 1: 0.3.
in some preferred embodiments, the polyethylene glycol copolymer is at least one selected from polyethylene glycol-polycaprolactone copolymer, polyethylene glycol-poly (lactic-co-glycolic acid), polyethylene glycol-poly (trimethylene carbonate), and methoxy polyethylene glycol-polycaprolactone copolymer.
In some preferred embodiments, the weight ratio of the polyethylene glycol copolymer to the cetyltrimethylammonium chloride is (0.2-0.5): 1.
in some preferred embodiments, the polyethylene glycol-based copolymer has a weight average molecular weight of 3200-9600.
In some preferred embodiments, the polyethylene glycol copolymer has a weight average molecular weight of 3200-7200.
In some preferred embodiments, the weight average molecular weight of the polyethylene glycol copolymer is 4800-7200.
In some preferred embodiments, the polyethylene glycol copolymer is selected from methoxy polyethylene glycol-polycaprolactone copolymer.
Methoxy polyethylene glycol-polycaprolactone copolymer
Methoxy polyethylene glycol-polycaprolactone (mPEG-PCL) is a block copolymer, one end is hydrophilic chain segment-methoxy polyethylene glycol, and the other end is oleophylic chain segment-polycaprolactone.
In some preferred embodiments, the methoxypolyethylene glycol-polycaprolactone copolymer has a weight average molecular weight of 4800-7200.
Methoxy polyethylene glycol-polycaprolactone copolymer, model mPEG-PCL0204, available from Wuhan Haishan science and technology Co.
In some preferred embodiments, the preparation raw materials comprise, 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 monomers comprise: acrylic acid, acrylate 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 monomers comprise, in weight percent: 30-50% of acrylic acid, 10-20% of acrylate 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 large amount of creative experimental researches, the applicant finds that the polycarboxylate dispersing agent prepared by selecting the methoxy polyethylene glycol-polycaprolactone copolymer and the hexadecyl trimethyl ammonium chloride can ensure that the obtained dispersing agent has a good dispersing effect in pesticide application. The applicant speculates the possible causes: the addition of the methoxy polyethylene glycol-polycaprolactone copolymer can affect the molecular chain segment of the macromolecular polycarboxylate formed by the synergistic action 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 macromolecular polycarboxylate particles have appropriate 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 dispersing performance of the particles is stable; in the experimental process, the applicant finds that when the selected ratio of the methoxypolyethylene glycol-polycaprolactone copolymer is lower than the range of the application, the competition between free ammonium cations and active groups such as carboxylate anions in a system is enhanced, the polymeric polycarboxylate adsorbed on the surface of the polymeric polycarboxylate pesticide preparation is reduced, and the dispersing performance is reduced.
On the other hand, the applicant finds that when the weight average molecular weight of the selected methoxypolyethylene glycol-polycaprolactone copolymer is too small, the three-dimensional barrier effect generated by a solvating chain is not obvious, the steric effect among particles cannot reach a balanced state, and the flocculation and precipitation among particles are caused to influence the pesticide effect; when the weight average molecular weight of the methoxypolyethylene glycol-polycaprolactone copolymer is too large, entanglement of solvated chains is enhanced, aggregation among particles is enhanced, and agglomeration among particles may occur.
In some preferred embodiments, the initiator is a free radical initiator.
The second aspect of the invention provides a preparation method of a polymeric polycarboxylate dispersant, which comprises the following steps:
s01: adding a reaction monomer into a reaction kettle, mixing, and stirring for 30-60 minutes;
s02: adding the polyethylene glycol copolymer, hexadecyl trimethyl ammonium chloride and an initiator into the step S01, controlling the stirring speed to be 1000-1500rpm, reacting for 10-20 minutes, then turning off the stirring, heating to 50-60 ℃, reacting for 1-3 hours, and then cooling to 25-30 ℃ to obtain a mixture A;
s03: adjusting ApH value of the mixture, and spray drying.
Note that in this application, the pH value adjusting reagent is 1M aqueous sodium hydroxide solution.
Has the advantages that: the macromolecular polycarboxylate prepared by the method can control the adsorption of the macromolecular polycarboxylate on the surface of pesticide particles, avoids the adsorption competition of other particles among molecules, ensures the stability of the prepared macromolecular polycarboxylate dispersing agent, ensures the dispersing performance of the original pesticide in the preparation when the macromolecular polycarboxylate dispersing agent is used in the pesticide, ensures the exertion of the pesticide effect, avoids the repeated use of the pesticide and reduces unnecessary environmental pollution.
Detailed Description
Examples
Example 1
A macromolecular 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 hexadecyl trimethyl ammonium chloride and 0.05 part of initiator.
The weight average molecular weight of the methoxypolyethylene glycol-polycaprolactone copolymer is 4800-7200.
The reaction monomer comprises the following components in percentage by weight: 35% of acrylic acid, 15% of acrylate compound, 12% of N, N-dimethylacrylamide and the balance of allyl polyoxyethylene ether to 100%.
The acrylic ester compound is hydroxypropyl acrylate and butyl acrylate, and the molar ratio of the acrylic ester compound to the butyl acrylate is 1: 0.3.
the allyl polyoxyethylene ether has a hydroxyl value of 53-59mgKOH/g and a model of APEG-1000, and is purchased from the Fine chemical company of Chachen Tai blue sky; methoxy polyethylene glycol-polycaprolactone copolymer, model mPEG-PCL0204, available from Wuhan Haishan science and technology Co.
The initiator is selected from ammonium persulfate.
A preparation method of a macromolecular polycarboxylate dispersant comprises the following steps:
s01: adding a reaction monomer into a reaction kettle, mixing and stirring for 30 minutes;
s02: adding the polyethylene glycol copolymer, hexadecyl trimethyl ammonium chloride and an initiator into the step S01, controlling the stirring speed to be 1200rpm, after reacting for 10 minutes, turning off the stirring, heating to 50 ℃, reacting for 2 hours, and then cooling to 25 ℃ to obtain a mixture A;
s03: and (3) adjusting the pH value of the mixture A to 6.8 by using a sodium hydroxide aqueous solution, and performing spray drying to obtain the compound A.
Example 2
A macromolecular 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 hexadecyl trimethyl ammonium chloride and 0.5 part of initiator.
The weight average molecular weight of the methoxypolyethylene glycol-polycaprolactone copolymer is 4800-7200.
The reaction monomer comprises the following components in percentage by weight: 35% of acrylic acid, 15% of acrylate compound, 12% of N, N-dimethylacrylamide and the balance of allyl polyoxyethylene ether to 100%.
The acrylic ester compound is hydroxypropyl acrylate and butyl acrylate, and the molar ratio of the acrylic ester compound to the butyl acrylate is 1: 0.3.
the allyl polyoxyethylene ether has a hydroxyl value of 53-59mgKOH/g and a model of APEG-1000, and is purchased from the Fine chemical company of Chachen Tai blue sky; methoxy polyethylene glycol-polycaprolactone copolymer, model mPEG-PCL0204, available from Wuhan Haishan science and technology Co.
The initiator is selected from potassium persulfate.
A preparation method of a macromolecular polycarboxylate dispersant comprises the following steps:
s01: adding a reaction monomer into a reaction kettle, mixing and stirring for 30 minutes;
s02: adding the polyethylene glycol copolymer, hexadecyl trimethyl ammonium chloride and an initiator into the step S01, controlling the stirring speed to be 1200rpm, after reacting for 10 minutes, turning off the stirring, heating to 50 ℃, reacting for 2 hours, and then cooling to 25 ℃ to obtain a mixture A;
s03: adjusting the pH value of the mixture A to 6.8 by using an aqueous solution of sodium hydroxide, and performing spray drying to obtain the compound.
Example 3
A macromolecular 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 hexadecyl trimethyl ammonium chloride and 0.2 part of initiator.
The weight average molecular weight of the methoxypolyethylene glycol-polycaprolactone copolymer is 4800-7200.
The reaction monomer comprises the following components in percentage by weight: 35% of acrylic acid, 15% of acrylate compound, 12% of N, N-dimethylacrylamide and the balance of allyl polyoxyethylene ether are supplemented to 100%.
The acrylic ester compound is hydroxypropyl acrylate and butyl acrylate, and the molar ratio of the acrylic ester compound to the butyl acrylate is 1: 0.3.
the allyl polyoxyethylene ether has a hydroxyl value of 53-59mgKOH/g and a model of APEG-1000, and is purchased from the Fine chemical company of Chachen Tai blue sky; methoxy polyethylene glycol-polycaprolactone copolymer, model mPEG-PCL0204, available from Wuhan Haishan science and technology Co.
The initiator is selected from potassium persulfate.
A preparation method of a macromolecular polycarboxylate dispersant comprises the following steps:
s01: adding a reaction monomer into a reaction kettle, mixing and stirring for 30 minutes;
s02: adding the polyethylene glycol copolymer, hexadecyl trimethyl ammonium chloride and an initiator into the step S01, controlling the stirring speed to be 1200rpm, after reacting for 10 minutes, turning off the stirring, heating to 50 ℃, reacting for 2 hours, and then cooling to 25 ℃ to obtain a mixture A;
s03: adjusting the pH value of the mixture A to 6.8 by using an aqueous solution of sodium hydroxide, and performing spray drying to obtain the compound.
Example 4
The specific implementation mode of the polymeric polycarboxylate dispersant is the same as that in example 3, except that the reaction monomers do not contain acrylic acid, and the weight percentage of the acrylate compounds is 55 percent.
Example 5
The embodiment of a polymeric polycarboxylate dispersant is the same as that in example 3, but the acrylate compound is butyl acrylate, which is different from example 3.
Example 6
A polymeric polycarboxylate dispersant is prepared in the same manner as in example 3 except that the polymeric polycarboxylate dispersant is prepared in an amount of 10 parts by weight of cetyltrimethylammonium chloride.
Example 7
The specific implementation manner of the polymeric polycarboxylate dispersant is the same as that in example 3, and the polymeric polycarboxylate dispersant is different from example 3 in that the weight-average molecular weight of the methoxypolyethylene glycol-polycaprolactone copolymer is 12000-18000, and the type mPEG-PCL0510 is purchased from Wuhan Haishan technologies, Inc.
And (3) performance testing:
the polymeric polycarboxylate dispersant prepared in the 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 of corn starch is 100%.
The prepared atrazine is tested for dispersibility, suspension rate and heat storage stability, and the test results are counted in the following table:
dispersibility: the test method is referred to GB/T32775-2016.
Suspension percentage: the test method refers to GB/T14825-2006, and the suspension rate calculation formula refers to R-m 1 -m 2 /m 1 X 10/9X 100, where m 1 The mass of the effective components in the sample taken for preparing the suspension is g; m is 2 The mass of the effective components left at the bottom of the measuring cylinder is g; 10/9 is a scaling factor.
Heat storage stability: the test method refers to GB/T19136-2003, and the decomposition rate of the effective components after the test is regulated to be less than or equal to 5%, and the suspension rate meeting the index is recorded as qualified, otherwise, the effective components are not qualified.
| Experiment of | Dispersibility in water | Suspension rate/% | Stability in Heat storage |
| Example 1 | No precipitation | 96.32 | Qualified |
| Example 2 | No precipitation | 96.56 | Qualified |
| Example 3 | No precipitation | 97.23 | Qualified |
| Example 4 | Precipitation occurs | 91.24 | Fail to be qualified |
| Example 5 | Precipitation occurred | 93.52 | Fail to be qualified |
| Example 6 | More precipitate | 89.32 | Fail to be qualified |
| Example 7 | More precipitate | 90.12 | Fail to be qualified |
The macromolecular polycarboxylate dispersing agent prepared by the method has a good dispersing effect and high heat storage stability, ensures the pesticide effect, avoids the use of pesticide by spraying for many times and protects the environment.
Claims (10)
1. A high-molecular polycarboxylate dispersant is characterized in that the preparation raw materials comprise: reaction monomer, polyethylene glycol copolymer, initiator and hexadecyl trimethyl ammonium chloride.
2. The polymeric polycarboxylate dispersant according to claim 1, wherein said reactive monomer is selected from one or more of acrylic acid, acrylate compounds, acrylamide compounds, and allyl polyoxyethylene ether.
3. The polymeric polycarboxylate dispersant of claim 2, wherein said acrylate compound is hydroxypropyl acrylate and/or butyl acrylate.
4. The polymeric polycarboxylate dispersant according to claim 3, wherein said hydroxypropyl acrylate and butyl acrylate are present in a molar ratio of 1: (0.1-1).
5. The polymeric polycarboxylate dispersant according to claim 1, wherein said polyethylene glycol copolymer is at least one selected from the group consisting of polyethylene glycol-polycaprolactone copolymer, polyethylene glycol-polylactic-glycolic acid copolymer, polyethylene glycol-polytrimethylene carbonate copolymer, and methoxypolyethylene glycol-polycaprolactone copolymer.
6. The polymeric polycarboxylate dispersant according to claim 5, wherein the weight ratio of said polyethylene glycol copolymer to said cetyltrimethylammonium chloride is (0.2-0.5): 1.
7. the polymeric polycarboxylate dispersant according to claim 6, wherein said polyethylene glycol copolymer has a weight average molecular weight of 3200-9600.
8. The polymeric polycarboxylate dispersant of claim 2, wherein said acrylamide-type compound is N, N-dimethylacrylamide.
9. The polymeric polycarboxylate dispersant according to claim 1, characterized in that 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.
10. A method of preparing a polymeric polycarboxylate dispersant according to any of the claims 1-9, comprising the steps of:
s01: adding a reaction monomer into a reaction kettle, mixing, and stirring for 30-60 minutes;
s02: adding the polyethylene glycol copolymer, hexadecyl trimethyl ammonium chloride and an initiator into the step S01, controlling the stirring speed to be 1000-1500rpm, reacting for 10-20 minutes, then turning off the stirring, heating to 50-60 ℃, reacting for 1-3 hours, and then cooling to 25-30 ℃ to obtain a mixture A;
s03: adjusting ApH value of the mixture, and spray drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110912989.3A CN115067324B (en) | 2021-08-10 | 2021-08-10 | High-molecular polycarboxylate dispersant and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110912989.3A CN115067324B (en) | 2021-08-10 | 2021-08-10 | High-molecular polycarboxylate dispersant and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115067324A true CN115067324A (en) | 2022-09-20 |
| CN115067324B CN115067324B (en) | 2024-03-26 |
Family
ID=83246013
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110912989.3A Active CN115067324B (en) | 2021-08-10 | 2021-08-10 | High-molecular polycarboxylate dispersant and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115067324B (en) |
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 |
-
2021
- 2021-08-10 CN CN202110912989.3A patent/CN115067324B/en active Active
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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115067324B (en) | 2024-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5468797A (en) | Polycarboxylic acid thickeners, emulsifiers, and suspending aids having improved wettability characteristics | |
| CN101514239A (en) | Amphoteric polyacrylamide and preparation method thereof | |
| CN108559018B (en) | Nano-scale water Narrow Molecular Weight Distribution acrylic acid copolymer ester and preparation method thereof | |
| CN105175749B (en) | dispersion of adsorbed emulsion polymer particles | |
| CN102911321A (en) | Pesticide suspension concentrate dispersing agent and novel preparation method thereof | |
| CN104403049A (en) | Method for preparing phase-change microcapsule through suspension polymerization | |
| CN109054101B (en) | Super-hydrophobic magnetic nanocellulose and preparation method thereof | |
| CN103059216B (en) | A kind of dispersion agent, its preparation method and the application in anionic polyacrylamide water-dispersible emulsion polymerization thereof | |
| CN111378075B (en) | Polycarboxylic acid superplasticizer with high slump loss resistance in high-temperature environment and preparation method thereof | |
| CN115067324A (en) | High-molecular polycarboxylate dispersant and preparation method thereof | |
| IL224310A (en) | Boron compound suspension | |
| JPH04185606A (en) | Redispersible acrylic resin powder prepared from emulsion containing protective colloid and production of the powder | |
| CA1286445C (en) | Absorbent polymers, their manufacture and uses | |
| Bastiat et al. | Micellar copolymerization of associative polymers: Study of the effect of acrylamide on sodium dodecyl sulfate–poly (propylene oxide) methacrylate mixed micelles | |
| CN111269462A (en) | Modified mica powder composite material and preparation and application thereof | |
| CN106582430A (en) | Novel carboxylate phosphate ternary polymerization dispersing agent and preparation process thereof | |
| CN111285953B (en) | Acrylic emulsion and preparation method thereof | |
| CN107955094A (en) | A kind of preparation method of electrolyte-resistant type hydrophobic association thickener | |
| CN103408698A (en) | In-situ redox initiation for preparing polyacrylamide water-drum water dispersion | |
| CN112920325A (en) | Dispersing agent and preparation method and application thereof | |
| CN111171215B (en) | Environment-friendly agricultural dispersant and preparation method thereof | |
| CN112940194B (en) | Preparation method and application of inorganic pigment and filler water-based dispersant | |
| CN110563892A (en) | water-based dispersant for transparent iron oxide and preparation method and application thereof | |
| CN111171214B (en) | Polycarboxylate agricultural dispersant and preparation method thereof | |
| JP2959796B2 (en) | Water dispersible resin composition and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |