CN113461604A - Method for preparing triclopyr butoxyethyl ester by aqueous phase synthesis method - Google Patents
Method for preparing triclopyr butoxyethyl ester by aqueous phase synthesis method Download PDFInfo
- Publication number
- CN113461604A CN113461604A CN202111023438.8A CN202111023438A CN113461604A CN 113461604 A CN113461604 A CN 113461604A CN 202111023438 A CN202111023438 A CN 202111023438A CN 113461604 A CN113461604 A CN 113461604A
- Authority
- CN
- China
- Prior art keywords
- reaction kettle
- triclopyr
- temperature
- controlling
- sodium
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
-
- 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
- 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
- A01N25/22—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 ingredients stabilising the active ingredients
-
- 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
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Dentistry (AREA)
- Environmental Sciences (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Toxicology (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pyridine Compounds (AREA)
Abstract
A method for preparing triclopyr butoxyethyl ester by a water phase synthesis method is characterized in that triclopyr sodium and chloracetyl chloride are used as raw materials to generate triclopyr acetyl chloride, and then the triclopyr acetyl chloride reacts with 2-butoxyethanol to generate triclopyr butoxyethyl ester, and all reactions are carried out in a water phase; the preparation method can improve the reaction efficiency, reduce side reactions, improve the product purity and improve the purity to 98.8-99.2%; the yield is improved to 99.2 to 99.5 percent; can also reduce the erosion of rainwater to the pesticide, and overcomes the defect that triclopyr butoxyethyl acetate can be effective only when no rainwater exists within 2 hours of using the pesticide.
Description
Technical Field
The invention relates to a method for preparing triclopyr butoxyethyl ester by a water phase synthesis method, belonging to the technical field of chemical synthesis.
Background
The pure product of triclopyr butoxyethyl acetate is a fluffy solid, the melting point is 149-150 ℃, the vapor pressure is 0.168mPa (25 ℃), the product is slightly soluble in water, ethanol, acetone and the like, and the solubility at 25 ℃ is as follows: 440mg/L of water, 989g/kg of acetone, 27.3g/kg of chloroform, 410mg/kg of hexane and 307g/kg of octanol.
Triclopyr butoxyethyl acetate belongs to agricultural herbicides, can be absorbed by leaves and roots of plants, is transferred to plants, can prevent and kill weeds in rice fields and wheat fields, and can also be used for plantation; in pastures, annual and perennial herbaceous weeds can be controlled; in forests, the herbicide can be used for breeding treatment, conifer treatment and weeding in industrial areas, and has the advantages of strong pesticide effect, good mixing property and good low temperature resistance; however, triclopyr butoxyethyl acetate is effective within 2 hours of administration without rain, and has poor soil adsorption capacity.
At present, the preparation method of triclopyr butoxyethyl ester is as follows: taking sodium trichloropyridinol as a raw material in an organic phase, carrying out etherification reaction with methyl chloroacetate to generate methyl trichloro-pyridoxyacetate, hydrolyzing to generate sodium trichloro-pyridoxyacetate, releasing methanol, acidifying to generate the trichloro-pyridoxyacetate, and carrying out esterification reaction with ethylene glycol monobutyl ether under the catalysis of sulfuric acid to obtain butoxy ethyl trichloro-pyridoxyacetate; reacting trichloropyridine sodium phenolate, methyl chloroacetate and dimethylformamide in a water phase to generate 2- (3,5, 6-trichloro-2-pyridyloxy) methyl acetate, and then reacting the 2- (3,5, 6-trichloro-2-pyridyloxy) methyl acetate with ethylene glycol monobutyl ether to generate trichloro-acetoxy ethyl acetate; in the organic phase, trichloropyridine sodium alcoholate is used as a raw material, hydrochloric acid is used for acidification, ethyl acetate is used for extraction, and after an organic layer is washed, the solvent is removed through desolventization to obtain an intermediate trichloropyritinol; reacting with oxalyl chloride, and removing oxalyl chloride to obtain triclopyr; then reacting with 2-butoxyethanol to obtain triclopyr butoxyethyl ester.
The preparation method of the triclopyr butoxyethyl ester still has the following problems: the reaction speed in the organic phase is slow, the generated three wastes are more, although the aqueous phase synthesis method can be used, the generation of the three wastes is reduced by the reaction in the aqueous phase, the large-scale preparation is difficult to carry out by the aqueous phase synthesis method, and the problem of layering is easy to occur in the reaction, so that the contact between reactants is incomplete, and the reaction is difficult to fully carry out.
Therefore, the development of a method for synthesizing triclopyr butoxyethyl ester is a problem which needs to be solved urgently at present, and the method can reduce the generation of three wastes, reduce layering, promote full reaction between reactants, modify pesticide effect and improve soil adsorption capacity.
Patent CN110204480A discloses a method for preparing butoxyethyl triclopyr by a water phase synthesis method, which comprises the following steps: adding tetrachloropyridine, sodium hydroxide, water and a catalyst into a high-pressure reaction kettle, carrying out heat preservation reaction, filtering, washing with water, and drying a filter cake to obtain trichloropyridine phenol sodium; adding trichloropyridine sodium phenolate, methyl chloroacetate and dimethylformamide into a flask provided with a dryer, a condenser, a thermometer and a stirrer, heating a reaction system under stirring, collecting a filter cake, and drying to obtain 2- (3,5, 6-trichloro-2-pyridyloxy) methyl acetate; adding methyl 2- (3,5, 6-trichloro-2-pyridyloxy) acetate, ethylene glycol monobutyl ether and a catalyst into a flask provided with a dryer, a condenser, a thermometer and a stirrer, and reacting to obtain butoxyethyl triclopyr; the patent has the following defects: the problem of delamination easily occurs during the reaction, which results in incomplete contact between reactants and difficulty in fully carrying out the reaction.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for preparing triclopyr butoxyethyl ester by a water phase synthesis method, which realizes the following purposes: the three wastes in the preparation process of the triclopyr butoxyethyl acetate can be reduced, layering can be reduced, the reactants are promoted to react fully, the pesticide effect can be modified, and the adsorption capacity on soil is improved.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for preparing triclopyr butoxyethyl ester by a water phase synthesis method comprises the steps of firstly using triclopyr sodium and chloracetyl chloride as raw materials to generate triclopyr, then reacting the triclopyr with 2-butoxyethanol to generate triclopyr butoxyethyl ester, and carrying out all reactions in a water phase.
a raw material for preparing triclopyr butoxyethyl ester by a water phase synthesis method comprises the following components in parts by weight: 20-25kg deionized water, 5-5.5kg sodium trichloropyridinol, 2.5-2.8kg chloroacetyl chloride, 0.1-0.2kg sodium dodecyl sulfate, 0.2-0.3kg ethanol, 0.15-0.18kg crosslinking catalyst, 0.05-0.06kg sodium hydroxide, 4-5kg 2-butoxyethanol, 0.2-0.3kg tween 80, 0.3-0.4kg ethyl acetate, 0.1-0.3kg composite catalyst, 0.02-0.03kg sodium bicarbonate and 0.01-0.03kg polyvinylamine.
The raw materials of the crosslinking catalyst comprise the following components in parts by weight: 0.8-1kg of lecithin, 1.5-1.8kg of sodium persulfate, 0.1-0.3kg of maleic anhydride and 0.2-0.3kg of azodiisobutyramidine hydrochloride.
The preparation method of the crosslinking catalyst specifically comprises the following steps: uniformly mixing lecithin, sodium persulfate, maleic anhydride and azodiisobutyramidine hydrochloride, performing microwave oscillation at 40 ℃, controlling the microwave power of the microwave oscillation to be 900W, controlling the microwave oscillation time to be 20min, and obtaining the crosslinking catalyst after the microwave oscillation is finished.
The composite catalyst comprises the following raw materials in parts by weight: 0.1-0.3kg of light calcium carbonate, 0.03-0.04kg of aluminate coupling agent DL-411-A, 2.5-3kg of absolute ethyl alcohol and 0.08-0.1kg of azobisisobutyronitrile.
The preparation method of the composite catalyst comprises the following specific steps: uniformly mixing light calcium carbonate, an aluminate coupling agent DL-411-A and absolute ethyl alcohol, carrying out vacuum reduced pressure distillation at 40-45 ℃, controlling the vacuum pressure at 0.083-0.09MPa, carrying out reduced pressure distillation for 10-12min to obtain a primary composite catalyst, and uniformly mixing the primary composite catalyst and azobisisobutyronitrile to obtain the composite catalyst.
A method for preparing triclopyr butoxyethyl ester by a water phase synthesis method comprises the following steps: the first raw material treatment is to prepare triclopyr chloride, the second raw material treatment is to prepare a triclopyr butoxyethyl ester product, and the product is dried.
The first raw material treatment comprises the steps of adding deionized water, sodium trichloropyridinol, chloroacetyl chloride, sodium dodecyl sulfate and ethanol into a reaction kettle at one time, controlling the temperature of the reaction kettle to be 40-45 ℃, controlling the stirring speed of the reaction kettle to be 110rpm, stopping stirring after stirring for 30-35min, controlling the temperature of the reaction kettle to be-5-10 ℃, gradually raising the temperature of the reaction kettle to be 40-45 ℃ after standing for 20-25min, and controlling the temperature raising speed to be 2-2.5 ℃/min.
After the temperature of the reaction kettle is increased to 40-45 ℃, controlling the stirring speed of the reaction kettle to 150-160rpm, adding a crosslinking catalyst and sodium hydroxide into the reaction kettle, preserving the temperature at 40-45 ℃ for 45-50min, and stopping stirring.
And (3) continuously adding 2-butoxyethanol, Tween 80 and ethyl acetate into the reaction kettle, controlling the temperature of the reaction kettle to be 45-50 ℃, controlling the stirring speed of the reaction kettle to be 150-160rpm, stopping stirring after stirring for 20-25min, controlling the temperature of the reaction kettle to be-5-10 ℃, gradually increasing the temperature of the reaction kettle to be 50-55 ℃ after standing for 30-35min, and controlling the heating speed to be 3-3.5 ℃/min.
After the temperature of a reaction kettle is raised to 45-50 ℃, adding the composite catalyst, sodium bicarbonate and polyvinylamine into the reaction kettle, preserving the heat at 45-50 ℃ for 1-1.5h, and stopping stirring.
And drying the product, namely washing the organic layer in the reaction kettle twice by using saturated salt solution, then carrying out vacuum drying, controlling the temperature of the vacuum drying to be 60-65 ℃, controlling the vacuum degree of the vacuum drying to be 100-120Pa, controlling the time of the vacuum drying to be 15-20min, and obtaining the triclopyr butoxyethyl ester after the vacuum drying is finished.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the method for preparing triclopyr butoxyethyl ester by the water phase synthesis method, the raw materials are subjected to secondary freezing treatment in the reaction, so that the reaction efficiency can be improved, the side reactions are reduced, and the product purity is improved, wherein the purity of the triclopyr butoxyethyl ester prepared by the method can reach 98.8% -99.2%;
(2) according to the method for preparing triclopyr butoxyethyl ester by the water phase synthesis method, a cross-linking catalyst is used in the preparation of triclopyr, and a composite catalyst is used in the preparation of the triclopyr butoxyethyl ester product, so that the reaction yield can be improved, and the yield of the triclopyr butoxyethyl ester can reach 99.2% -99.5%;
(3) the method for preparing the triclopyr butoxyethyl ester by the water phase synthesis method can improve the adsorption capacity of the triclopyr butoxyethyl ester on soil, reduce the erosion of rainwater on pesticides, overcome the defect that the triclopyr butoxyethyl ester can be effective only when no rain exists within 2 hours after the triclopyr butoxyethyl ester is used, and by adding 5g of 62% triclopyr butoxyethyl ester missible oil into 20g of completely air-dried soil sample, then respectively carrying out sealing oscillation for 10min and then carrying out simulated rainfall, controlling the rainfall time to be 15min and the simulated rainfall to be 5mm, then testing the soil percolate which passes through the soil after the simulated rainfall, wherein the content of the triclopyr butoxyethyl ester in the soil penetrating fluid is 0.02-0.05 mg/L;
(4) the method for preparing triclopyr butoxyethyl ester by the aqueous phase synthesis method of the invention generates less three wastes and has little pollution to the environment;
(5) the method for preparing triclopyr butoxyethyl ester by the aqueous phase synthesis method does not need high-temperature treatment in production, and reduces energy consumption.
Detailed Description
In order to more clearly understand the technical features, objects, and effects of the present invention, specific embodiments of the present invention will now be described.
Example 1
A method for preparing triclopyr butoxyethyl ester by a water phase synthesis method comprises the following steps:
1. adding 20kg of deionized water, 5kg of sodium trichloropyridinol, 2.5kg of chloroacetyl chloride, 0.1kg of sodium dodecyl sulfate and 0.2kg of ethanol into a reaction kettle at one time, controlling the temperature of the reaction kettle to 40 ℃, controlling the stirring speed of the reaction kettle to 100rpm, stirring for 30min, stopping stirring, controlling the temperature of the reaction kettle to-5 ℃, standing for 20min, gradually increasing the temperature of the reaction kettle to 40 ℃, and controlling the temperature rising speed to be 2 ℃/min;
2. after the temperature of the reaction kettle rises to 40 ℃, controlling the stirring speed of the reaction kettle to 150rpm, adding 0.15kg of crosslinking catalyst and 0.05kg of sodium hydroxide into the reaction kettle, preserving the temperature at 40 ℃ for 45min, and stopping stirring;
the preparation method of the crosslinking catalyst specifically comprises the following steps: uniformly mixing 0.8kg of lecithin, 1.5kg of sodium persulfate, 0.1kg of maleic anhydride and 0.2kg of azodiisobutyramidine hydrochloride, and then carrying out microwave oscillation at 40 ℃, wherein the microwave power of the microwave oscillation is controlled to be 900W, the microwave oscillation time is controlled to be 20min, and the crosslinking catalyst is obtained after the microwave oscillation is finished.
3. Continuously adding 4kg of 2-butoxyethanol, 0.2kg of Tween 80 and 0.3kg of ethyl acetate into the reaction kettle, controlling the temperature of the reaction kettle to 45 ℃, controlling the stirring speed of the reaction kettle to 150rpm, stirring for 20min, stopping stirring, controlling the temperature of the reaction kettle to-5 ℃, standing for 30min, gradually increasing the temperature of the reaction kettle to 50 ℃, and controlling the heating speed to be 3 ℃/min;
4. after the temperature of the reaction kettle rises to 45 ℃, adding 0.1kg of composite catalyst, 0.02kg of sodium bicarbonate and 0.01kg of polyvinylamine into the reaction kettle, preserving the heat at 45 ℃ for 1 hour, and stopping stirring;
the preparation method of the composite catalyst comprises the following specific steps: uniformly mixing 0.1kg of light calcium carbonate, 0.03kg of aluminate coupling agent DL-411-A and 2.5kg of absolute ethyl alcohol, carrying out vacuum reduced pressure distillation at 40 ℃, controlling the vacuum pressure at 0.083MPa, carrying out reduced pressure distillation for 10min to obtain a primary composite catalyst, and uniformly mixing the primary composite catalyst and 0.08kg of azobisisobutyronitrile to obtain a composite catalyst;
5. and (3) washing the organic layer in the reaction kettle twice by using saturated salt solution, then carrying out vacuum drying, controlling the temperature of the vacuum drying to be 60 ℃, controlling the vacuum degree of the vacuum drying to be 100Pa, controlling the time of the vacuum drying to be 15min, and finally obtaining the triclopyr butoxyethyl ester after the vacuum drying is finished.
Example 2
A method for preparing triclopyr butoxyethyl ester by a water phase synthesis method comprises the following steps:
1. adding 22kg of deionized water, 5.2kg of trichloropyridine sodium alcoholate, 2.6kg of chloroacetyl chloride, 0.1kg of sodium dodecyl sulfate and 0.2kg of ethanol into a reaction kettle at one time, controlling the temperature of the reaction kettle to 42 ℃, controlling the stirring speed of the reaction kettle to 105rpm, stirring for 32min, stopping stirring, controlling the temperature of the reaction kettle to-7 ℃, standing for 22min, gradually increasing the temperature of the reaction kettle to 42 ℃, and controlling the temperature-increasing speed to be 2.2 ℃/min;
2. after the temperature of the reaction kettle rises to 42 ℃, controlling the stirring speed of the reaction kettle to 155rpm, adding 0.17kg of crosslinking catalyst and 0.05kg of sodium hydroxide into the reaction kettle, keeping the temperature at 42 ℃ for 47min, and stopping stirring;
the preparation method of the crosslinking catalyst specifically comprises the following steps: uniformly mixing 0.9kg of lecithin, 1.7kg of sodium persulfate, 0.2kg of maleic anhydride and 0.2kg of azodiisobutyramidine hydrochloride, and then carrying out microwave oscillation at 42 ℃, wherein the microwave power of the microwave oscillation is controlled to be 910W, the microwave oscillation time is 22min, and the crosslinking catalyst is obtained after the microwave oscillation is finished.
3. Continuously adding 4.5kg of 2-butoxyethanol, 0.2kg of Tween 80 and 0.3kg of ethyl acetate into the reaction kettle, controlling the temperature of the reaction kettle to 47 ℃, controlling the stirring speed of the reaction kettle to 155rpm, stopping stirring after stirring for 22min, controlling the temperature of the reaction kettle to-7 ℃, gradually increasing the temperature of the reaction kettle to 52 ℃ after standing for 32min, and controlling the temperature-increasing speed to 3.2 ℃/min;
4. after the temperature of the reaction kettle rises to 47 ℃, 0.2kg of composite catalyst, 0.02kg of sodium bicarbonate and 0.02kg of polyvinylamine are added into the reaction kettle, and the mixture is kept warm at 47 ℃ for 1.2h and then is stopped stirring;
the preparation method of the composite catalyst comprises the following specific steps: uniformly mixing 0.2kg of light calcium carbonate, 0.03kg of aluminate coupling agent DL-411-A and 2.7kg of absolute ethyl alcohol, carrying out vacuum reduced pressure distillation at 42 ℃, controlling the vacuum pressure at 0.085MPa, carrying out reduced pressure distillation for 11min to obtain a primary composite catalyst, and uniformly mixing the primary composite catalyst and 0.08kg of azobisisobutyronitrile to obtain a composite catalyst;
5. and (3) washing the organic layer in the reaction kettle twice by using saturated salt solution, then carrying out vacuum drying, controlling the temperature of the vacuum drying to be 62 ℃, controlling the vacuum degree of the vacuum drying to be 110Pa, controlling the time of the vacuum drying to be 17min, and finally obtaining the triclopyr butoxyethyl ester after the vacuum drying is finished.
Example 3
A method for preparing triclopyr butoxyethyl ester by a water phase synthesis method comprises the following steps:
1. adding 25kg of deionized water, 5.5kg of trichloropyridine sodium alcoholate, 2.8kg of chloroacetyl chloride, 0.2kg of sodium dodecyl sulfate and 0.3kg of ethanol into a reaction kettle at one time, controlling the temperature of the reaction kettle to be 45 ℃, controlling the stirring speed of the reaction kettle to be 110rpm, stirring for 35min, stopping stirring, controlling the temperature of the reaction kettle to be-10 ℃, standing for 25min, gradually increasing the temperature of the reaction kettle to be 45 ℃, and controlling the temperature increase speed to be 2.5 ℃/min;
2. after the temperature of the reaction kettle rises to 45 ℃, controlling the stirring speed of the reaction kettle to 160rpm, adding 0.18kg of crosslinking catalyst and 0.06kg of sodium hydroxide into the reaction kettle, preserving the heat at 45 ℃ for 50min, and stopping stirring;
the preparation method of the crosslinking catalyst specifically comprises the following steps: uniformly mixing 1kg of lecithin, 1.8kg of sodium persulfate, 0.3kg of maleic anhydride and 0.3kg of azodiisobutyl amidine hydrochloride, and then carrying out microwave oscillation at 45 ℃, wherein the microwave power of the microwave oscillation is controlled to be 920W, the microwave oscillation time is 25min, and obtaining the crosslinking catalyst after the microwave oscillation is finished.
3. Continuously adding 5kg of 2-butoxyethanol, 0.3kg of Tween 80 and 0.4kg of ethyl acetate into the reaction kettle, controlling the temperature of the reaction kettle to 50 ℃, controlling the stirring speed of the reaction kettle to 160rpm, stirring for 25min, stopping stirring, controlling the temperature of the reaction kettle to-10 ℃, standing for 35min, gradually increasing the temperature of the reaction kettle to 55 ℃, and controlling the heating speed to be 3.5 ℃/min;
4. after the temperature of the reaction kettle rises to 50 ℃, adding 0.3kg of composite catalyst, 0.03kg of sodium bicarbonate and 0.03kg of polyvinylamine into the reaction kettle, preserving the heat at 50 ℃ for 1.5h, and stopping stirring;
the preparation method of the composite catalyst comprises the following specific steps: uniformly mixing 0.3kg of light calcium carbonate, 0.04kg of aluminate coupling agent DL-411-A and 3kg of absolute ethyl alcohol, carrying out vacuum reduced pressure distillation at 45 ℃, controlling the vacuum pressure at 0.09MPa, carrying out reduced pressure distillation for 12min to obtain a primary composite catalyst, and uniformly mixing the primary composite catalyst and 0.1kg of azobisisobutyronitrile to obtain a composite catalyst;
5. and (3) washing the organic layer in the reaction kettle twice by using saturated salt solution, then carrying out vacuum drying, controlling the temperature of the vacuum drying to be 65 ℃, controlling the vacuum degree of the vacuum drying to be 120Pa, controlling the time of the vacuum drying to be 20min, and finally obtaining the triclopyr butoxyethyl ester after the vacuum drying is finished.
Comparative example 1
The method of preparation of butoxyethyl triclopyr described in example 1 was used with the following exceptions: no sodium persulfate was added to prepare the crosslinking catalyst in step 2.
Comparative example 2
The method of preparation of butoxyethyl triclopyr described in example 1 was used with the following exceptions: the step 1 and the step 3 are not subjected to freezing treatment, namely the step 1 is changed into the following steps:
20kg of deionized water, 5kg of sodium trichloropyridinol, 2.5kg of chloroacetyl chloride, 0.1kg of sodium dodecyl sulfate and 0.2kg of ethanol are added into a reaction kettle at one time, then the temperature of the reaction kettle is controlled to be 40 ℃, the stirring speed of the reaction kettle is controlled to be 100rpm, and the stirring is stopped after 30min of stirring.
The step 3 is changed into the following steps:
4kg of 2-butoxyethanol, 0.2kg of Tween 80 and 0.3kg of ethyl acetate are continuously added into the reaction kettle, then the temperature of the reaction kettle is controlled to 45 ℃, the stirring speed of the reaction kettle is controlled to 150rpm, and the stirring is stopped after 20min of stirring.
Comparative example 3
The method of preparation of butoxyethyl triclopyr described in example 1 was used with the following exceptions: no sodium bicarbonate was added in step 4.
The purity of butoxyethyl triclopyr in the products of examples 1-3 and comparative examples 1-3 was checked using a chromatograph while calculating the reaction yield, and the results are shown in the following graph:
soil adsorption capacity tests were performed on the products of examples 1-3 and comparative examples 1-3, and the test methods and test results are as follows:
setting six groups of parallel experiments which are divided into experiments 1-6, respectively weighing 20g of completely air-dried soil samples of the experiments 1-6, respectively adding 5g of 62% triclopyr butoxyethyl acetate missible oil prepared by the products in the examples 1-3 and the comparative examples 1-3 into the soil samples of the experiments 1-6, respectively, and then respectively sealing and vibrating for 10min to obtain six groups of adsorbed soil samples;
and then respectively carrying out simulated rainfall on the six groups of soil samples, controlling the rainfall time to be 15min and the simulated rainfall to be 5mm, and respectively collecting all soil percolate passing through the soil after the simulated rainfall.
The soil leachate collected in experiments 1-6 was tested by chromatograph, and the test results are shown below:
all percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (1)
1. A method for preparing triclopyr butoxyethyl ester by a water phase synthesis method is characterized in that triclopyr sodium and chloracetyl chloride are used as raw materials to generate triclopyr acetyl chloride, and then the triclopyr acetyl chloride reacts with 2-butoxyethanol to generate triclopyr butoxyethyl ester, and all reactions are carried out in a water phase;
the raw material of the triclopyr butoxyethyl ester comprises the following components in parts by weight: 20-25kg deionized water, 5-5.5kg sodium trichloropyridinol, 2.5-2.8kg chloroacetyl chloride, 0.1-0.2kg sodium dodecyl sulfate, 0.2-0.3kg ethanol, 0.15-0.18kg crosslinking catalyst, 0.05-0.06kg sodium hydroxide, 4-5kg 2-butoxyethanol, 0.2-0.3kg tween 80, 0.3-0.4kg ethyl acetate, 0.1-0.3kg composite catalyst, 0.02-0.03kg sodium bicarbonate, 0.01-0.03kg polyvinylamine;
the raw materials of the crosslinking catalyst comprise the following components in parts by weight: 0.8-1kg of lecithin, 1.5-1.8kg of sodium persulfate, 0.1-0.3kg of maleic anhydride and 0.2-0.3kg of azodiisobutyramidine hydrochloride;
the preparation method of the crosslinking catalyst specifically comprises the following steps: uniformly mixing lecithin, sodium persulfate, maleic anhydride and azodiisobutyramidine hydrochloride, and then carrying out microwave oscillation at 40 ℃, wherein the microwave power of the microwave oscillation is controlled to be 900W, the microwave oscillation time is controlled to be 20min, and a crosslinking catalyst is obtained after the microwave oscillation is finished;
the composite catalyst comprises the following raw materials in parts by weight: 0.1-0.3kg of light calcium carbonate, 0.03-0.04kg of aluminate coupling agent DL-411-A, 2.5-3kg of absolute ethyl alcohol and 0.08-0.1kg of azobisisobutyronitrile;
the preparation method of the composite catalyst comprises the following specific steps: uniformly mixing light calcium carbonate, an aluminate coupling agent DL-411-A and absolute ethyl alcohol, then carrying out vacuum reduced pressure distillation at 40-45 ℃, controlling the vacuum pressure at 0.083-0.09MPa, carrying out reduced pressure distillation for 10-12min to obtain a primary composite catalyst, and uniformly mixing the primary composite catalyst and azobisisobutyronitrile to obtain a composite catalyst;
the method for preparing triclopyr butoxyethyl ester comprises the following steps: primary raw material treatment, namely preparing triclopyr, secondary raw material treatment, preparing a triclopyr butoxyethyl ester product, and drying the product;
the first raw material treatment comprises the steps of adding deionized water, sodium trichloropyridinol, chloroacetyl chloride, sodium dodecyl sulfate and ethanol into a reaction kettle at one time, controlling the temperature of the reaction kettle to be 40-45 ℃, controlling the stirring speed of the reaction kettle to be 110rpm, stopping stirring after stirring for 30-35min, controlling the temperature of the reaction kettle to be-5-10 ℃, gradually raising the temperature of the reaction kettle to be 40-45 ℃ after standing for 20-25min, and controlling the temperature raising speed to be 2-2.5 ℃/min;
after the temperature of the reaction kettle is raised to 40-45 ℃, controlling the stirring speed of the reaction kettle to 150-160rpm, adding a crosslinking catalyst and sodium hydroxide into the reaction kettle, preserving the temperature at 40-45 ℃ for 45-50min, and stopping stirring;
the secondary raw material treatment, 2-butoxyethanol, Tween 80 and ethyl acetate are continuously added into the reaction kettle, then the temperature of the reaction kettle is controlled to be 45-50 ℃, the stirring speed of the reaction kettle is controlled to be 160rpm at 150-;
after the temperature of a reaction kettle is raised to 45-50 ℃, adding the composite catalyst, sodium bicarbonate and polyvinylamine into the reaction kettle, preserving the heat at 45-50 ℃ for 1-1.5h, and stopping stirring.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111023438.8A CN113461604B (en) | 2021-09-02 | 2021-09-02 | Method for preparing triclopyr butoxyethyl ester by aqueous phase synthesis method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111023438.8A CN113461604B (en) | 2021-09-02 | 2021-09-02 | Method for preparing triclopyr butoxyethyl ester by aqueous phase synthesis method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113461604A true CN113461604A (en) | 2021-10-01 |
| CN113461604B CN113461604B (en) | 2022-01-25 |
Family
ID=77867203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111023438.8A Active CN113461604B (en) | 2021-09-02 | 2021-09-02 | Method for preparing triclopyr butoxyethyl ester by aqueous phase synthesis method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113461604B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295597A (en) * | 2011-07-13 | 2011-12-28 | 迈克斯(如东)化工有限公司 | Preparation method of triclopyr butoxyethyl ester |
| CN107325044A (en) * | 2017-07-08 | 2017-11-07 | 杨子辉 | A kind of preparation method of herbicide triclopyr butoxyethyl ester |
| CN109180570A (en) * | 2018-06-29 | 2019-01-11 | 湖北犇星农化有限责任公司 | A kind of preparation method of trichlopyr fourth 2-ethoxyethyl acetate |
| CN110204480A (en) * | 2019-07-16 | 2019-09-06 | 潍坊新绿化工有限公司 | A kind of method that aqueous phase synthesis method prepares triclopyr butoxyethyl ester |
-
2021
- 2021-09-02 CN CN202111023438.8A patent/CN113461604B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295597A (en) * | 2011-07-13 | 2011-12-28 | 迈克斯(如东)化工有限公司 | Preparation method of triclopyr butoxyethyl ester |
| CN107325044A (en) * | 2017-07-08 | 2017-11-07 | 杨子辉 | A kind of preparation method of herbicide triclopyr butoxyethyl ester |
| CN109180570A (en) * | 2018-06-29 | 2019-01-11 | 湖北犇星农化有限责任公司 | A kind of preparation method of trichlopyr fourth 2-ethoxyethyl acetate |
| CN110204480A (en) * | 2019-07-16 | 2019-09-06 | 潍坊新绿化工有限公司 | A kind of method that aqueous phase synthesis method prepares triclopyr butoxyethyl ester |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113461604B (en) | 2022-01-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101634841B1 (en) | Preparation Method of Pimaric Acid Type Resin Acid | |
| CN106508523A (en) | Degradable corn field mulching film | |
| CN106832430B (en) | The production method of stalk composite liquid mulching film | |
| CN113461604B (en) | Method for preparing triclopyr butoxyethyl ester by aqueous phase synthesis method | |
| CN102372757B (en) | Method for preparing chenodeoxycholic acid in pig bile by esterification method | |
| CN101974043A (en) | Method for preparing punicalagin and ellagic acid from pomegranate rind | |
| CN114773407A (en) | Extraction method and application of rutin | |
| CN105831161A (en) | Method for preparing compounded brassinolide plant growth regulator easy to degrade | |
| CN117105841A (en) | Preparation method of bilirubin | |
| CN105130810A (en) | Method for extracting chlorogenic acid from honeysuckle | |
| CN112846220A (en) | Method for synthesizing nano-silver based on alfalfa extract | |
| CN101054475A (en) | Golden rod natural dyestuff, preparation method and use thereof | |
| CN109775912B (en) | Waste liquid treatment process of methoxybenzofuranone | |
| CN105968057A (en) | Synthetic technology of azoxystrobin | |
| CN110938020B (en) | Preparation process of lauroyl arginine ethyl ester hydrochloride | |
| CN107254356A (en) | A kind of method of utilization preparing fatty acid by illegal cooking oil | |
| CN106962374A (en) | A kind of biomass carbon particle for loading matrine chitosan sustained-release microsphere and preparation method thereof | |
| CN105777335A (en) | Production method achieving co-production of seaweed organic fertilizer by means of seaweed extracting solution | |
| CN105439864A (en) | Method for extracting high-purity ferulic acid from Szechwan lovage rhizome stems | |
| CN104069178A (en) | Extracting method for machilus salicina volatile oil | |
| CN105601395A (en) | Production method for co-production of macroelement and microelement type water-soluble fertilizer by utilizing seaweed extracts | |
| CN105820312B (en) | A kind of Chinese medicine dreg prepares the preparation method of epoxy resin | |
| CN109879732A (en) | A kind of preparation method of 1- (5- isopropyl -2,4- Dimethoxyphenyl) ethyl ketone | |
| CN105732202A (en) | Production method for utilizing seaweed extract for co-producing secondary element water-soluble fertilizer | |
| CN108812716A (en) | A kind of biology molluscicide and preparation method thereof |
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 |