CN114403136B - Mixed solvent mainly containing N, N-dimethyl caproamide, preparation method and application - Google Patents
Mixed solvent mainly containing N, N-dimethyl caproamide, preparation method and application Download PDFInfo
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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Abstract
The application relates to the technical field of solvents, and particularly discloses a mixed solvent mainly containing N, N-dimethylcaproamide, a preparation method and application thereof, wherein the acid value of the mixed solvent mainly containing N, N-dimethylcaproamide is 1.8-3.89mgKOH/g, the freezing point is-25 ℃, and the mixed solvent consists of 50.40-80.64% of N, N-dimethylcaproamide, 2.98-34.04% of N, N-dimethylcaprylamide, 15.31-16.52% of micromolecular aldehyde and ketone substances and the balance of water in percentage by weight. The preparation method comprises the steps of taking crude fatty acid with caproic acid as a main raw material and dimethylamine as raw materials, and sequentially carrying out salt forming and acylation reactions to obtain the product. The solubility to tebuconazole is 806-883g/kg, and the solubility to abamectin is 554-638g/kg. The obtained mixed solvent mainly containing N, N-dimethylcaproamide has small molecular weight and high pesticide solubility, is applied to pesticide preparations, and reduces the production cost.
Description
Technical Field
The application relates to the technical field of solvents, in particular to a mixed solvent mainly containing N, N-dimethyl caproamide, a preparation method thereof and application thereof in pesticide preparations.
Background
The solvent is widely applied to various fields such as pesticides, coatings, printing ink, building materials, industrial cleaning, household cleaning, cosmetics and the like, and at present, most of the solvents are derived from petrochemical products, such as common benzene solvents: toluene, xylene, aromatic hydrocarbon solvent oil, dimethylformamide, dimethylacetamide, dimethyl sulfoxide and the like, and the petrochemical solvents have the advantages of low cost, good solubility, easiness in obtaining and the like, and are still the main solvent types at present. However, these solvents have fatal disadvantages: the solvent has high volatility, is inflammable and explosive, is II or III carcinogen and reproduction teratogen in many solvents, influences the health and safety of human beings, and pays more attention to the living environment and health along with the trend that people tend to have good life, and needs to develop green, environment-friendly and environment-friendly solvents without influences on the environment and health to replace harmful solvents.
Because the pesticide is inconvenient to use and the pesticide effect cannot be effectively exerted, the original pesticide needs to be dissolved by adding a solvent, and other auxiliary agents and synergists are matched to prepare different preparations for use. The most used solvents are xylene and aromatic solvents, which are highly volatile, flammable, carcinogenic, teratogenic, as mentioned above, and which, in particular when sprayed on the ground or on crops, penetrate into ground water with rain and irrigation water, and which, due to their petrochemical origin, are very difficult to biodegrade and permanently contaminate soil and ground water resources. On the other hand, when the pesticide preparation prepared by the petrochemical solvent with low molecular weight is diluted by water in use, the original pesticide is often crystallized and separated out, and the activity and the efficacy of the pesticide are reduced. Therefore, there is an increasing demand for developing green and environmentally friendly solvents for human health and environmental protection.
There are two routes for developing environment-friendly, green, low-toxicity or nontoxic green solvents: firstly, petrochemical base material makes the alcohol ether solvent through the addition of ethylene oxide, for example, ethylene glycol butyl ether, diethylene glycol butyl ether etc. these new generation's environmental protection solvent have solved traditional harmful solvent's high volatility, flammable and explosive performance, but the dilution crystallization problem of a lot of pesticide preparations appears, and because all carbon and hydrogen elements that constitute the solvent all derive from petrochemical raw materials, so these new green solvent's biodegradability is poor, and long-term a large amount of uses also can cause the pollution to the environment. And secondly, developing a green plant solvent by taking vegetable oil as a raw material, such as coconut oil, palm oil, soybean oil and the like as a basic raw material. Akzo Nobel, hallstar, c.p. hall these companies produce dimethyloctanamide, dimethyloctanamide/decanamide and make a large amount of data on toxicological and ecological environments, proving that such products are the most environmentally and human friendly green solvents.
The green solvents are used for pesticide preparations and have the following advantages: 1. it is nontoxic to human body and environment, and has high solubility to pesticide active substance. 2. No crystallization occurred upon dilution with water. 3. It has no toxicity to crops. 4. Without reducing the activity of the pesticidal active. 5. Can be used in the formulation of various pesticide preparations, such as missible oil and water agent. However, the main raw materials for producing dimethyl caprylamide, dimethyl octyl/capramide, namely caprylic acid (or methyl caprylate) and octyl/capric acid (or octyl/capric acid) are prepared by hydrolyzing or methyl esterifying refined coconut oil or palm kernel oil and then rectifying to cut the caprylic acid (or methyl caprylate) and the octyl/capric acid (or octyl/capric acid). Considering the loss in the refining process and the rectification process, the production flow is complicated, various manual and energy consumptions and the like, the cost of the caprylic acid (or the methyl caprylate) and the caprylic/capric acid (or the caprylic/capric acid) is increased greatly.
At present, no mixed solvent mainly comprising N, N-dimethylcaproamide is reported.
Disclosure of Invention
The preparation method not only solves the problem of waste treatment in the refining process of the crude vegetable oil, but also greatly reduces the production cost of the mixed solvent mainly containing the N, N-dimethylcaproamide, and is beneficial to market popularization.
Technical principle of the present application
A preparation method of a mixed solvent mainly containing N, N-dimethylcaproamide comprises the steps of firstly, salifying reaction of hexanoic acid and octanoic acid in dimethylamine and crude fatty acid (the crude fatty acid is a by-product in the processing of vegetable oil and fat or animal oil and fat, the acid value of the by-product in the processing of the vegetable oil and fat or the animal oil and fat is 357.53-400.71mgKOH/g, and the by-product comprises 50.65-81.00% of hexanoic acid, 3.00-34.21% of octanoic acid and 15.14-16.00% of micromolecule aldehyde and ketone substances according to weight percentage, the by-product in the processing of the vegetable oil and fat is preferably the by-product in the processing of the vegetable oil and fat such as palm kernel oil or coconut oil) to respectively generate dimethylamine caproate and dimethylamine caprylate, and the reaction equations of the salifying reaction are respectively shown as follows:
CH 3 CH 2 CH 2 CH 2 CH 2 COOH+HN(CH 3 ) 2 →CH 3 CH 2 CH 2 CH 2 CH 2 COO-H 2 N + (CH 3 ) 2 ；
CH 3 (CH 2 ) 6 COOH+NH(CH 3 ) 2 →CH 3 (CH 2 ) 6 COO-H 2 N + (CH 3 ) 2 ；
then, under the action of molybdenum trioxide at 120-145 ℃, hexanoic acid dimethylamine salt and octanoic acid dimethylamine salt are respectively dehydrated in molecules to carry out acylation reaction to respectively form N, N-dimethyl caproamide and water, N-dimethyl caprylamide and water, and the acylation reaction equations are respectively as follows:
CH 3 CH 2 CH 2 CH 2 CH 2 COO-H 2 N + (CH 3 ) 2 →CH 3 CH 2 CH 2 CH 2 CH 2 CON(CH 3 ) 2 +H 2 O；
CH 3 (CH 2 ) 6 COO-H 2 N + (CH 3 ) 2 →CH3(CH 2 ) 6 CON(CH 3 ) 2 +H 2 O。
technical scheme of the application
The preparation method of the mixed solvent mainly containing N, N-dimethylcaproamide comprises the following steps:
(1) And salt formation reaction
Adding crude fatty acid into a reaction kettle, introducing dimethylamine into the reaction kettle under the control of pressure of 0.1-0.2Mpa and flow of 40-60L/h, and carrying out salt forming reaction on the crude fatty acid and the dimethylamine at normal temperature;
the crude fatty acid is a by-product in the processing of vegetable oil or animal fat, preferably a by-product in the processing of vegetable oil such as palm kernel oil or coconut oil, wherein the acid value of the by-product in the processing of vegetable oil or animal fat is 357.53-400.71mgKOH/g, and the by-product in the processing of vegetable oil or animal fat consists of 50.65-81.00% of caproic acid, 3.00-34.21% of caprylic acid and 15.14-16.00% of micromolecular aldehyde and ketone substances according to weight percentage;
the temperature of the salt-forming reaction liquid at the initial stage of the salt-forming reaction is increased, the temperature of the salt-forming reaction liquid can reach about 60 ℃, the bubbling phenomenon of the salt-forming reaction liquid is severe, when the temperature of the salt-forming reaction liquid in the container is not increased any more and the salt-forming reaction is basically finished, or the obtained salt-forming reaction liquid is sampled and detected, when the color of the salt-forming reaction liquid is yellow through a methyl red indicator, the salt-forming reaction is finished, and the introduction of dimethylamine is stopped;
(2) Acylation reaction
Adding a catalyst into the obtained salt-forming reaction liquid, and controlling the temperature to be 100-130 ℃ to enable the salt-forming reaction liquid to carry out total reflux reaction for 1-2h;
after the total reflux reaction is finished, controlling the pressure to be 0.1-0.2Mpa and the flow rate to be 20-60L/h, introducing dimethylamine into the reaction kettle again, controlling the temperature to be 120-145 ℃ to carry out acylation reaction, and stopping the reaction when the acid value of the reaction liquid obtained by the final acylation reaction reaches 1.8-2.0% to obtain acylation reaction liquid;
the catalyst is molybdenum trioxide, and the addition amount of the catalyst is 0.3-5.0% of the mass of the crude fatty acid; preferably 1.0-5.0%;
the form of the molybdenum oxide may be powder or granular, and the molybdenum oxide catalyst used in the present application is not particularly limited in terms of average particle diameter, particle size distribution, and particle form, and in the examples of the present application, powdered molybdenum trioxide is used;
(3) After the acylation reaction in the step (2) is finished, dimethylamine feeding is stopped, the temperature is controlled to be 160-180 ℃, heat preservation is carried out for 2 hours to promote the complete acylation reaction, after 2 hours, a sample is taken to measure the acid value, when the acid value of the acylation reaction liquid is more than 1%, heat preservation is continued, the acid value is measured once per hour until the acid value of the acylation reaction liquid is less than 1%, heating is stopped, and inert gas N is introduced into the reaction kettle under normal pressure 2 Removing unreacted dimethylamine and water vapor generated by reaction, and naturally cooling the temperature of the acylation reaction liquid to 20-30 ℃ at room temperatureWhen it is stopped, the power on N is stopped 2 And filtering to remove the catalyst to obtain a filtrate, namely the mixed solvent mainly containing the N, N-dimethylcaproamide.
The filter residue obtained by the filtration is a catalyst and can be continuously used in the next batch production, and the recycling frequency is 5-6 times.
The mixed solvent mainly containing N, N-dimethylcaproamide obtained by the preparation method has the freezing point of-25 ℃ and the acid value of 1.8-3.89mgKOH/g. The mixed solvent mainly containing N, N-dimethyl caproamide consists of N, N-dimethyl caproamide 50.40-80.64 wt%, N-dimethyl caprylamide 2.98-34.04 wt%, small molecular aldehyde and ketone 15.31-16.52 wt% and water for the rest.
The above-obtained mixed solvent mainly comprising N, N-dimethylhexanamide has high solubility in agricultural chemical raw materials such as difenoconazole and tebuconazole, and therefore, when dissolving the same agricultural chemical, a smaller amount of mixed solvent mainly comprising N, N-dimethylhexanamide can be used. Furthermore, since the molecular weight of the mixed solvent mainly composed of N, N-dimethylhexanamide is small, the mixed solvent can be easily emulsified, and the amount of the emulsifier used is small, the production cost of the agricultural chemical preparation can be reduced, and therefore the obtained mixed solvent mainly composed of N, N-dimethylhexanamide can be used for producing the agricultural chemical preparation. The pesticide preparation is difenoconazole missible oil containing difenoconazole, tebuconazole missible oil containing tebuconazole or tebuconazole aqueous emulsion containing tebuconazole.
In the specific application examples of the mixed solvent mainly containing N, N-dimethylcaproamide in the present application in preparing various pesticide formulations, the formulations such as emulsifiable solutions and aqueous emulsions are only exemplified, but the application in preparing other formulations such as microemulsions, suspensions, granules, powders, capsules, seed coatings and the like is not limited.
Advantageous effects of the present application
The mixed solvent mainly containing N, N-dimethylhexanamide has the advantages of high solubility compared with dimethyloctanamide and dimethyldecanamide due to the characteristics of short carbon chain and small molecular weight of dimethylhexanamide, and the solubility of difenoconazole, tebuconazole, oxyfluorfen, acetamiprid, abamectin and cypermethrin is higher than that of the commercially available dimethyloctadecanamide.
Further, the mixed solvent mainly comprising N, N-dimethylcaproamide according to the present invention has the advantage of a low freezing point, compared with commercially available dimethylcaprylamide and dimethylcapramide, because of the characteristics of a short carbon chain and a low molecular weight of N, N-dimethylcaproamide, and the freezing point can be lowered by about 10 ℃ compared with that of the commercially available dimethylcaprylamide, dimethylcapramide, or a mixed solvent of dimethylcaprylamide and dimethylcapramide.
Furthermore, according to the preparation method of the mixed solvent mainly comprising the N, N-dimethylhexanamide, in the preparation process, due to the addition of the catalyst molybdenum trioxide, the temperature of the amidation reaction can be greatly reduced, the reduction amplitude can reach 130 ℃ at most, and meanwhile, the reaction time can be shortened by 1.5-2h, so that the energy consumption for production is further reduced.
Furthermore, according to the preparation method of the mixed solvent mainly containing the N, N-dimethylhexanamide, the catalyst used in the preparation process can be recycled for multiple times, and the activity of the catalyst is not reduced after the catalyst is recycled for multiple times, so that the using amount of the catalyst in industrial production can be reduced, and the production cost of a product with unit mass is reduced.
Furthermore, the mixed solvent mainly containing N, N-dimethylhexanamide has high solubility to pesticides such as difenoconazole, tebuconazole or abamectin, so that less mixed solvent mainly containing N, N-dimethylhexanamide can be used when the same pesticide raw material is dissolved. In addition, the molecular weight of the mixed solvent mainly containing N, N-dimethylcaproamide is small, so that the mixed solvent is easy to emulsify, and the dosage of the used emulsifier is small, so that the preparation cost of the pesticide preparation can be reduced.
Detailed Description
The present application will be described in further detail with reference to specific examples, but the present application is not limited thereto.
The starting materials used in the examples of the present application are all technical grades, and are commercially available, except as specifically indicated in the following table:
the equipment used in the examples of this application:
GC Agilent 7890 gas chromatograph, produced by Agilent corporation;
METTLER-TOLEDO moisture meter, manufactured by Mettlerlatidol corporation;
a small-sized automatic amide reaction device provided by the institute of essence and spice of Shanghai applied technology university;
METTLER-TOLEDO electronic balance, produced by mettleltordo corporation;
electric mixers, model JJ-1, manufactured by shanghai sele instruments ltd;
SDCS type oven, tianjinseideris laboratory analytical instruments manufacturer.
In the mixed solvent based on N, N-dimethylcaproamide obtained in each example of the present application:
the acid value was measured according to AOCS Te 1a-64, and the water content was measured according to AOCS Tb 2-64 or GB/T606 (Karl-Fischer method) (METTLER-TOLEDO V20S Karl-Fischer titrator);
the content of N, N-dimethylhexanamide and N, N-dimethyloctanamide is measured by GB/T9722-2006 (gas chromatography) (Agilent GC Agilent 7890 gas chromatograph);
the content of other micromolecular aldehyde and ketone substances is measured by an Agilent GC Agilent 7890 gas chromatograph according to GB/T9722-2006.
The indexes of the pesticide preparation in the application example are measured according to Q/SHP 71-2017 (250 g/L standard of Difenoconazole emulsifiable concentrate enterprise), GB/T22605-2008 (national standard of tebuconazole emulsifiable concentrate), GB22604-2008 (national standard of tebuconazole water emulsion) and GB/T28137 (detection method of durable foamability of pesticide).
Example 1
A preparation method of a mixed solvent mainly containing N, N-dimethylhexanamide comprises the following steps:
(1) And salt-forming reaction
Adding 1000g of 06# crude fatty acid into a reaction kettle of a small-sized automatic amide reaction device, controlling the pressure to be 0.15Mpa and the flow to be 50L/h, introducing dimethylamine into the reaction kettle, carrying out salt forming reaction on the crude fatty acid and the dimethylamine at normal temperature, wherein the bubbling phenomenon of a salt forming reaction liquid is severe in the reaction process, when the temperature of the salt forming reaction liquid in the reaction kettle does not rise any more and the salt forming reaction is finished, or sampling and detecting the salt forming reaction liquid obtained in the reaction kettle, when the color of the salt forming reaction liquid is yellow through a methyl red indicator, finishing the salt forming reaction, and stopping introducing the dimethylamine;
the 06# crude fatty acid is a vegetable oil processing by-product, the vegetable oil processing by-product is a refined palm kernel oil by-product, the refined palm kernel oil by-product comprises 81.00% of caproic acid, 3.00% of caprylic acid, 16.00% of micromolecule aldehyde and ketone substances according to weight percentage, and the acid value is as follows: 400.71mgKOH/g;
(2) Acylation reaction
Adding 3g of catalyst into the salt-forming reaction liquid obtained in the step (1), and controlling the temperature to be 120 ℃ to enable the salt-forming reaction liquid to carry out total reflux reaction for 2 hours;
after the total reflux reaction is finished, controlling the pressure to be 0.2Mpa and the flow to be 40L/h, introducing dimethylamine into the reaction kettle again, controlling the temperature to be 145 ℃ to carry out acylation reaction for 5.5h, stopping the reaction when the acid value of the reaction liquid obtained by the acylation reaction reaches 1.9 percent, and obtaining acylation reaction liquid;
the catalyst is molybdenum trioxide, and the addition amount of the catalyst is 0.3 percent of the mass of the crude fatty acid; the form of the molybdenum oxide is powder;
(3) And (3) after the acylation reaction in the step (2) is finished, dimethylamine feeding is stopped, the temperature is controlled to be 160-180 ℃, heat preservation is carried out for 2 hours to promote the complete acylation reaction, after 2 hours, a sample is taken to measure the acid value, when the acid value of the acylation reaction liquid is more than 1%, heat preservation is continued, the acid value is measured once per hour, when the acid value of the acylation reaction liquid is less than 1%, heating is stopped, and inert gas N is introduced into the reaction kettle under normal pressure 2 Removing unreacted dimethylamine and water vapor generated by reaction, and stopping introducing N when the temperature of acylation reaction liquid naturally drops to 20-30 ℃ of room temperature 2 And filtering by using a 200-mesh filter screen, wherein filter residues obtained by filtering, namely the catalyst, are used for the next batch production, and the obtained filtrate is the mixed solvent mainly containing the N, N-dimethylcaproamide.
Example 2
A preparation method of a mixed solvent mainly containing N, N-dimethylcaproamide comprises the following steps:
(1) And salt-forming reaction
Same as in step (1) of example 1;
(2) Acylation reaction
Adding 5g of catalyst into the salt forming reaction liquid obtained in the step (1), and then controlling the temperature to be 120 ℃ to enable the salt forming reaction liquid to carry out total reflux reaction for 2h;
then, continuously introducing dimethylamine into the container under the conditions that the pressure is 0.2Mpa and the flow rate is 40L/h, and simultaneously controlling the temperature to be 145 ℃ to perform acylation reaction for 5.5h, stopping the reaction when the acid value of the reaction liquid obtained by the acylation reaction reaches below 2 percent, and ending the acylation reaction to obtain an acylation reaction liquid;
the catalyst is molybdenum trioxide, and the addition amount of the catalyst is 0.5 percent of the mass of the crude fatty acid; the form of the molybdenum oxide is powder;
(3) In the same manner as in step (3) of example 1, a mixed solvent mainly composed of N, N-dimethylcaproamide was finally obtained.
Example 3
A preparation method of a mixed solvent mainly containing N, N-dimethylcaproamide comprises the following steps:
(1) And salt formation reaction
Same as in step (1) of example 1;
(2) Acylation reaction
Adding 10g of catalyst into the salt forming reaction liquid obtained in the step (1), and then controlling the temperature to be 120 ℃ to enable the salt forming reaction liquid to carry out total reflux reaction for 2h;
then, controlling the pressure to be 0.2Mpa and the flow rate to be 40L/h, continuously introducing dimethylamine into the container, simultaneously controlling the temperature to be 140 ℃ for acylation reaction for 5.0h, stopping the reaction when the acid value of the reaction liquid obtained by the acylation reaction reaches below 2 percent, and finishing the acylation reaction to obtain an acylation reaction liquid;
the catalyst is molybdenum trioxide, and the addition amount of the catalyst is 1% of the mass of the crude fatty acid; the form of the molybdenum oxide is powder;
(3) In the same manner as in step (3) of example 1, a mixed solvent mainly composed of N, N-dimethylcaproamide was finally obtained.
Example 4
A preparation method of a mixed solvent mainly containing N, N-dimethylcaproamide comprises the following steps:
(1) And salt formation reaction
Same as in step (1) of example 1;
(2) Acylation reaction
Adding 30g of catalyst into the salt forming reaction liquid obtained in the step (1), and then controlling the temperature to be 120 ℃ to enable the salt forming reaction liquid to carry out total reflux reaction for 2h;
then, controlling the pressure to be 0.2Mpa and the flow rate to be 40L/h, continuously introducing dimethylamine into the container, controlling the temperature to be 130 ℃ at the same time, carrying out acylation reaction for 5.0h, stopping the reaction when the acid value of the reaction liquid obtained by the acylation reaction reaches below 2 percent, and finishing the acylation reaction to obtain an acylation reaction liquid;
the catalyst is molybdenum trioxide, and the addition amount of the catalyst is 3% of the mass of the crude fatty acid; the form of the molybdenum oxide is powder;
(3) In the same manner as in step (3) of example 1, a mixed solvent mainly composed of N, N-dimethylhexanamide was finally obtained.
Example 5
A preparation method of a mixed solvent mainly containing N, N-dimethylcaproamide comprises the following steps:
(1) And salt-forming reaction
Same as in step (1) of example 1;
(2) Acylation reaction
Adding 50g of catalyst into the salt-forming reaction liquid obtained in the step (1), and controlling the temperature to be 120 ℃ to enable the salt-forming reaction liquid to carry out total reflux reaction for 2 hours;
then, controlling the pressure to be 0.2Mpa and the flow rate to be 40L/h, continuously introducing dimethylamine into the container, simultaneously controlling the temperature to be 120 ℃ to carry out acylation reaction for 5.0h, stopping the reaction when the acid value of the reaction liquid obtained by the acylation reaction reaches below 2 percent, and finishing the acylation reaction to obtain an acylation reaction liquid;
the catalyst is molybdenum trioxide, and the addition amount of the catalyst is 5% of the mass of the crude fatty acid; the form of the molybdenum oxide is powder;
(3) In the same manner as in step (3) of example 1, a mixed solvent mainly composed of N, N-dimethylcaproamide was finally obtained.
Comparative example 1
A preparation method of a mixed solvent mainly containing N, N-dimethylhexanamide comprises the following steps:
(1) And salt formation reaction
Same as in step (1) of example 1;
(2) Acylation reaction
Adding no catalyst, and controlling the temperature of the salt forming reaction solution obtained in the step (1) to be 120 ℃ to perform total reflux reaction on the salt forming reaction solution for 2 hours;
then, controlling the pressure to be 0.2Mpa and the flow rate to be 40L/h, continuously introducing dimethylamine into the container, simultaneously controlling the temperature to be 250 ℃ to carry out acylation reaction for 7.0h, stopping the reaction when the acid value of the reaction liquid obtained by the acylation reaction reaches below 2 percent, and finishing the acylation reaction to obtain an acylation reaction liquid;
(3) In the same manner as in step (3) of example 1, a mixed solvent mainly composed of N, N-dimethylhexanamide was finally obtained.
Comparative example 2
A preparation method of a mixed solvent mainly containing N, N-dimethylcaproamide comprises the following steps:
(1) And salt formation reaction
Same as in step (1) of example 1;
(2) Acylation reaction
Adding 3g of cerium dioxide catalyst, and controlling the temperature of the salt-forming reaction solution obtained in the step (1) to be 120 ℃ so as to enable the salt-forming reaction solution to carry out total reflux reaction for 2 hours;
then, continuously introducing dimethylamine into the container under the conditions that the pressure is 0.2Mpa and the flow rate is 40L/h, and simultaneously controlling the temperature to be 190 ℃ to perform acylation reaction for 6.5h, stopping the reaction when the acid value of the reaction liquid obtained by the acylation reaction reaches below 2 percent, and ending the acylation reaction to obtain an acylation reaction liquid;
(3) In the same manner as in step (3) of example 1, a mixed solvent mainly composed of N, N-dimethylcaproamide was finally obtained.
Comparative example 3
A preparation method of a mixed solvent mainly containing N, N-dimethylhexanamide comprises the following steps:
(1) And salt formation reaction
Same as in step (1) of example 1;
(2) Acylation reaction
Adding 3g of silica gel catalyst, and controlling the temperature of the salt-forming reaction solution obtained in the step (1) to be 120 ℃ so as to carry out total reflux reaction on the salt-forming reaction solution for 2 hours;
then, controlling the pressure to be 0.2Mpa and the flow rate to be 40L/h, continuously introducing dimethylamine into the container, simultaneously controlling the temperature to be 190 ℃ to carry out acylation reaction for 7h, stopping the reaction when the acid value of the reaction liquid obtained by the acylation reaction reaches below 2 percent, and finishing the acylation reaction to obtain an acylation reaction liquid;
(3) In the same manner as in step (3) of example 1, a mixed solvent mainly composed of N, N-dimethylhexanamide was finally obtained.
Comparative example 4
A preparation method of a mixed solvent mainly containing N, N-dimethylhexanamide comprises the following steps:
(1) And salt formation reaction
Same as in step (1) of example 1;
(2) Acylation reaction
Adding 3g of sodium methoxide catalyst, and controlling the temperature of the salt forming reaction liquid obtained in the step (1) to be 120 ℃ to perform total reflux reaction on the salt forming reaction liquid for 2 hours;
then, controlling the pressure to be 0.2Mpa and the flow rate to be 40L/h, continuously introducing dimethylamine into the container, simultaneously controlling the temperature to be 190 ℃ to carry out acylation reaction for 7h, stopping the reaction when the acid value of the reaction liquid obtained by the acylation reaction reaches below 2 percent, and finishing the acylation reaction to obtain an acylation reaction liquid;
(3) In the same manner as in step (3) of example 1, a mixed solvent mainly composed of N, N-dimethylhexanamide was finally obtained.
Comparative example 5
A preparation method of a mixed solvent mainly containing N, N-dimethylcaproamide comprises the following steps:
(1) And salt formation reaction
Same as in step (1) of example 1;
(2) Acylation reaction
Adding 3g of titanium dioxide catalyst, and controlling the temperature of the salt forming reaction liquid obtained in the step (1) to be 120 ℃ to perform total reflux reaction on the salt forming reaction liquid for 2 hours;
then, controlling the pressure to be 0.2Mpa and the flow rate to be 40L/h, continuously introducing dimethylamine into the container, simultaneously controlling the temperature to be 190 ℃ to carry out acylation reaction for 7h, stopping the reaction when the acid value of the reaction liquid obtained by the acylation reaction reaches below 2 percent, and finishing the acylation reaction to obtain an acylation reaction liquid;
(3) In the same manner as in step (3) of example 1, a mixed solvent mainly composed of N, N-dimethylhexanamide was finally obtained.
Comparative example 6
A preparation method of a mixed solvent mainly containing N, N-dimethylhexanamide comprises the following steps:
(1) And salt formation reaction
Same as in step (1) of example 1;
(2) Acylation reaction
Adding 3g of zirconium dioxide catalyst, and controlling the temperature of the salt forming reaction liquid obtained in the step (1) to be 120 ℃ to perform full reflux reaction on the salt forming reaction liquid for 2 hours;
then, controlling the pressure to be 0.2Mpa and the flow rate to be 40L/h, continuously introducing dimethylamine into the container, simultaneously controlling the temperature to be 190 ℃ to carry out acylation reaction for 7h, stopping the reaction when the acid value of the reaction liquid obtained by the acylation reaction reaches below 2 percent, and finishing the acylation reaction to obtain an acylation reaction liquid;
(3) In the same manner as in step (3) of example 1, a mixed solvent mainly composed of N, N-dimethylcaproamide was finally obtained.
The amounts of the catalysts used in the preparation of the mixed solvent based on N, N-dimethylhexanamide in examples 1 to 5 and comparative examples 1 to 6, the control temperature of the acylation reaction process in step (2), the acylation reaction time in step (2), the acid value of the finished product in step (3), i.e., the mixed solvent based on N, N-dimethylhexanamide, the conversion of crude fatty acid into N, N-dimethylhexanamide (i.e., the conversion of hexanoic acid in crude fatty acid into N, N-dimethylhexanamide = (raw acid value-finished acid value)/raw acid value 100%) are as follows:
note: the acid value of the raw material used for the calculation of the conversion is the acid value of the crude fatty acid, and the acid value of the finished product used is the acid value of the mixed solvent mainly containing N, N-dimethylcaproamide.
As can be seen from the above-mentioned examples 1-5, in the preparation process of the mixed solvent mainly containing N, N-dimethylcaproamide, when the amount of the catalyst is 0.3-5.0%, the conversion rate of caproic acid in the crude fatty acid into N, N-dimethylcaproamide is greater than 99%, and the addition of the catalyst can greatly reduce the temperature of the amidation reaction, and the temperature of the acylation reaction gradually decreases with the increase of the amount of the catalyst. Compared with the method without adding the catalyst (comparative example 1), when the using amount of the catalyst molybdenum oxide reaches 5%, the acylation reaction temperature can be reduced by 130 ℃, and the acylation reaction time can be shortened by 2 hours.
Further, as can be seen from the comparison between the above-mentioned example 1 and the comparative example 1, in the present application, molybdenum oxide is used as the catalyst, and when the amount of the catalyst added is 0.3% of the crude fatty acid, the acylation reaction temperature can be reduced by 105 ℃, and the reaction time can be shortened by 1.5 hours, so that the production energy consumption can be reduced, the production efficiency can be improved, and the production cost can be reduced.
Further, as can be seen from the comparison between the above-mentioned example 1 and the comparative examples 2 to 6, when the amount of the catalyst added is 0.3% of the crude fatty acid, the acylation reaction temperature can be lowered by 45 ℃ by using molybdenum oxide as the catalyst, as compared with other catalysts such as sodium methoxide, silica gel, zirconium dioxide, titanium dioxide, and cerium dioxide, the reaction time can be shortened by 1 to 1.5 hours, and the conversion rate of the crude fatty acid into caproamide by using molybdenum oxide as the catalyst is higher than that by using other catalysts, so that the preparation of the mixed solvent mainly containing N, N-dimethylcaproamide by using molybdenum oxide as the catalyst is preferable, and not only the energy consumption for production can be reduced, the production cost can be reduced, but also the conversion rate of the crude fatty acid into amide can be improved.
Further, the mixed solvent mainly containing N, N-dimethylhexanamide prepared in examples 1 to 5 was measured, and the acid value was measured according to AOCS Te 1a-64, and the water content in the obtained mixed solvent mainly containing N, N-dimethylhexanamide was measured according to AOCS Tb 2-64 or GB/T606 (karl-fischer method) (METTLER-TOLEDO V20S karl fisher titrator), and the contents of N, N-dimethylhexanamide and N, N-dimethyloctanamide were measured according to GB/T9722-2006 (gas chromatography) (Agilent GC Agilent 7890 gas chromatograph), and the contents of other small molecular aldehydes and ketones were measured according to GB/T9722-2006 (Agilent GC Agilent 7890 gas chromatograph). The results are shown in the following table:
as can be seen from the above table, the final mixed solvent with N, N-dimethylcaproamide as the main component has stable index of composition, the acid value is 2.1-3.89mgKOH/g, the content of N, N-dimethylcaproamide in the mixed solvent with N, N-dimethylcaproamide as the main component is 80.27-80.64%, the content of N, N-dimethylcaprylamide is 2.98-2.99%, the content of micromolecular aldehyde and ketone substances is 16.07-16.52%, and the balance is water.
Example 6
After the reaction in the step (3) in the example 5 is finished, the catalyst separated by filtration is directly used as the catalyst for the second circulation, and the rest is the same as that in the example 5;
example 7
After the reaction in the step (3) in the example 6 is finished, the catalyst separated by filtration is directly used as the catalyst for the third circulation, and the rest is the same as that in the example 6;
example 8
After the reaction in the step (3) in the example 7 is finished, the catalyst separated by filtration is directly used as the catalyst for the fourth time for recycling, and the rest is the same as that in the example 7;
example 9
After the reaction in the step (3) in the example 8 is finished, the catalyst separated by filtration is directly used as the catalyst for the fifth circulation, and the rest is the same as that in the example 8;
example 10
After the reaction in the step (3) in the example 9 is finished, the catalyst separated by filtration is directly used as the catalyst for the sixth cycle, and the rest is the same as that in the example 9;
examples 5-10 number of cycles of final catalyst, acid value of the resulting mixed solvent based on N, N-dimethylhexanamide, conversion of crude fatty acid to N, N-dimethylfatty amide (= (raw acid value-finished acid value)/raw acid value 100%) are specified in the following table:
note: the acid value of the raw material used for calculating the conversion rate is the acid value of crude fatty acid, namely 400.71mgKOH/g of the acid value of No. 06 crude fatty acid, and the acid value of the finished product used is the acid value of a mixed solvent mainly containing N, N-dimethylcaproamide.
As can be seen from the above table, the catalyst used in the preparation process of the mixed solvent mainly containing N, N-dimethylhexanamide of the present application can be recycled for many times, and particularly, after recycling for 5-6 times, the conversion rate of the fatty acid in the crude fatty acid into N, N-dimethylhexanamide is still greater than 99.28%, thereby indicating that the catalyst used in the preparation process of the mixed solvent mainly containing N, N-dimethylhexanamide of the present application can be recycled for many times, and the activity of the catalyst is not reduced, so that the production cost of the mixed solvent containing N, N-dimethylhexanamide can be saved in industrial production.
Example 11
A preparation method of a mixed solvent mainly containing N, N-dimethylcaproamide comprises the following steps:
(1) And salt formation reaction
Except that 07# crude fatty acid was added to the reaction vessel of the small-sized automated amide reaction apparatus, the other steps were the same as in the step (1) of example 1;
the 07# crude fatty acid is a vegetable oil processing by-product, the vegetable oil processing by-product is a refined palm kernel oil by-product, the refined palm kernel oil by-product comprises, by weight, 64.05% of caproic acid, 20.61% of caprylic acid, 15.34% of micromolecular aldehyde and ketone substances, and the acid value is as follows: 366.77mgKOH/g;
(2) Acylation reaction
Step (2) of the same example;
(3) In the same manner as in step (3) of example 1, a mixed solvent mainly composed of N, N-dimethylhexanamide was finally obtained.
Example 12
A preparation method of a mixed solvent mainly containing N, N-dimethylhexanamide comprises the following steps:
(1) And salt formation reaction
Except that 08# crude fatty acid was added to the reaction vessel of the small-sized automated amide reaction apparatus, the other steps were the same as in the step (1) of example 1;
the 08# crude fatty acid is a vegetable oil processing by-product, the vegetable oil processing by-product is a refined palm kernel oil and coconut oil by-product, the refined palm kernel oil and coconut oil by-product comprises, by weight, 50.65% of caproic acid, 34.21% of caprylic acid, 15.14% of micromolecular aldehyde and ketone substances, and the acid value is as follows: 357.53mgKOH/g;
(2) Acylation reaction
Same as in step (2) of example 1;
(3) In the same manner as in step (3) of example 1, a mixed solvent mainly composed of N, N-dimethylhexanamide was finally obtained.
The acid value, water content, N-dimethylcaproamide and N, N-dimethylcaprylamide contents, aldehyde and ketone contents of other small molecules, and freezing point of the mixed solvents based on N, N-dimethylcaproamide prepared in examples 11 and 12 were measured, and the results are shown in the following table:
as can be seen from the acid value, water content, N-dimethylcaproamide and N, N-dimethylcaprylamide contents and other small molecular aldehyde and ketone contents of the mixed solvent mainly composed of N, N-dimethylcaproamide prepared in the above-mentioned examples 1 to 5 and examples 11 to 12, when the raw material crude fatty acid (by-product of refined palm kernel oil and coconut oil) used in the present invention is composed of 50.65 to 81.00% of caproic acid, 3.00 to 34.21% of caprylic acid and 15.14 to 16.00% of small molecular aldehyde and ketone substances in terms of weight percentage, the crude fatty acid and dimethylamine are subjected to salt formation and acylation reaction in sequence to finally obtain N, the mixed solvent mainly containing N-dimethylcaproamide comprises, by weight, 50.40-80.64% of N, N-dimethylcaproamide, 2.98-34.04% of N, N-dimethylcaprylamide, 15.31-16.52% of small molecular aldehyde and ketone substances and the balance of water, namely the small molecular aldehyde and ketone substances in the crude fatty acid raw material directly enter the finally obtained mixed solvent mainly containing N, N-dimethylcaproamide, and the finally obtained mixed solvent mainly containing N, N-dimethylcaproamide has an acid value of 1.80-3.89mgKOH/g and a freezing point of less than-25 ℃.
The finished products obtained in the above examples 1, 11 and 12 were compared with a commercial mixed solvent of dimethyloctyldecanoamide and measured for solubility in tebuconazole (the measurement method was referred to "journal of pharmaceutical analysis" 2010,30 (4), P762, equilibrium solubility measurement method.), solubility in abamectin (referred to "journal of pharmaceutical analysis" 2010,30 (4), P762, equilibrium solubility measurement method.) and respective freezing points (the measurement method was referred to ASTM D1493-97, industrial organic chemical freezing point measurement standard method), as shown in the following table:
as can be seen from the above table, compared with the mixed solvent of dimethyloctyldecanoamide which is widely used in the market at present, the mixed solvent based on N, N-dimethylhexanoamide obtained in examples 1, 11 and 12 of the present application has improved solubility for tebuconazole by 25.07%, 18.13% and 14.16% respectively, and improved solubility for abamectin by 31.28%, 20.78% and 13.99% respectively, compared with the mixed solvent of dimethyloctyldecanoamide which is commercially available. The freezing point of the mixed solvent mainly containing N, N-dimethylcaproamide can be reduced by about 10 ℃ compared with that of the mixed solvent containing dimethylcaprylocapramide. Therefore, the mixed solvent mainly containing N, N-dimethyl caproamide has a lower freezing point, and has higher solubility to tebuconazole and abamectin technical products.
Application example 1
Using the mixed solvent mainly comprising N, N-dimethylcaproamide obtained in example 1, a difenoconazole emulsifiable concentrate containing 25% of difenoconazole is prepared according to the pesticide preparation processing suite book 'liquid preparation', the scheme of Guowu Kechiei, chemical industry publishers, P108, and the processing technology of the emulsifiable concentrate, and the raw materials used for preparing the difenoconazole emulsifiable concentrate comprise the following components and contents in each 1000g of difenoconazole emulsifiable concentrate containing 25% of difenoconazole:
the preparation method of the difenoconazole emulsifiable concentrate containing 25% of difenoconazole comprises the following specific steps:
260g of difenoconazole (with the purity of 96.2 wt%), 634g of mixed solvent mainly containing N, N-dimethyl caproamide obtained in example 1 and 106g of emulsifier Kelonem810EM are sequentially added into a reaction kettle, the rotating speed is controlled to be 80-100r/min, and the materials are uniformly stirred to obtain the difenoconazole emulsifiable concentrate containing 25% of difenoconazole.
The obtained difenoconazole missible oil containing 25% of difenoconazole is detected according to Q/SHP 71-2017 (250 g/L of the enterprise standard of the difenoconazole missible oil), and the technical indexes are shown in the following table:
from the above table, it can be seen that, with the mixed solvent mainly containing N, N-dimethylcaproamide obtained in example 1 of the present application as a solvent and Kelonem810EM as an emulsifier, the difenoconazole emulsifiable concentrate containing 25% difenoconazole is prepared, and each index meets the requirements of Q/SHP 71-2017 (250 g/L of difenoconazole emulsifiable concentrate enterprise standard). It is thus shown that the mixed solvent based on N, N-dimethylhexanamide of the present application can be used as a solvent for preparing a difenoconazole cream.
Application example 2
The mixed solvent mainly containing N, N-dimethylhexanamide obtained in example 1 is used for preparing tebuconazole emulsifiable concentrate containing 25 percent of tebuconazole, and the components and the content of the raw materials used for preparing the tebuconazole emulsifiable concentrate containing 25 percent of tebuconazole are as follows according to the calculation of every 1000g of the tebuconazole emulsifiable concentrate containing 25 percent of tebuconazole:
the preparation method of the tebuconazole emulsifiable concentrate containing 25 percent of tebuconazole comprises the following specific steps:
263.2g of tebuconazole (purity of 95 wt%), 630.8g of the mixed solvent mainly containing N, N-dimethylhexanamide obtained in the example 1 and 106g of the emulsifier Kelonem810EM are sequentially added into a reaction kettle, and the rotation speed is controlled to be 80-100r/min to be uniformly stirred, so that tebuconazole emulsifiable concentrate containing 25% of tebuconazole is obtained.
The tebuconazole missible oil containing 25% tebuconazole obtained by the method is detected according to GB/T22605-2008 standard (national standard of tebuconazole missible oil), and the technical indexes of the tebuconazole missible oil containing 25% tebuconazole finally obtained are shown in the following table:
as can be seen from the above table, the tebuconazole emulsifiable concentrate containing 25% tebuconazole prepared by using the mixed solvent mainly containing N, N-dimethylhexanamide obtained in example 1 of the present application as a solvent and Kelonem810EM as an emulsifier has the requirements of each index symbol GB/T22605-2008 standard (national standard for tebuconazole emulsifiable concentrate). Thus, the mixed solvent mainly containing N, N-dimethylhexanamide can be used as a solvent for preparing tebuconazole missible oil.
Application example 3
1000g of tebuconazole aqueous emulsion containing 25 percent of tebuconazole is prepared by utilizing the mixed solvent which is mainly prepared from N, N-dimethylhexanamide and is obtained in the example 1, and the raw materials used for the preparation comprise the following components in percentage by mass:
the preparation method of the tebuconazole aqueous emulsion containing 25 percent of tebuconazole comprises the following specific steps:
264g of tebuconazole (the purity is 95wt percent), 456g of the mixed solvent which is mainly N, N-dimethyl caproamide and is obtained in the example 1, 160g of emulsifier Kelonem810EM and 120g of deionized water are sequentially added into a reaction kettle, and the rotation speed is controlled to be 80-100r/min and the mixture is uniformly stirred, so that the tebuconazole aqueous emulsion containing 25 percent of tebuconazole is obtained.
The tebuconazole aqueous emulsion containing 25% tebuconazole prepared by using the mixed solvent mainly containing N, N-dimethylhexanamide as the finished product obtained in the example 1 is detected according to GB22604-2008 (national standard of tebuconazole aqueous emulsion), and the indexes are as follows:
as can be seen from the above table, the tebuconazole aqueous emulsion containing 25% tebuconazole prepared by using the mixed solvent mainly containing N, N-dimethylhexanamide obtained in example 1 of the present application as a main solvent and Kelonem810EM as an emulsifier meets the requirements of GB22604-2008 (national standard for tebuconazole aqueous emulsion).
Comparative example of application example 3
The method comprises the following steps of preparing 1000g of tebuconazole aqueous emulsion containing 25% tebuconazole by using a mixed solvent of dimethyl octyl capramide sold in the market, wherein the raw materials used for the preparation comprise the following components in percentage by mass:
the preparation method of the tebuconazole aqueous emulsion containing 25 percent of tebuconazole prepared by utilizing the mixed solvent of dimethyl octyl capramide sold in the market comprises the following specific steps:
264g of tebuconazole (the purity is 95wt percent), 486g of a commercial dimethyl octyl capramide mixed solvent, 180g of emulsifier Kelonem810EM and 80g of deionized water are sequentially added into a reaction kettle, and the rotation speed is controlled to be 80-100r/min for even stirring, so that the tebuconazole aqueous emulsion containing 25 percent of tebuconazole is obtained.
The tebuconazole aqueous emulsion containing 25% tebuconazole prepared by using the commercial mixed solvent of dimethyl octyl capramide is detected according to GB22604-2008 (national standard of tebuconazole aqueous emulsion), and the indexes are as follows:
as can be seen from the table above, the tebuconazole aqueous emulsion containing 25% tebuconazole prepared by using the commercial mixed solvent of dimethyl octyl capramide and the emulsifier Kelonem810EM meets the requirements of GB22604-2008 (national standard of tebuconazole aqueous emulsion) in all indexes.
However, from the comparison of the raw materials used for preparing the final products of the application example 3 and the comparative example of the application example 3, it can be seen that when preparing tebuconazole aqueous emulsion with the same concentration, because the mixed solvent mainly containing N, N-dimethylhexanamide of the present application has high solubility to tebuconazole raw drug, when dissolving the same tebuconazole, less mixed solvent mainly containing N, N-dimethylhexanamide can be used, and the rest of the solvent can be supplemented with water, compared with the comparative example of the application example 3, the application example 3 has the advantages that the solvent is reduced by 3% and the water dosage is increased by 5%, so that the preparation cost of the tebuconazole aqueous emulsion containing 25% of tebuconazole can be greatly reduced;
further, since the mixed solvent mainly composed of N, N-dimethylcaproamide of the present invention has a smaller molecular weight than a commercially available mixed solvent of dimethylcaprylocapramide, it is easily emulsified, and the amount of the emulsifier used is small. Compared with the comparative example of the application example 3, the use amount of the emulsifier is reduced by 2%, and thus, the preparation cost of the tebuconazole aqueous emulsion containing 25% tebuconazole can be further greatly reduced.
Furthermore, the tebuconazole aqueous emulsion containing 25% of tebuconazole prepared by using the mixed solvent of dimethyl octyl capramide in the market has 2.3% of residues after pouring and 0.3% of residues after washing, while the mixed solvent mainly containing N, N-dimethyl caproamide obtained in the application example 1 is used for preparing 0.6% of residues after pouring and 0.1% of residues after washing, namely the comparison example of the application example 3 is 2.8 times higher and 2 times higher than the residues after pouring of the application example 3 in the application example, thereby showing that the tebuconazole aqueous emulsion product containing 25% of tebuconazole prepared by using the mixed solvent mainly containing N, N-dimethyl caproamide in the application example has small residue of pesticide preparations in a packaging bottle after using up, is not easy to cause pesticide waste and environmental pollution, while the tebuconazole aqueous emulsion product containing 25% of tebuconazole prepared by using the mixed solvent of dimethyl octyl capramide in the market has large residue in the packaging bottle after using up, and is easy to cause the waste of pesticide preparations in the packaging bottle.
The above description is only a preferred embodiment of the present application, and the protection scope of the present application is not limited to the above embodiments, and all technical solutions belonging to the idea of the present application belong to the protection scope of the present application. It should be noted that modifications and embellishments within the scope of the present disclosure may occur to those of ordinary skill in the art without departing from the spirit of the present disclosure, and such modifications and embellishments are considered to be within the scope of the present disclosure.
Claims (8)
1. A mixed solvent mainly comprising N, N-dimethylhexanamide, which is characterized in that;
the mixed solvent mainly containing N, N-dimethyl caproamide comprises the following raw materials in percentage by weight:
50.40 to 80.64 percent of N, N-dimethylhexanamide
2.98 to 34.04 percent of N, N-dimethyl octanoyl amide
Small molecular aldehyde ketone 15.31-16.52%
The balance of water;
the mixed solvent mainly containing N, N-dimethylhexanamide is prepared by the following method:
raw materials are crude fatty acid and dimethylamine, the crude fatty acid is a by-product in palm kernel oil or coconut oil processing, the acid value of the crude fatty acid is 357.53-400.71mgKOH/g, and the crude fatty acid consists of 50.65-81.00 percent of caproic acid, 3.00-34.21 percent of caprylic acid and 15.14-16.00 percent of micromolecular aldehyde ketone substances according to weight percentage;
the preparation process of the mixed solvent mainly comprising N, N-dimethylcaproamide comprises the following steps:
firstly, carrying out salt-forming reaction on hexanoic acid and octanoic acid in byproducts of dimethylamine and palm kernel oil or coconut oil to respectively generate hexanoic acid dimethylamine salt and octanoic acid dimethylamine salt;
then, respectively dehydrating the hexanoic acid dimethylamine salt and the octanoic acid dimethylamine salt in the molecule for acylation reaction at the temperature of 120-145 ℃ under the action of a catalyst molybdenum trioxide to respectively form N, N-dimethyl caproamide and N, N-dimethyl caprylamide;
micromolecular aldoketone substances in the crude fatty acid are directly used as components of a mixed solvent mainly containing N, N-dimethylcaproamide.
2. The mixed solvent based on N, N-dimethylhexanamide as claimed in claim 1, wherein:
the acid value of the mixed solvent mainly containing the N, N-dimethylcaproamide is 1.80-3.89mgKOH/g, and the freezing point is < -25 ℃;
the mixed solvent mainly containing N, N-dimethyl caproamide has solubility of 806-883g/kg for tebuconazole and 554-638g/kg for abamectin.
3. A method for preparing a mixed solvent based on N, N-dimethylcaproamide according to claim 1 or 2, characterized in that:
taking crude fatty acid and dimethylamine as raw materials, wherein the crude fatty acid is a by-product in palm kernel oil or coconut oil processing, has an acid value of 357.53-400.71mgKOH/g, and consists of 50.65-81.00 percent of caproic acid, 3.00-34.21 percent of caprylic acid and 15.14-16.00 percent of micromolecular aldone substances according to weight percentage;
the preparation process of the mixed solvent mainly comprising N, N-dimethylcaproamide comprises the following steps:
firstly, carrying out salt-forming reaction on hexanoic acid and octanoic acid in byproducts of dimethylamine and palm kernel oil or coconut oil to respectively generate hexanoic acid dimethylamine salt and octanoic acid dimethylamine salt;
then, respectively dehydrating the hexanoic acid dimethylamine salt and the octanoic acid dimethylamine salt in molecules for acylation reaction at 120-145 ℃ under the action of a catalyst of molybdenum trioxide to respectively form N, N-dimethylhexanamide and N, N-dimethyloctanamide;
micromolecular aldehyde ketone substances in the crude fatty acid are directly used as components of a mixed solvent mainly containing N, N-dimethyl caproamide.
4. The method for preparing the mixed solvent mainly comprising N, N-dimethylhexanamide as claimed in claim 3, which comprises the following steps:
(1) And salt-forming reaction
Adding crude fatty acid into a reaction kettle, controlling the pressure to be 0.1-0.2Mpa and the flow to be 40-60L/h, introducing dimethylamine into the reaction kettle, carrying out salt forming reaction, finishing the salt forming reaction when the temperature of a salt forming reaction liquid is not increased any more, or finishing the salt forming reaction when the color of the salt forming reaction liquid is yellow through a methyl red indicator, and stopping introducing the dimethylamine;
(2) Acylation reaction
Firstly, adding a catalyst into the salifying reaction liquid obtained in the step (1), and then controlling the temperature to be 100-130 ℃ to enable the reaction liquid to carry out total reflux reaction for 1-2h;
after the total reflux reaction is finished, continuously controlling the pressure to be 0.1-0.2Mpa and the flow rate to be 20-60L/h, introducing dimethylamine into the reaction kettle, simultaneously controlling the temperature to be 120-145 ℃ for acylation reaction, stopping the reaction when the acid value of the reaction liquid obtained by the acylation reaction reaches 1.8-2.0%, and finishing the acylation reaction to obtain acylation reaction liquid;
the catalyst is molybdenum trioxide, and the addition amount of the catalyst is 0.3-5.0% of the mass of the crude fatty acid;
(3) And (2) after the acylation reaction is finished, stopping feeding dimethylamine, controlling the temperature to be 160-180 ℃, keeping the temperature, stopping heating until the acid value of the acylation reaction liquid is less than 1%, and introducing inert gas N into the reaction kettle under normal pressure 2 Stopping introducing N when the temperature of the acylation reaction liquid is reduced to 20-30 ℃ at room temperature 2 And filtering to remove the catalyst to obtain a filtrate, namely the mixed solvent mainly containing N, N-dimethylcaproamide.
5. The method for preparing a mixed solvent based on N, N-dimethylhexanamide as claimed in claim 4, wherein the amount of the catalyst added in the step (2) is 1.0-5.0% by weight based on the crude fatty acid.
6. The difenoconazole emulsifiable concentrate containing 25% of difenoconazole is characterized in that the difenoconazole emulsifiable concentrate is prepared from the following raw materials in percentage by weight:
26.0 percent of difenoconazole
63.4 percent of mixed solvent mainly comprising N, N-dimethylhexanamide
Emulsifier Kelonem810EM 10.6%;
the purity of the difenoconazole is 96.2 wt%;
the mixed solvent mainly comprising N, N-dimethylcaproamide according to claim 1 or 2.
7. The tebuconazole emulsifiable concentrate containing 25% of tebuconazole is characterized by comprising the following raw materials in percentage by weight:
tebuconazole 26.4%
45.6 percent of mixed solvent mainly comprising N, N-dimethylhexanamide
Emulsifier Kelonem810EM 16.0%;
the purity of the tebuconazole is 95wt%;
the mixed solvent mainly comprising N, N-dimethylcaproamide according to claim 1 or 2.
8. The tebuconazole aqueous emulsion containing 25 percent of tebuconazole is characterized by comprising the following raw materials in percentage by weight:
tebuconazole 26.4%
45.6 percent of mixed solvent mainly comprising N, N-dimethylhexanamide
Emulsifier Kelonem810EM 16.0%
12.0 percent of water;
the purity of the tebuconazole is 95wt%;
the mixed solvent mainly comprising N, N-dimethylcaproamide according to claim 1 or 2.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5385948A (en) * | 1993-02-16 | 1995-01-31 | Isp Investments Inc. | Alkoxyalkyl lactams as solvents for macro and microemulsions |
| WO2008069822A1 (en) * | 2006-02-21 | 2008-06-12 | Phibro-Tech Inc. | Biocidal azole emulsion concentrates having high active ingredient content |
| CN102907418A (en) * | 2012-10-24 | 2013-02-06 | 深圳诺普信农化股份有限公司 | Pesticide solvent using jatropha curcas source, and preparation method and application for pesticide solvent |
| CN103381359A (en) * | 2013-07-29 | 2013-11-06 | 张家港市大伟助剂有限公司 | Preparation method for catalyst for N,N-dimethyl-caprylamide/decanamide |
| JP2016056099A (en) * | 2014-09-05 | 2016-04-21 | 住友化学株式会社 | Liquid agrochemical |
| JP2020011954A (en) * | 2018-07-09 | 2020-01-23 | 日産化学株式会社 | Agrochemical emulsifying composition |
| WO2020121344A1 (en) * | 2018-12-14 | 2020-06-18 | Isagro S.P.A. | Emulsifiable concentrate containing fluindapyr and use thereof as fungicide in crop plants |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9730439B2 (en) * | 2010-03-10 | 2017-08-15 | Isp Investments Llc | Preformed concentrate for delivery of water insoluble film forming polymers |
-
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- 2021-11-18 CN CN202111371589.2A patent/CN114403136B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5385948A (en) * | 1993-02-16 | 1995-01-31 | Isp Investments Inc. | Alkoxyalkyl lactams as solvents for macro and microemulsions |
| WO2008069822A1 (en) * | 2006-02-21 | 2008-06-12 | Phibro-Tech Inc. | Biocidal azole emulsion concentrates having high active ingredient content |
| CN102907418A (en) * | 2012-10-24 | 2013-02-06 | 深圳诺普信农化股份有限公司 | Pesticide solvent using jatropha curcas source, and preparation method and application for pesticide solvent |
| CN103381359A (en) * | 2013-07-29 | 2013-11-06 | 张家港市大伟助剂有限公司 | Preparation method for catalyst for N,N-dimethyl-caprylamide/decanamide |
| JP2016056099A (en) * | 2014-09-05 | 2016-04-21 | 住友化学株式会社 | Liquid agrochemical |
| JP2020011954A (en) * | 2018-07-09 | 2020-01-23 | 日産化学株式会社 | Agrochemical emulsifying composition |
| WO2020121344A1 (en) * | 2018-12-14 | 2020-06-18 | Isagro S.P.A. | Emulsifiable concentrate containing fluindapyr and use thereof as fungicide in crop plants |
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