CN115581231A - Mixed emulsifier containing propiconazole missible oil - Google Patents
Mixed emulsifier containing propiconazole missible oil Download PDFInfo
- Publication number
- CN115581231A CN115581231A CN202211290320.6A CN202211290320A CN115581231A CN 115581231 A CN115581231 A CN 115581231A CN 202211290320 A CN202211290320 A CN 202211290320A CN 115581231 A CN115581231 A CN 115581231A
- Authority
- CN
- China
- Prior art keywords
- isomeric
- block copolymer
- mixed emulsifier
- tristyrylphenol
- propiconazole
- 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.)
- Pending
Links
- 239000005822 Propiconazole Substances 0.000 title claims abstract description 41
- STJLVHWMYQXCPB-UHFFFAOYSA-N propiconazole Chemical compound O1C(CCC)COC1(C=1C(=CC(Cl)=CC=1)Cl)CN1N=CN=C1 STJLVHWMYQXCPB-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 39
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 68
- 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 claims abstract description 65
- 229920001400 block copolymer Polymers 0.000 claims abstract description 42
- 125000005233 alkylalcohol group Chemical group 0.000 claims abstract description 32
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims abstract description 32
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 27
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 239000004495 emulsifiable concentrate Substances 0.000 claims abstract description 20
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- OOCMUZJPDXYRFD-UHFFFAOYSA-L calcium;2-dodecylbenzenesulfonate Chemical compound [Ca+2].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O OOCMUZJPDXYRFD-UHFFFAOYSA-L 0.000 claims abstract description 11
- -1 alkyl phenol Chemical compound 0.000 claims abstract description 6
- 239000000575 pesticide Substances 0.000 claims abstract description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 31
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 230000000379 polymerizing effect Effects 0.000 claims description 15
- 239000003999 initiator Substances 0.000 claims description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 10
- 229920000570 polyether Polymers 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 238000007670 refining Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 239000011552 falling film Substances 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000006071 cream Substances 0.000 claims description 3
- 239000004322 Butylated hydroxytoluene Substances 0.000 claims description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 2
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 2
- 229940095259 butylated hydroxytoluene Drugs 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 239000010408 film Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims 2
- 230000005540 biological transmission Effects 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 235000011056 potassium acetate Nutrition 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- 238000000926 separation method Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 241000233866 Fungi Species 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 1
- 241000235349 Ascomycota Species 0.000 description 1
- 241000221198 Basidiomycota Species 0.000 description 1
- 241000221785 Erysiphales Species 0.000 description 1
- 240000005561 Musa balbisiana Species 0.000 description 1
- 235000018290 Musa x paradisiaca Nutrition 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- IXKCDYCGOZFZFK-UHFFFAOYSA-N calcium;dodecylbenzene Chemical compound [Ca].CCCCCCCCCCCCC1=CC=CC=C1 IXKCDYCGOZFZFK-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000002888 effect on disease Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 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
- A01N25/30—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 characterised by the surfactants
-
- 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
-
- 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
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P3/00—Fungicides
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Zoology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Toxicology (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Microbiology (AREA)
- Mycology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention discloses a mixed emulsifier containing propiconazole missible oil, which relates to the technical field of pesticide preparations and comprises three components C of an isomeric alkyl alcohol block copolymer A, a tristyrylphenol polyoxyethylene polyoxypropylene ether B and calcium dodecylbenzene sulfonate, which are mixed according to a certain proportion, wherein the proportion of the isomeric alkyl phenol block copolymer to the tristyrylphenol polyoxyethylene polyoxypropylene ether is 1-9: the ratio of C is 1: ethylene oxide: the input amount of the propylene oxide =1: 2-4: 3-5, the addition amount of the catalyst is 0.2-0.6 ‰ of the isomeric tridecanol, and the mixed emulsifier is used for preparing emulsifiable concentrate containing propiconazole in pesticide preparations.
Description
Technical Field
The invention relates to the technical field of pesticide preparations, in particular to a mixed emulsifier containing propiconazole missible oil.
Background
The molecular formula of propiconazole is C 15 H 17 Cl 2 N 3 O 2， The propiconazole emulsifiable solution has the relative molecular mass of 342.2, the melting point of-23 ℃, the solubility in water of 100mg/L (20 ℃), and is mutually soluble with ethanol, acetone, toluene and n-octanol at 25 ℃, has better control effect on diseases caused by ascomycetes, basidiomycetes and imperfect fungi such as wheat take-all, powdery mildew, rust disease and banana leaf spot, can effectively control diseases caused by most of higher fungi, and has good control effect on anthracnose. The stability under the conditions of low temperature and high temperature is good, the educt after cold storage is less than 0.3ml, the mass fraction of the propiconazole after hot storage is more than 95 percent before hot storage, and the pH value and the stability meet the requirements.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a mixed emulsifier containing propiconazole emulsifiable concentrate, which solves the problems of insufficient stability, easy oil separation, paste separation and turbid cold storage of the conventional propiconazole emulsion.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a mixed emulsifier containing propiconazole missible oil comprises three components C of an isomeric alkyl alcohol block copolymer A, a tristyrylphenol polyoxyethylene polyoxypropylene ether B and calcium dodecyl benzene sulfonateMixing according to a certain proportion, wherein the proportion of the isomeric alkylphenol block copolymer to the tristyrylphenol polyoxyethylene polyoxypropylene ether is 1 to 9: the proportion of C is 1: iso-C 13 H 27 O(C 2 H 4 O) n (C 3 H 8 O) m (C 2 H 4 O) n And H, wherein m = 6-8, n = 3-5, and the mixed emulsifier is used for preparing emulsifiable concentrate containing propiconazole in pesticide preparations.
Preferably, the preferable ratio of the isomeric alkylphenol block copolymer to the tristyrylphenol polyoxyethylene polyoxypropylene ether is 2-3.
Preferably, the (component a + component B): the preferable proportion of C is 3.
Preferably, the mixed emulsifier accounts for 1 to 20 percent of the percentage of the missible oil containing the propiconazole.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation process of a mixed emulsifier containing propiconazole emulsifiable concentrate comprises the following steps:
step S1, preparing an isomeric alkyl alcohol block copolymer: the isomeric alkyl alcohol block copolymer is prepared by polymerizing ethylene oxide and propylene oxide in a certain mode by taking isomeric tridecanol as an initiator;
s2, preparing tristyrylphenol polyoxyethylene polyoxypropylene ether B, polymerizing tristyrylphenol and ethylene oxide to generate tristyrylphenol polyoxyethylene ether, then carrying out aftertreatment refining on the tristyrylphenol polyoxyethylene ether, and finally carrying out propoxylation reaction on the refined phenol polyoxyethylene ether under the action of a double-metal cyanide complex catalyst to obtain the tristyrylphenol polyoxyethylene ether B;
and S3, mixing the isomeric alkyl alcohol block copolymer A, the tristyrylphenol polyoxyethylene polyoxypropylene ether B and the calcium dodecyl benzene sulfonate according to a certain proportion to obtain the mixed emulsifier for the propiconazole emulsifiable concentrate.
Preferably, the preparation of the isomeric alkyl alcohol block copolymer comprises the steps of:
step S01, pretreatment: premixing isomeric tridecanol and sodium hydroxide catalyst according to a certain proportion, then putting into a reaction kettle, then removing air in the reaction kettle by using nitrogen displacement, and heating to 65-75 ℃;
step S02, polymerization: adding propylene oxide, isomeric tridecanol initiator and strong base catalyst into a reaction kettle to form negative oxygen ions, breaking carbon-oxygen bonds of the propylene oxide to form terminal hydroxyl groups, quickly dehydrating and connecting the terminal hydroxyl groups with the hydroxyl groups in the initiator, continuously injecting nitrogen gas in the reaction to ensure an anaerobic environment, growing a chain by transferring anionic charges, neutralizing charges of a chain segment by adding a chain terminator after reaching an expected chain length to terminate the reaction, and obtaining isomeric tridecanol polypropylene ether, namely iso-C 13 H 27 O(C 3 H 8 O) m H；
Step S03, front-stage Polymer: adding ethylene oxide into isotridecanol polypropylene alkane, neutralizing the charge of chain segment by adding chain terminator to terminate reaction after reaching the desired chain length, and adding ethylene oxide to obtain propylene oxide-ethylene oxide block copolymer, i.e. iso-C 13 H 27 O(C 2 H 4 O) n (C 3 H 8 O) m (C 2 H 4 O) n H；
And step S04, post-processing: neutralizing the obtained crude product of alcohol polyether to remove alkaline catalyst, filtering to remove salt, adsorbing to remove residual catalyst and colored substances, and rectifying to obtain isomeric tridecanol polyether product with low impurity content, light color and narrow molecular weight distribution, wherein the distillation of polyether is carried out at reduced pressure of about 100 deg.C to remove trace water and other impurities in polyether.
Preferably, the post-treatment adopts a falling film evaporator, the block copolymer is continuously conveyed to a high-speed centrifugal dispersion plate at the upper part of the evaporator to form a liquid film to be reduced, the falling film height can be controlled under certain temperature and reduced pressure conditions, impurities in the product are removed, and 0.05-0.5 percent of di-tert-butyl antioxidant, butylated hydroxytoluene and amine antioxidant are also added to avoid the oxidation of the polyether product.
The process for preparing the mixed emulsifier containing propiconazole cream according to claim 5, wherein the process comprises the following steps: the isomeric tridecanol: ethylene oxide: the input amount of the propylene oxide =1 and is from 2 to 4, and the addition amount of the catalyst is from 0.2 to 0.6 per thousand of the isomeric tridecanol.
Preferably, in the reaction of tristyrylphenol polyoxyethylene polyoxypropylene ether, the addition number of propylene oxide is 32, and the addition number of ethylene oxide is 28.
Preferably, in the reaction of tristyrylphenol polyoxyethylene polyoxypropylene ether, the tristyrylphenol polyoxyethylene polyoxypropylene ether has a cloud point of 73-79, a pH value of 5-7, a water content of less than 0.5, and an HLB value of 16.2-16.9.
(III) advantageous effects
The invention provides a mixed emulsifier containing propiconazole missible oil, which comprises an isomeric alkyl alcohol block copolymer and tristyrylphenol polyoxyethylene polyoxypropylene ether, wherein an emulsifier with excellent performance is obtained by optimizing the addition number of ethylene oxide and propylene oxide in the preparation of the isomeric alkyl alcohol block copolymer; by introducing EO chains into tristyrylphenol, the salt resistance and the solubility of the product can be improved, the Krafft point can be reduced, and the hydrophilic-lipophilic balance value can be adjusted; the introduction of a PO chain can improve the dispersion force of the product to substances such as dye and the like in oil and water; the mixed emulsifier suitable for propiconazole is obtained by optimizing the proportion of three components, namely isomeric alkyl alcohol block copolymer, tristyrylphenol polyoxyethylene polyoxypropylene ether and calcium dodecylbenzene sulfonate, and the problems that the stability of the conventional propiconazole emulsion is insufficient, and oil separation, paste separation and cold storage turbidity are easy to occur are solved.
Detailed Description
All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
The invention provides a technical scheme that: the preparation process of the mixed emulsifier containing the propiconazole emulsifiable concentrate comprises the following steps:
step S1, preparing an isomeric alkyl alcohol block copolymer: the isomeric alkyl alcohol block copolymer is prepared by polymerizing isomeric tridecanol serving as an initiator and ethylene oxide and propylene oxide according to a certain mode, and the obtained structural general formula is as follows: iso-C 13 H 27 O(C 2 H 4 O) n (C 3 H 8 O) m (C 2 H 4 O) n H, wherein m =6,n =3;
s2, preparing tristyrylphenol polyoxyethylene polyoxypropylene ether B, polymerizing tristyrylphenol and ethylene oxide to generate tristyrylphenol polyoxyethylene ether, then carrying out aftertreatment refining on the tristyrylphenol polyoxyethylene ether, and finally carrying out propoxylation reaction on the refined phenol polyoxyethylene ether under the action of a double-metal cyanide complex catalyst to obtain the tristyrylphenol polyoxyethylene ether B;
and S3, mixing the isomeric alkyl alcohol block copolymer A, the tristyrylphenol polyoxyethylene polyoxypropylene ether B and the calcium dodecyl benzene sulfonate according to a ratio of 1.
Example 2
The invention provides a technical scheme that: the preparation process of the mixed emulsifier containing the propiconazole emulsifiable concentrate comprises the following steps:
step S1, preparing an isomeric alkyl alcohol block copolymer: the isomeric alkyl alcohol block copolymer is prepared by polymerizing ethylene oxide and propylene oxide in a certain mode by using isomeric tridecanol as an initiator, and the obtained structural general formula is as follows: iso-C 13 H 27 O(C 2 H 4 O) n (C 3 H 8 O) m (C 2 H 4 O) n H, wherein m =6,n =3;
s2, preparing tristyrylphenol polyoxyethylene polyoxypropylene ether B, polymerizing tristyrylphenol and ethylene oxide to generate tristyrylphenol polyoxyethylene ether, then carrying out aftertreatment refining on the tristyrylphenol polyoxyethylene ether, and finally carrying out propoxylation reaction on the refined phenol polyoxyethylene ether under the action of a double-metal cyanide complex catalyst to obtain the tristyrylphenol polyoxyethylene ether B;
and S3, mixing the isomeric alkyl alcohol block copolymer A, the tristyrylphenol polyoxyethylene polyoxypropylene ether B and the calcium dodecyl benzene sulfonate according to a ratio of 1.
Example 3
The invention provides a technical scheme that: the preparation process of the propiconazole-containing missible oil mixed emulsifier comprises the following steps:
step S1, preparing an isomeric alkyl alcohol block copolymer: the isomeric alkyl alcohol block copolymer is prepared by polymerizing ethylene oxide and propylene oxide in a certain mode by using isomeric tridecanol as an initiator, and the obtained structural general formula is as follows: iso-C 13 H 27 O(C 2 H 4 O) n (C 3 H 8 O) m (C 2 H 4 O) n H, wherein m =7,n =4;
s2, preparing tristyrylphenol polyoxyethylene polyoxypropylene ether B, polymerizing tristyrylphenol and ethylene oxide to generate tristyrylphenol polyoxyethylene ether, then carrying out aftertreatment refining on the tristyrylphenol polyoxyethylene ether, and finally carrying out propoxylation reaction on the refined phenol polyoxyethylene ether under the action of a double-metal cyanide complex catalyst to obtain the tristyrylphenol polyoxyethylene ether B;
and S3, mixing the isomeric alkyl alcohol block copolymer A, the tristyrylphenol polyoxyethylene polyoxypropylene ether B and the calcium dodecyl benzene sulfonate according to the proportion of 9.
Example 4
The invention provides a technical scheme that: the preparation process of the mixed emulsifier containing the propiconazole emulsifiable concentrate comprises the following steps:
step S1, preparing an isomeric alkyl alcohol block copolymer: the isomeric alkyl alcoholThe block copolymer is prepared by polymerizing ethylene oxide and propylene oxide in a certain mode by taking isomeric tridecanol as an initiator to obtain a copolymer with a structural general formula: iso-C 13 H 27 O(C 2 H 4 O) n (C 3 H 8 O) m (C 2 H 4 O) n H, wherein m =8,n =4;
s2, preparing tristyrylphenol polyoxyethylene polyoxypropylene ether B, polymerizing tristyrylphenol and ethylene oxide to generate tristyrylphenol polyoxyethylene ether, then carrying out aftertreatment refining on the tristyrylphenol polyoxyethylene ether, and finally carrying out propoxylation reaction on the refined phenol polyoxyethylene ether under the action of a double-metal cyanide complex catalyst to obtain the tristyrylphenol polyoxyethylene ether B;
and S3, mixing three components C of the isomeric alkyl alcohol block copolymer A, the tristyrylphenol polyoxyethylene polyoxypropylene ether B and the calcium dodecyl benzene sulfonate according to the proportion of 6.
Example 5
The invention provides a technical scheme that: the preparation process of the mixed emulsifier containing the propiconazole emulsifiable concentrate comprises the following steps:
step S1, preparing an isomeric alkyl alcohol block copolymer: the isomeric alkyl alcohol block copolymer is prepared by polymerizing isomeric tridecanol serving as an initiator and ethylene oxide and propylene oxide according to a certain mode, and the obtained structural general formula is as follows: iso-C 13 H 27 O(C 2 H 4 O) n (C 3 H 8 O) m (C 2 H 4 O) n H, wherein m =8, n =5;
s2, preparing tristyrylphenol polyoxyethylene polyoxypropylene ether B, polymerizing tristyrylphenol and ethylene oxide to generate tristyrylphenol polyoxyethylene ether, then carrying out aftertreatment refining on the tristyrylphenol polyoxyethylene ether, and finally carrying out propoxylation reaction on the refined phenol polyoxyethylene ether under the action of a double-metal cyanide complex catalyst to obtain the tristyrylphenol polyoxyethylene ether B;
and S3, mixing three components C of the isomeric alkyl alcohol block copolymer A, the tristyrylphenol polyoxyethylene polyoxypropylene ether B and the calcium dodecyl benzene sulfonate according to the proportion of 6.
Examples of the experiments
The emulsifying dispersion effect of the mixed emulsifiers of examples 1 to 5 was investigated by experiments, and the following table was obtained:
in conclusion, the mixed emulsifier containing the propiconazole missible oil comprises isomeric alkyl alcohol block copolymers and tristyrylphenol polyoxyethylene polyoxypropylene ether, and the emulsifier with excellent performance is obtained by optimizing the addition number of ethylene oxide and propylene oxide in the preparation of the isomeric alkyl alcohol block copolymers; by introducing EO chains into tristyrylphenol, the salt resistance and the solubility of the product can be improved, the Krafft point can be reduced, and the hydrophilic-lipophilic balance value can be adjusted; the introduction of a PO chain can improve the dispersing force of the product to substances such as dye and the like in oil and water; the mixed emulsifier suitable for propiconazole is obtained by optimizing the proportion of three components, namely isomeric alkyl alcohol block copolymer, tristyrylphenol polyoxyethylene polyoxypropylene ether and calcium dodecylbenzene sulfonate, and the problems that the stability of the conventional propiconazole emulsion is insufficient, and oil separation, paste separation and cold storage turbidity are easy to occur are solved.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. Propiconazole-containing missible oil mixtureThe emulsifier is characterized by comprising an isomeric alkyl alcohol block copolymer A, a tristyrylphenol polyoxyethylene polyoxypropylene ether B and calcium dodecyl benzene sulfonate which are mixed according to a certain proportion, wherein the ratio of the isomeric alkyl alcohol block copolymer to the tristyrylphenol polyoxyethylene polyoxypropylene ether is 1: the proportion of C is 1 13 H 27 O(C 2 H 4 O) n (C 3 H 8 O) m (C 2 H 4 O) n And H, wherein m = 6-8, n = 3-5, and the mixed emulsifier is used for preparing emulsifiable concentrate containing propiconazole in pesticide preparations.
2. The mixed emulsifier containing propiconazole emulsifiable concentrate as set forth in claim 1, wherein: the preferable proportion of the isomeric alkylphenol block copolymer to the tristyrylphenol polyoxyethylene polyoxypropylene ether is 2 to 3, and the dosage of the mixed emulsifier accounts for 1 to 20 percent of the emulsifiable concentrate containing the propiconazole.
3. The mixed emulsifier containing propiconazole emulsifiable concentrate as set forth in claim 1, wherein: the (component A + component B): the preferable proportion of C is 3.
4. The mixed emulsifier containing propiconazole emulsifiable concentrate as set forth in claim 1, wherein: the dosage of the mixed emulsifier accounts for 1 to 20 percent of the emulsifiable concentrate containing the propiconazole.
5. The process for preparing a mixed emulsifier containing propiconazole cream according to any one of claims 1 to 4, wherein: the preparation process of the mixed emulsifier comprises the following steps:
step S1, preparing an isomeric alkyl alcohol block copolymer: the isomeric tridecanol alkyl alcohol block copolymer is prepared by polymerizing ethylene oxide and propylene oxide in a certain mode by taking isomeric tridecanol as an initiator;
s2, preparing tristyrylphenol polyoxyethylene polyoxypropylene ether B, polymerizing tristyrylphenol and ethylene oxide to generate tristyrylphenol polyoxyethylene ether, then carrying out aftertreatment refining on the tristyrylphenol polyoxyethylene ether, and finally carrying out propoxylation reaction on the refined phenol polyoxyethylene ether under the action of a double-metal cyanide complex catalyst to obtain the tristyrylphenol polyoxyethylene ether B;
and S3, mixing the isomeric alkyl alcohol block copolymer A, the tristyrylphenol polyoxyethylene polyoxypropylene ether B and the calcium dodecyl benzene sulfonate according to a certain proportion to obtain the mixed emulsifier for the propiconazole emulsifiable concentrate.
6. The process for preparing the mixed emulsifier containing propiconazole cream according to claim 5, wherein the isomeric alkyl alcohol block copolymer is obtained by using isomeric tridecanol as a starting material and ethylene oxide and propylene oxide are polymerized in a certain manner, and the preparation of the isomeric alkyl alcohol block copolymer comprises the following steps:
step S01: pretreatment: premixing isomeric tridecanol and a sodium hydroxide catalyst according to a certain proportion, putting into a reaction kettle, then removing air in the reaction kettle by using nitrogen replacement, and heating to 65-75 ℃;
step S02: polymerization: adding propylene oxide, an isomeric tridecanol initiator and a strong base catalyst into a reaction kettle to form negative oxygen ions, breaking carbon-oxygen bonds of the propylene oxide to form terminal hydroxyl groups, quickly dehydrating and connecting the terminal hydroxyl groups with the hydroxyl groups in the initiator, continuously injecting nitrogen gas in the reaction to ensure an anaerobic environment, increasing a chain through the transmission of anionic charges, and neutralizing the charges of a chain segment by adding a chain terminator after reaching an expected chain length to terminate the reaction to obtain the isomeric tridecanol polypropylene ether, namely iso-C 13 H 27 O(C 3 H 8 O) m H；
Step S03: polymer of the preceding stage: ethylene oxide was added to the isomeric tridecanol polypropene and chain termination was performed by adding chain terminator after the desired chain length was reachedNeutralizing the charge of the chain segment with an agent to terminate the reaction, and adding ethylene oxide to obtain a propylene oxide ethylene oxide block copolymer, i.e., iso-C 13 H 27 O(C 2 H 4 O) n (C 3 H 8 O) m (C 2 H 4 O) n H；
Step S04: and (3) post-treatment: neutralizing the obtained crude product of alcohol polyether to remove alkaline catalyst, filtering to remove salt, adsorbing to remove residual catalyst and colored substances, and rectifying to obtain isomeric tridecanol polyether product with low impurity content, light color and narrow molecular weight distribution, wherein the distillation of polyether is carried out at reduced pressure of about 100 deg.C to remove trace water and other impurities in polyether.
7. The process for preparing a mixed emulsifier containing propiconazole emulsifiable concentrate as set forth in claim 6, wherein: in step S04, a falling film evaporator is adopted in the post-treatment, the block copolymer is continuously conveyed to a high-speed centrifugal dispersion disc at the upper part of the evaporator to form a liquid film to be reduced, the falling film height can be controlled under a certain temperature and reduced pressure condition, impurities in the product are removed, and 0.05-0.5 percent of di-tert-butyl antioxidant, butylated hydroxytoluene and amine antioxidant are added to avoid oxidation of the polyether product.
8. The process for preparing a mixed emulsifier containing propiconazole emulsifiable concentrate as set forth in claim 6, wherein: the isomeric tridecanol: ethylene oxide: the input amount of the propylene oxide =1 and is from 2 to 4, and the addition amount of the catalyst is from 0.2 to 0.6 per thousand of the isomeric tridecanol.
9. The process for preparing a mixed emulsifier containing propiconazole emulsifiable concentrate as set forth in claim 6, wherein: the tristyrylphenol polyoxyethylene polyoxypropylene ether is prepared by polymerizing tristyrylphenol and ethylene oxide through potassium acetate and a catalyst to generate tristyrylphenol polyoxyethylene ether, then carrying out aftertreatment refining on the tristyrylphenol polyoxyethylene ether, and finally carrying out propoxylation reaction on the refined phenol polyoxyethylene ether under the action of a double-metal cyanide complex catalyst to obtain the tristyrylphenol polyoxyethylene polyoxypropylene ether with the molecular weight dispersion coefficient of less than 1.12.
10. The process for preparing a mixed emulsifier containing propiconazole emulsifiable concentrate as set forth in claim 9, wherein: the addition number of the propylene oxide is 32, the addition number of the ethylene oxide is 28, the cloud point of the tristyrylphenol polyoxyethylene polyoxypropylene ether is 73-79, the pH value is 5-7, the water content is less than 0.5, and the HLB value is 16.2-16.9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211290320.6A CN115581231A (en) | 2022-10-21 | 2022-10-21 | Mixed emulsifier containing propiconazole missible oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211290320.6A CN115581231A (en) | 2022-10-21 | 2022-10-21 | Mixed emulsifier containing propiconazole missible oil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115581231A true CN115581231A (en) | 2023-01-10 |
Family
ID=84779394
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211290320.6A Pending CN115581231A (en) | 2022-10-21 | 2022-10-21 | Mixed emulsifier containing propiconazole missible oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115581231A (en) |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235138A (en) * | 2008-02-22 | 2008-08-06 | 江苏钟山化工有限公司 | Epoxy propane/epoxy ethane block copolyether and its preparation method and use |
| CN101779624A (en) * | 2010-02-05 | 2010-07-21 | 深圳诺普信农化股份有限公司 | Difenoconazole and propiconazole compound water emulsion and preparation method thereof |
| CN102197803A (en) * | 2010-03-26 | 2011-09-28 | 招远市新亚化工有限公司 | Pesticide emulsifier |
| CN103461357A (en) * | 2013-09-15 | 2013-12-25 | 上海悦萌环保科技有限公司 | Triptonide plant source emulsifiable concentrate |
| CN105660654A (en) * | 2016-02-19 | 2016-06-15 | 河北岗恩生物科技有限公司 | Propiconazole arene-free missible oil and preparation method thereof |
| CN106554492A (en) * | 2015-09-28 | 2017-04-05 | 上海东大化学有限公司 | A kind of isomery alcohol alkoxy polyether and preparation method thereof |
| CN107141465A (en) * | 2017-06-05 | 2017-09-08 | 浙江皇马科技股份有限公司 | A kind of styrylphenol polyoxyethylene ether and preparation method thereof |
| CN109938014A (en) * | 2019-04-30 | 2019-06-28 | 江苏艾津农化有限责任公司 | A kind of environmental-protecting and high-efficient type propiconazole emulsifiable concentrate and preparation method thereof |
| CN110540638A (en) * | 2019-08-21 | 2019-12-06 | 佳化化学科技发展（上海）有限公司 | Preparation method of emulsifier and application of emulsifier in preparation of pesticide emulsifiable concentrate |
| CN112300380A (en) * | 2020-10-14 | 2021-02-02 | 上海科沣新材料有限公司 | Alkoxylation block copolymer of agricultural auxiliary agent and preparation method and application thereof |
| CN112385650A (en) * | 2019-08-16 | 2021-02-23 | 南京科翼新材料有限公司 | Emulsifier suitable for multiple pesticide emulsion in water and application method thereof |
| CN112841189A (en) * | 2021-01-26 | 2021-05-28 | 河南远见农业科技有限公司 | Rice field herbicide and preparation method and application thereof |
| CN113214466A (en) * | 2021-06-04 | 2021-08-06 | 浙江皇马科技股份有限公司 | Tristyryl phenol block polyether, sulfate ammonium salt and preparation method thereof |
-
2022
- 2022-10-21 CN CN202211290320.6A patent/CN115581231A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235138A (en) * | 2008-02-22 | 2008-08-06 | 江苏钟山化工有限公司 | Epoxy propane/epoxy ethane block copolyether and its preparation method and use |
| CN101779624A (en) * | 2010-02-05 | 2010-07-21 | 深圳诺普信农化股份有限公司 | Difenoconazole and propiconazole compound water emulsion and preparation method thereof |
| CN102197803A (en) * | 2010-03-26 | 2011-09-28 | 招远市新亚化工有限公司 | Pesticide emulsifier |
| CN103461357A (en) * | 2013-09-15 | 2013-12-25 | 上海悦萌环保科技有限公司 | Triptonide plant source emulsifiable concentrate |
| CN106554492A (en) * | 2015-09-28 | 2017-04-05 | 上海东大化学有限公司 | A kind of isomery alcohol alkoxy polyether and preparation method thereof |
| CN105660654A (en) * | 2016-02-19 | 2016-06-15 | 河北岗恩生物科技有限公司 | Propiconazole arene-free missible oil and preparation method thereof |
| CN107141465A (en) * | 2017-06-05 | 2017-09-08 | 浙江皇马科技股份有限公司 | A kind of styrylphenol polyoxyethylene ether and preparation method thereof |
| CN109938014A (en) * | 2019-04-30 | 2019-06-28 | 江苏艾津农化有限责任公司 | A kind of environmental-protecting and high-efficient type propiconazole emulsifiable concentrate and preparation method thereof |
| CN112385650A (en) * | 2019-08-16 | 2021-02-23 | 南京科翼新材料有限公司 | Emulsifier suitable for multiple pesticide emulsion in water and application method thereof |
| CN110540638A (en) * | 2019-08-21 | 2019-12-06 | 佳化化学科技发展（上海）有限公司 | Preparation method of emulsifier and application of emulsifier in preparation of pesticide emulsifiable concentrate |
| CN112300380A (en) * | 2020-10-14 | 2021-02-02 | 上海科沣新材料有限公司 | Alkoxylation block copolymer of agricultural auxiliary agent and preparation method and application thereof |
| CN112841189A (en) * | 2021-01-26 | 2021-05-28 | 河南远见农业科技有限公司 | Rice field herbicide and preparation method and application thereof |
| CN113214466A (en) * | 2021-06-04 | 2021-08-06 | 浙江皇马科技股份有限公司 | Tristyryl phenol block polyether, sulfate ammonium salt and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE69403967T2 (en) | METHOD FOR PRODUCING AQUEOUS POLYMER EMULSIONS | |
| US9353195B2 (en) | Emulsifier for emulsion polymerization and emulsion polymerization method using same | |
| CN110760035B (en) | Self-thickening associated acrylate emulsion and preparation method thereof | |
| US20020045703A1 (en) | Processes for preparing aqueous polymer emulsions | |
| WO1995004771A1 (en) | Reaction products from olefinically unsaturated carboxylic acids and polyetherols and their use as demulsifying agents for crude oil emulsions | |
| WO2013051205A1 (en) | Emulsion polymerization method using reactive emulsifying agent, aqueous polymer dispersion obtained by same, and polymer film | |
| NO171682B (en) | REACTION BLENDS CONTAINING COPOLYMERS OF HYDROPHOBE ACRYLIC RESP. METACRYLIC ACID ESTERS AND HYDROPHILIC COMMONOMERS, PREPARING AND USING THEREOF | |
| CN105418835A (en) | Preparing method for core-shell structure functionality acrylate polymer particles for toughening polycarbonate | |
| CN115581231A (en) | Mixed emulsifier containing propiconazole missible oil | |
| CN108570131B (en) | Preparation method of hybrid emulsion of epoxy ester resin aqueous dispersion and acrylic resin | |
| CN106366246B (en) | A kind of butadiene styrene vinyl pyridine latex and preparation method thereof | |
| CN115746173B (en) | Block chain transfer agent, preparation method and application thereof, and preparation method of ABS grafted latex | |
| CN112279968B (en) | Preparation method of unsaturated fatty acid glycidyl ester modified soap-free acrylic emulsion | |
| CN106543298A (en) | A kind of method that addition assistant for emulsifying agent prepares EVA emulsions | |
| CN105949408B (en) | The preparation method of low viscosity polymer polyols | |
| CN113278442A (en) | Multi-branch silicon-containing polyether demulsifier, compound demulsifier and preparation method thereof | |
| CN104761687B (en) | The preparation method of heatproof fluoro containing polymerses surfactant | |
| CN107075107A (en) | Method for producing polyalkylene glycol, viscosity index improver, lubricating oil composition, and method for producing lubricating oil composition | |
| CN113004455B (en) | Macromolecular anionic-nonionic emulsifier and preparation method thereof | |
| CN117866134B (en) | Vinyl chloride suspension polymerization dispersing agent with defoaming function and preparation method and application thereof | |
| US2671760A (en) | Lubricating oil compositions | |
| Ayhan et al. | Effect of anionic/nonionic surfactant systems on the properties of water-based styrene/acrylic copolymer latexes | |
| CN106543328B (en) | A method of alcohols solvent is added and prepares EVA lotion | |
| CN115160508B (en) | Polycarboxylate viscosity reducing agent containing polyether chain segments, and preparation method and application thereof | |
| CN110862476B (en) | Free radical dispersion polymerization method of surfactant solvent system |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20230110 |
|
| RJ01 | Rejection of invention patent application after publication |