CN109293604A - Less toxic Gao Minyi for confined space decomposes pyrethrins and its manufacturing method - Google Patents
Less toxic Gao Minyi for confined space decomposes pyrethrins and its manufacturing method Download PDFInfo
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- CN109293604A CN109293604A CN201811284972.2A CN201811284972A CN109293604A CN 109293604 A CN109293604 A CN 109293604A CN 201811284972 A CN201811284972 A CN 201811284972A CN 109293604 A CN109293604 A CN 109293604A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/12—Radicals substituted by oxygen atoms
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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
- A01N61/00—Biocides, pest repellants or attractants, or plant growth regulators containing substances of unknown or undetermined composition, e.g. substances characterised only by the mode of action
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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
- A01N63/00—Biocides, pest repellants or attractants, or plant growth regulators containing microorganisms, viruses, microbial fungi, animals or substances produced by, or obtained from, microorganisms, viruses, microbial fungi or animals, e.g. enzymes or fermentates
- A01N63/10—Animals; Substances produced thereby or obtained therefrom
Abstract
The invention discloses a kind of less toxic Gao Minyi for confined space to decompose pyrethrins and its manufacturing method, the pyrethrins is divided into A, two kinds of components of B, component A is with magnesium powder, 2- methyltetrahydrofuran, Bromoethyl phenyl ether, trishydroxymethylaminomethane, iodine is brilliant, the fluoro- 3- phenoxy benzaldehyde of 4-, acetaldehyde, phosphorus tribromide is raw material, with ethyl alcohol, nickel powder, the sodium hydrate aqueous solution of mass concentration 20%, toluene, deionized water, the hydrochloric acid of 5% mass concentration is technique auxiliary material, through aldol polycondensation, grignard reaction, add hydrogen, bromo hydrogen, coupling, degradable modification and finally obtain；B component is to be made using fresh liver as raw material through degreasing, rupture of membranes, purification, Purified in electrophoresis, dusting, preservation.The present invention have the high contact toxicity of mosquito, mosquito height it is stomach toxicity, to people's hypotoxicity, degradable, easy metabolism, without to metal protection.
Description
Technical field
The present invention relates to decompose deinsectization except mosquito technical field more particularly to a kind of less toxic Gao Minyi for confined space
Pyrethroids and its manufacturing method.
Background technique
Confined space is an industry security term, refers to the environment of a sealing and occlusion, such as husky well, tunnel and pump
Room etc..Because disengaging place is restricted, in addition confined space is normally filled with room air pollution；It goes to make outlet air from fire-fighting angle
Danger assessment, there are titanic perils for confined space, including easily cause and strile-back and the fatefulue phenomena such as flash burn.
Pyrethrins is a kind of broad spectrum pesticide that can prevent and treat various pests, insecticidal toxicity than older generation insecticide if any
Machine chlorine, organic phosphorus, carbamates improve 10-100 times.Pyrethroid has strong action of contace poison to insect, some
Kind has both stomach toxicity or fumigation action, but all without systemic action.Its mechanism of action is to upset the normal physiological of insect nerve, is made
By excited, spasm to benumbing and dead.Pyrethroid is therefore safer to people and animals because dosage is small, low using concentration, to environment
Pollution very little.Its disadvantage mainly to fish toxicity height, also has injury to certain beneficial insects, and long-term reuse also results in pest
It develops drug resistance.
When in confined space, since air composition is mixed and disorderly, space environment is damp and hot, rather dark, mosquito preferably
It breeds and is not suitable for mankind's activity, due to bad environments, the people of Working in confined space endure mosquito invasion to the fullest extent, and long-acting Dalmatian chrysanthemum
Ester is generally also harmful to people, more since environment is special and closes, and is difficult to degrade, long time integration can be brought greatly in human body
Killing；On the other hand, general pyrethrins is aqueous organopolysiloxane, and perishable metal after atomization leads to the branch in confined space
The rotten speed of support structure is accelerated, and security risk is brought.
Therefore need in the market a kind of high contact toxicity of mosquito, mosquito height it is stomach toxicity, to people's hypotoxicity, degradable, easy metabolism,
Pyrethrins is decomposed without the less toxic Gao Minyi for confined space to metal protection.
Summary of the invention
To solve drawbacks described above existing in the prior art, the present invention is intended to provide a kind of high contact toxicity of mosquito, mosquito are high
It is stomach toxicity, to people's hypotoxicity, degradable, easy metabolism, without the less toxic Gao Minyi decomposition for confined space to metal protection
Pyrethrins.
In order to achieve the above-mentioned object of the invention, the invention adopts the following technical scheme: a kind of low toxicity for confined space is high
The quick easy manufacturing method for decomposing pyrethrins, comprising the following steps:
1) raw material prepare
1. raw material prepare: preparation 2.5 parts -3 parts of magnesium powder, 16 parts -18 parts of 2- methyltetrahydrofuran, bromobenzene second by weight
7 parts -8 parts of ether, 120 parts -150 parts of trishydroxymethylaminomethane, iodine brilliant 0.1 part -0.2 part, the fluoro- 3- phenoxy benzaldehyde 22 of 4-
Part -24 parts, 5 parts -6 parts of acetaldehyde, 7 parts -8 parts of phosphorus tribromide, 100 parts -120 parts of fresh liver；
2. technique auxiliary material prepares: it is water-soluble to prepare enough ethyl alcohol, enough nickel powders, the sodium hydroxide of enough mass concentrations 20%
Liquid, sufficient toluene, Enough Dl water, the hydrochloric acid of 5% mass concentration, enough nitrogen, enough mass concentrations 40% ammonium sulfate
Solution, enough polyacrylamide-sodium dodecyl sulfate gels；
3. equipment and tooling prepare: enough reaction vessels plus hydrogen kettle；
2) the first pre product synthesizes
1. by the stage 1) the step magnesium powder, 2- methyltetrahydrofuran and the iodine crystalline substance that 1. prepare successively put into the stage 1) step is 3. quasi-
It is standby, maintain the stage 1 for being equal to atmospheric pressure) the first reaction vessel of nitrogen flow for 2. preparing of step, it is anti-by heating
It answers container to carry out initiation hair to answer, until after reaction, obtaining and causing product；
2. in 1. initiation product that step obtains, keep it is temperature-resistant, by 0.8% based on Bromoethyl phenyl ether gross mass/
Bromoethyl phenyl ether is uniformly slowly added dropwise in the quality drop rate of min-1%/min, and temperature-resistant 40min- is kept after being added dropwise to complete
50min obtains solvent to be processed；
3. in the stage 1) step 3. prepare, maintain the stage 1 for being equal to atmospheric pressure) nitrogen flow that 2. prepares of step
The second reaction vessel in put into the stage 1) 1. whole trishydroxymethylaminomethanes that step prepares, then 2. step is obtained
The quality drop rate of solvent to be processed 5%/min-8%/min in terms of solvent gross mass to be processed is uniformly slowly added drop-wise to three
In hydroxymethyl aminomethane, 45 DEG C -50 DEG C of maintaining reaction temperature is simultaneously persistently stirred with the rate of 20rpm/min-30rpm/min
4h-5h filters out Solid content, then by surplus solution negative pressure precipitation, rectifying simultaneously collects main fraction, obtains the first pre product；
3) the second pre product synthesizes
1. with the stage 1) sodium hydrate aqueous solution of 2. ethyl alcohol that step prepares and mass concentration 20% by volume 1:
0.5-1.5 is made into miscible fluid, and the stage 1 is successively put into miscible fluid) step 1. prepare the fluoro- 3- phenoxy benzaldehyde of 4-, second
Aldehyde is warming up to 70 DEG C -80 DEG C, and then heat preservation to reaction is completed, and obtains reaction solution；
2. using the stage 1) for the toluene that 2. prepares of step as extracting solution, extracting liquid volume is the 40%- of reaction solution volume
60%, extracting solution is added drop-wise to stirring in 4. reaction solution that step obtains and removes aqueous solution part to natural layering, remains with
Solvent part, then using deionized water oscillation cleaning organic solvent to pH value neutrality, then vacuum distillation recycling design, is received
155 DEG C/100Pa-165 DEG C/100Pa of collection evaporates the fraction in area, obtains fraction to be processed；
3. by 2. fraction to be processed that step obtains and stage 1) the step ethyl alcohol, the nickel powder that 2. prepare successively put into and add hydrogen kettle
In, hydrogen is filled with disposably with the pressure of kettle pressure 3MPa-4MPa, the middle control after kettle pressure drop to 1.5MPa, when fraction to be processed is residual
Surplus filters out Solid content after being lower than 1.5%, and then vacuum distillation recycling design, obtains stand-by solvent；
4. 3. stand-by solvent that step obtains is put into the stage 1) in the toluene solvant that 2. prepares of step, then by 15%/
The stage 1 is added dropwise in the quality drop rate of min-20%/min) 1. phosphorus tribromide that step prepares, 2.5h- is stood after being added dropwise to complete
3h obtains miscible agent, and using deionized water oscillation cleaning, to miscible agent pH value, neutral, vacuum distillation recycling design, collection master evaporate
Part to get to the second pre product；
4) synthesis and modification of component A
1. using toluene as solvent, by the stage 1) the step remaining magnesium powder, residue 2- methyltetrahydrofuran and the residue that 1. prepare
Iodine crystalline substance successively puts into the stage 1) in the third reaction vessel that 3. prepares of step, carries out causing hair by heating reaction vessel and answer, until
After reaction, the stage 3 is added dropwise with the quality drop rate of 40%/min-50%/min immediately) the second pre product for obtaining,
2.5h-3h is stood after being added dropwise to complete, and the dropwise addition stage 2 is then added dropwise with the quality drop rate of 10%/min-12%/min) it obtains
The first pre product, stand 10h-12h after being added dropwise to complete, obtain end solution to be processed；
2. successively using the stage 1) 1. the hydrochloric acid of 5% mass concentration that 2. prepares of step and deionized water obtain step
End solution to be processed is washed, and is then used organic phase vacuum distillation, is obtained product of distillation, which is prefabricated Dalmatian chrysanthemum
Ester；
3. using deionized water by the stage 1) sodium hydrate aqueous solution of mass concentration 20% that 2. prepares of step is diluted to
After the sodium hydrate aqueous solution of mass concentration 1%, using dilution as the medium prefabricated pyrethrins that repeatedly 2. Washing obtains
No longer change to pH value, that is, component A needed for obtaining；
5) manufacture of component B
1. by the stage 1) fresh liver that 1. prepares of step machine barking and is chopped into the cell of partial size 1mm-2mm after cleaning
Grain, is then immersed in the stage 1) 2. step shakes degreasing using 200W-250W power ultrasonic in ethyl alcohol, obtain defatted cells grain；
2. -70 DEG C are put into after 1. defatted cells grain that step obtains is mixed with 5 times of its quality of deionized water immediately --
It is quick-frozen in 100 DEG C of household freezers, until taking out simultaneously mechanical grinding grinds after fully charge, rupture of membranes mixing ice slag is obtained, it is natural to ice slag
After dissolution, centrifugal treating is carried out using the rate of 9000rpm/min-12000rpm/min, supernatant is intercepted, obtains prefabricated
B component solution；
3. 2. prefabricated B component solution injection stage 1 that step is obtained) in the ammonium sulfate that 2. prepares of step, it is shaken to mixed
Centrifugal treating is carried out with the rate of 6000rpm/min-8000rpm/min again after uniformly, takes supernatant, obtains purifying B component
Solution；
4. use the stage 1) polyacrylamide-sodium dodecyl sulfate gel for 2. preparing of step 3. step is obtained it is pure
Change B component solution and carry out purifying electrophoretic process, obtains powder after separation product dehydration, which fills B component needed for object is；
6) whole pyrethrins processed
1. by the stage 5) obtain B component and the stage 4) obtain component A after mixing, that is, obtain needed for Dalmatian chrysanthemum
Ester, the pyrethrins are pyrethroids organic solution and the mixed uniformly dirty solution of powdered curing object.
The pyrethrins manufactured using the above method, the pyrethrins are divided into two kinds of components of A, B, and component A is with by weight
Part meter 2.5 parts -3 parts of magnesium powder, 16 parts -18 parts of 2- methyltetrahydrofuran, 7 parts -8 parts of Bromoethyl phenyl ether, trishydroxymethylaminomethane 120
- 150 parts of part, iodine brilliant 0.1 part -0.2 part, 22 parts -24 parts of the fluoro- 3- phenoxy benzaldehyde of 4-, 5 parts -6 parts of acetaldehyde, phosphorus tribromide 7
- 8 parts of part are raw material, dense with ethyl alcohol, nickel powder, the sodium hydrate aqueous solution of mass concentration 20%, toluene, deionized water, 5% mass
The hydrochloric acid of degree be technique auxiliary material, through aldol polycondensation, grignard reaction, plus hydrogen, bromo hydrogen, coupling, degradable modification and finally obtain；
B component is to be made using fresh liver as raw material through degreasing, rupture of membranes, purification, Purified in electrophoresis, dusting, preservation.
Compared with prior art, by adopting the above-described technical solution, the invention has the following advantages that (1) is different from
The numerous and complicated pyrethroids of the prior art or pyrethroids mixture, most of raw material that the present invention uses are that market is common, this field
Common raw material are easy to purchase, are easy to cost and quality control (being all mature technology mostly), and the invention core
Intermediate material fluorine 3-Phenoxy-benzaldehyde and last modification be also can be realized with a low cost, quality controllable system, index can be measured, thus right
Industrialized production of the present invention realizes and expands that the scope of application has very great help.(2) component A of the invention is using silafluofene as desinsection
Main ingredient object, this pyrethroids is to people's small toxicity but big to worm poison, mainly realizes desinsection purpose with stomach toxicity by tagging, and
What the special synthetic route of the present invention and method were different from the prior art is the 2- methyltetrahydrofuran with low toxicity instead of high poison
Tetrahydrofuran, selected the trishydroxymethylaminomethane for having facilitation to subsequent electrophoretic process, passed through grignard reaction, bromine
Generation, hydrogen generation and etc. activated pyrethroids and make obtain polymer organic molecular size range it is more controllable, more conducively detection and product control.
(3) present invention is due to using 2- methyltetrahydrofuran, trishydroxymethylaminomethane, the fluoro- 3- phenoxy benzaldehyde of 4-, finally
The silafluofene average molecular weight of acquisition, which is less than, commonly uses commercially available silafluofene, and activity/toxicity is higher, degrades faster.(4) of the invention
The either pure organic solution of component A or the dry powder of B component will not all generate additional corrosion to metal, not destroy metal
Structure, therefore additional security risk will not be brought.(5) present invention carries out hydroxylation modification using the sodium hydroxide of 1% concentration, and one
After hydroxylation is utilized in aspect, on the other hand silafluofene is made to alkalize, it is well known that other than a small number of high activity metals such as aluminium, titanium,
It is the most metals material of base easily by acid corrosion without by caustic corrosion, due to the particularity of closed environment, this ring using iron
Border is typically all acidic environment (humus, damp and hot etc.), and weakly alkaline solution can cause more effectively the biology in this system
Killing (drug resistance is low), while electrophoresis can also be such that pyrethroids further activates, and come into force more efficient.(6) present invention utilizes electrophoresis
Component B is further purified, and (according to actual measurement, the component B structure obtained after electrophoresis of the present invention is very unified, there is cholinesterases to be
Protein, molecular weight float 75000 or so, 20%) escalation rate is no more than, and on the other hand make to obtain by Purified in electrophoresis
(the cholinesterase proteinoid most highly active PH environment that the actual measurement present invention obtains is nominal for the component B composition preferably for decomposing alkalinity
Value is 8.3, is weakly alkaline environment, just corresponding with the pyrethroids through being hydroxylated).(7) present invention is most more cleverly exactly component B
Not mutability or the activation in the environment of the anhydrous room temperature of anaerobic, and the silafluofene of component A is entirely non-polar organic liquids, because
And they can't react when being cured in the same space, but (mention above close when being applied to confined space
Closing space is mainly hygrothermal environment), since humidity is big in air, temperature is high, and two kinds of components of the invention are all again high activity objects,
Thus component A a part of atomization (is tagged) by mosquito epidermal absorption, and a part is by (stomach toxicity) in mosquito suction body, bigger portion
Dispersion is fallen in confined space, by component B by the water and hotter environment bring activity rapid catabolism in air, most
Technical purpose of the invention is realized eventually.Therefore the present invention have the high contact toxicity of mosquito, mosquito height it is stomach toxicity, to people's hypotoxicity, easily
Degradation, easily metabolism have excellent comprehensive performance without the characteristic to metal protection.
Specific embodiment
Embodiment 1:
A kind of less toxic Gao Minyi decomposition pyrethrins for confined space, the pyrethrins are divided into two kinds of components of A, B, A
Component is with magnesium powder 3g, 2- methyltetrahydrofuran 18g by weight, Bromoethyl phenyl ether 8g, trishydroxymethylaminomethane 150g, iodine
The fluoro- 3- phenoxy benzaldehyde 24g of brilliant 0.2g, 4-, acetaldehyde 6g, phosphorus tribromide 8g are raw material, with ethyl alcohol, nickel powder, mass concentration
20% sodium hydrate aqueous solution, toluene, deionized water, 5% mass concentration hydrochloric acid be technique auxiliary material, through aldol polycondensation, lattice
Family name reaction, plus hydrogen, bromo hydrogen, coupling, degradable modification and finally obtain；B component is using fresh liver 100g as raw material, through de-
Rouge, rupture of membranes, purification, Purified in electrophoresis, dusting, preservation are made.
The manufacturing method of above-mentioned pyrethrins, comprising the following steps:
1) raw material prepare
1. raw material prepare: preparation magnesium powder 3g, 2- methyltetrahydrofuran 18g, Bromoethyl phenyl ether 8g, trihydroxy methyl by weight
The fluoro- 3- phenoxy benzaldehyde 24g of aminomethane 150g, iodine crystalline substance 0.2g, 4-, acetaldehyde 6g, phosphorus tribromide 8g, fresh liver 100g；
2. technique auxiliary material prepares: it is water-soluble to prepare enough ethyl alcohol, enough nickel powders, the sodium hydroxide of enough mass concentrations 20%
Liquid, sufficient toluene, Enough Dl water, the hydrochloric acid of 5% mass concentration, enough nitrogen, enough mass concentrations 40% ammonium sulfate
Solution, enough polyacrylamide-sodium dodecyl sulfate gels；
3. equipment and tooling prepare: enough reaction vessels plus hydrogen kettle；
2) the first pre product synthesizes
1. by the stage 1) the step magnesium powder, 2- methyltetrahydrofuran and the iodine crystalline substance that 1. prepare successively put into the stage 1) step is 3. quasi-
It is standby, maintain the stage 1 for being equal to atmospheric pressure) the first reaction vessel of nitrogen flow for 2. preparing of step, it is anti-by heating
It answers container to carry out initiation hair to answer, until after reaction, obtaining and causing product；
2. keeping temperature-resistant, by the 1%/min based on Bromoethyl phenyl ether gross mass in 1. initiation product that step obtains
Bromoethyl phenyl ether is uniformly slowly added dropwise in quality drop rate, and temperature-resistant 50min is kept after being added dropwise to complete, and obtains to be processed molten
Agent；
3. in the stage 1) step 3. prepare, maintain the stage 1 for being equal to atmospheric pressure) nitrogen flow that 2. prepares of step
The second reaction vessel in put into the stage 1) 1. whole trishydroxymethylaminomethanes that step prepares, then 2. step is obtained
The quality drop rate of solvent to be processed 8%/min in terms of solvent gross mass to be processed is uniformly slowly added drop-wise to trihydroxy methyl ammonia
In methylmethane, 45 DEG C -50 DEG C of maintaining reaction temperature simultaneously persistently stirs 5h with the rate of 30rpm/min, filters out Solid content, then will remain
Remaining solution negative pressure precipitation, rectifying simultaneously collect main fraction, obtain the first pre product；
3) the second pre product synthesizes
1. with the stage 1) sodium hydrate aqueous solution of 2. ethyl alcohol that step prepares and mass concentration 20% by volume 1: 1.5
It is made into miscible fluid, the stage 1 is successively put into miscible fluid) the step fluoro- 3- phenoxy benzaldehyde of 4-, the acetaldehyde that 1. prepare, heating
To 80 DEG C, then heat preservation to reaction is completed, and obtains reaction solution；
2. using the stage 1) for the toluene that 2. prepares of step as extracting solution, extracting liquid volume is the 60% of reaction solution volume, it will
Extracting solution is added drop-wise to stirring in 4. reaction solution that step obtains and removes aqueous solution part to natural layering, retain organic solvent
Part, then using deionized water oscillation cleaning organic solvent to pH value neutrality, then vacuum distillation recycling design, collects 155
DEG C/100Pa-165 DEG C/100Pa evaporates the fraction in area, obtain fraction to be processed；
3. by 2. fraction to be processed that step obtains and stage 1) the step ethyl alcohol, the nickel powder that 2. prepare successively put into and add hydrogen kettle
In, hydrogen is filled with disposably with the pressure of kettle pressure 4MPa, the middle control after kettle pressure drop to 1.5MPa, when fraction residual volume to be processed is low
Solid content is filtered out after 1.5%, then vacuum distillation recycling design, obtain stand-by solvent；
4. 3. stand-by solvent that step obtains is put into the stage 1) in the toluene solvant that 2. prepares of step, then by 20%/
The stage 1 is added dropwise in the quality drop rate of min) 1. phosphorus tribromide that step prepares, 3h is stood after being added dropwise to complete, and obtains miscible agent,
Using deionized water oscillation cleaning to miscible agent pH value neutrality, vacuum distillation recycling design collects main fraction to get pre- to second
Product processed；
4) synthesis and modification of component A
1. using toluene as solvent, by the stage 1) the step remaining magnesium powder, residue 2- methyltetrahydrofuran and the residue that 1. prepare
Iodine crystalline substance successively puts into the stage 1) in the third reaction vessel that 3. prepares of step, carries out causing hair by heating reaction vessel and answer, until
After reaction, the stage 3 is added dropwise with the quality drop rate of 50%/min immediately) the second pre product for obtaining, it is added dropwise to complete
After stand 3h, the dropwise addition stage 2 is then added dropwise with the quality drop rate of 12%/min) the first pre product for obtaining, drip
At rear standing 12h, end solution to be processed is obtained；
2. successively using the stage 1) 1. the hydrochloric acid of 5% mass concentration that 2. prepares of step and deionized water obtain step
End solution to be processed is washed, and is then used organic phase vacuum distillation, is obtained product of distillation, which is prefabricated Dalmatian chrysanthemum
Ester；
3. using deionized water by the stage 1) sodium hydrate aqueous solution of mass concentration 20% that 2. prepares of step is diluted to
After the sodium hydrate aqueous solution of mass concentration 1%, using dilution as the medium prefabricated pyrethrins that repeatedly 2. Washing obtains
No longer change to pH value, that is, component A needed for obtaining；
5) manufacture of component B
1. by the stage 1) fresh liver that 1. prepares of step machine barking and is chopped into the cell of partial size 1mm-2mm after cleaning
Grain, is then immersed in the stage 1) 2. step shakes degreasing using 250W power ultrasonic in ethyl alcohol, obtain defatted cells grain；
2. -100 DEG C of investment is cold immediately after 1. defatted cells grain that step obtains is mixed with 5 times of its quality of deionized water
It is quick-frozen in jelly case, until taking out simultaneously mechanical grinding grinds after fully charge, rupture of membranes mixing ice slag is obtained, dissolves and finishes naturally to ice slag
Afterwards, centrifugal treating is carried out using the rate of 12000rpm/min, intercepts supernatant, obtains prefabricated B component solution；
3. 2. prefabricated B component solution injection stage 1 that step is obtained) in the ammonium sulfate that 2. prepares of step, it is shaken to mixed
Centrifugal treating is carried out with the rate of 8000rpm/min again after uniformly, takes supernatant, obtains purifying B component solution；
4. use the stage 1) polyacrylamide-sodium dodecyl sulfate gel for 2. preparing of step 3. step is obtained it is pure
Change B component solution and carry out purifying electrophoretic process, obtains powder after separation product dehydration, which fills B component needed for object is；
6) whole pyrethrins processed
1. by the stage 5) obtain B component and the stage 4) obtain component A after mixing, that is, obtain needed for Dalmatian chrysanthemum
Ester, the pyrethrins are pyrethroids organic solution and the mixed uniformly dirty solution of powdered curing object.
Embodiment 2
It is whole consistent with embodiment 1, it is in place of difference:
A kind of less toxic Gao Minyi decomposition pyrethrins for confined space, the pyrethrins are divided into two kinds of components of A, B, A
Component be with magnesium powder 2.5g, 2- methyltetrahydrofuran 16g by weight, Bromoethyl phenyl ether 7g, trishydroxymethylaminomethane 120g,
The fluoro- 3- phenoxy benzaldehyde 22g of iodine crystalline substance 0.1g, 4-, acetaldehyde 5g, phosphorus tribromide 7g, fresh liver 120g be raw material, with ethyl alcohol,
Nickel powder, the sodium hydrate aqueous solution of mass concentration 20%, toluene, deionized water, 5% mass concentration hydrochloric acid be technique auxiliary material,
Through aldol polycondensation, grignard reaction, plus hydrogen, bromo hydrogen, coupling, degradable modification and finally obtain；B component is to be with fresh liver
Raw material is made through degreasing, rupture of membranes, purification, Purified in electrophoresis, dusting, preservation.
The manufacturing method of above-mentioned pyrethrins, comprising the following steps:
1) raw material prepare
1. raw material prepare: preparation magnesium powder 2.5g, 2- methyltetrahydrofuran 16g, Bromoethyl phenyl ether 7g, three hydroxyl first by weight
The fluoro- 3- phenoxy benzaldehyde 22g of base aminomethane 120g, iodine crystalline substance 0.1g, 4-, acetaldehyde 5g, phosphorus tribromide 7g, fresh liver
120g；
2) the first pre product synthesizes
2. keeping temperature-resistant, by the 0.8%/min based on Bromoethyl phenyl ether gross mass in 1. initiation product that step obtains
Quality drop rate Bromoethyl phenyl ether is uniformly slowly added dropwise, keep temperature-resistant 40min after being added dropwise to complete, obtain to be processed molten
Agent；
3. in the stage 1) step 3. prepare, maintain the stage 1 for being equal to atmospheric pressure) nitrogen flow that 2. prepares of step
The second reaction vessel in put into the stage 1) 1. whole trishydroxymethylaminomethanes that step prepares, then 2. step is obtained
The quality drop rate of solvent to be processed 5%/min in terms of solvent gross mass to be processed is uniformly slowly added drop-wise to trihydroxy methyl ammonia
In methylmethane, 45 DEG C -50 DEG C of maintaining reaction temperature simultaneously persistently stirs 4h with the rate of 20rpm/min, filters out Solid content, then will remain
Remaining solution negative pressure precipitation, rectifying simultaneously collect main fraction, obtain the first pre product；
3) the second pre product synthesizes
1. with the stage 1) sodium hydrate aqueous solution of 2. ethyl alcohol that step prepares and mass concentration 20% by volume 1: 0.5
It is made into miscible fluid, the stage 1 is successively put into miscible fluid) the step fluoro- 3- phenoxy benzaldehyde of 4-, the acetaldehyde that 1. prepare, heating
To 70 DEG C, then heat preservation to reaction is completed, and obtains reaction solution；
2. using the stage 1) for the toluene that 2. prepares of step as extracting solution, extracting liquid volume is the 40% of reaction solution volume, it will
Extracting solution is added drop-wise to stirring in 4. reaction solution that step obtains and removes aqueous solution part to natural layering, retain organic solvent
Part, then using deionized water oscillation cleaning organic solvent to pH value neutrality, then vacuum distillation recycling design, collects 155
DEG C/100Pa-165 DEG C/100Pa evaporates the fraction in area, obtain fraction to be processed；
3. by 2. fraction to be processed that step obtains and stage 1) the step ethyl alcohol, the nickel powder that 2. prepare successively put into and add hydrogen kettle
In, hydrogen is filled with disposably with the pressure of kettle pressure 3MPa, the middle control after kettle pressure drop to 1.5MPa, when fraction residual volume to be processed is low
Solid content is filtered out after 1.5%, then vacuum distillation recycling design, obtain stand-by solvent；
4. 3. stand-by solvent that step obtains is put into the stage 1) in the toluene solvant that 2. prepares of step, then by 15%/
The stage 1 is added dropwise in the quality drop rate of min) 1. phosphorus tribromide that step prepares, 2.5h is stood after being added dropwise to complete, and is obtained miscible
Agent, using deionized water oscillation cleaning to miscible agent pH value neutral, vacuum distillation recycling design, collect main fraction to get to the
Two pre products；
4) synthesis and modification of component A
1. using toluene as solvent, by the stage 1) the step remaining magnesium powder, residue 2- methyltetrahydrofuran and the residue that 1. prepare
Iodine crystalline substance successively puts into the stage 1) in the third reaction vessel that 3. prepares of step, carries out causing hair by heating reaction vessel and answer, until
After reaction, the stage 3 is added dropwise with the quality drop rate of 40%/min immediately) the second pre product for obtaining, it is added dropwise to complete
After stand 2.5h, the dropwise addition stage 2 is then added dropwise with the quality drop rate of 10%/min) the first pre product for obtaining, be added dropwise
10h is stood after the completion, obtains end solution to be processed；
5) manufacture of component B
1. by the stage 1) fresh liver that 1. prepares of step machine barking and is chopped into the cell of partial size 1mm-2mm after cleaning
Grain, is then immersed in the stage 1) 2. step shakes degreasing using 200W power ultrasonic in ethyl alcohol, obtain defatted cells grain；
2. -70 DEG C of investment is cold immediately after 1. defatted cells grain that step obtains is mixed with 5 times of its quality of deionized water
It is quick-frozen in jelly case, until taking out simultaneously mechanical grinding grinds after fully charge, rupture of membranes mixing ice slag is obtained, dissolves and finishes naturally to ice slag
Afterwards, centrifugal treating is carried out using the rate of 9000rpm/min, intercepts supernatant, obtains prefabricated B component solution；
3. 2. prefabricated B component solution injection stage 1 that step is obtained) in the ammonium sulfate that 2. prepares of step, it is shaken to mixed
Centrifugal treating is carried out with the rate of 6000rpm/min again after uniformly, takes supernatant, obtains purifying B component solution；
The foregoing description of the disclosed embodiments, only for can be realized professional and technical personnel in the field or use this
Invention.Various modifications to these embodiments will be readily apparent to those skilled in the art, institute herein
The General Principle of definition can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore,
The present invention will not be limited to the embodiments shown herein, and is to fit to special with principles disclosed herein and novelty
The consistent widest scope of point.
Claims (2)
1. the manufacturing method that a kind of less toxic Gao Minyi for confined space decomposes pyrethrins, it is characterised in that including following step
It is rapid:
1) raw material prepare
1. raw material prepare: preparation 2.5 parts -3 parts of magnesium powder, 16 parts -18 parts of 2- methyltetrahydrofuran, Bromoethyl phenyl ether 7 by weight
- 8 parts of part, 120 parts -150 parts of trishydroxymethylaminomethane, iodine are 0.1 part -0.2 part, 22 part -24 of the fluoro- 3- phenoxy benzaldehyde of 4- brilliant
Part, 5 parts -6 parts of acetaldehyde, 7 parts -8 parts of phosphorus tribromide, 100 parts -120 parts of fresh liver；
2. technique auxiliary material prepares: preparing enough ethyl alcohol, enough nickel powders, the sodium hydrate aqueous solution of enough mass concentrations 20%, foot
Measure toluene, Enough Dl water, the hydrochloric acid of 5% mass concentration, enough nitrogen, enough mass concentrations 40% ammonium sulfate,
Enough polyacrylamide-sodium dodecyl sulfate gels；
3. equipment and tooling prepare: enough reaction vessels plus hydrogen kettle；
2) the first pre product synthesizes
1. by the stage 1) the step magnesium powder, 2- methyltetrahydrofuran and the iodine crystalline substance that 1. prepare successively put into the stage 1) 3. step prepares
, maintain the stage 1 for being equal to atmospheric pressure) 2. the first reaction vessel of nitrogen flow that step prepares, pass through heating reaction
Container cause sending out and be answered, until after reaction, obtaining and causing product；
2. keeping temperature-resistant, by the 0.8%/min- based on Bromoethyl phenyl ether gross mass in 1. initiation product that step obtains
Bromoethyl phenyl ether is uniformly slowly added dropwise in the quality drop rate of 1%/min, and temperature-resistant 40min- is kept after being added dropwise to complete
50min obtains solvent to be processed；
3. in the stage 1) step 3. prepare, maintain the stage 1 for being equal to atmospheric pressure) step 2. prepare the of nitrogen flow
The stage 1 is put into two reaction vessels) whole trishydroxymethylaminomethanes for 1. preparing of step, then by step 2. obtain wait locate
The quality drop rate of reason solvent 5%/min-8%/min in terms of solvent gross mass to be processed is uniformly slowly added drop-wise to three hydroxyl first
In base aminomethane, 45 DEG C -50 DEG C of maintaining reaction temperature simultaneously persistently stirs 4h-5h with the rate of 20rpm/min-30rpm/min,
Solid content is filtered out, then by surplus solution negative pressure precipitation, rectifying simultaneously collects main fraction, obtains the first pre product；
3) the second pre product synthesizes
1. with the stage 1) sodium hydrate aqueous solution of 2. ethyl alcohol that step prepares and mass concentration 20% by volume 1: 0.5-1.5
It is made into miscible fluid, the stage 1 is successively put into miscible fluid) the step fluoro- 3- phenoxy benzaldehyde of 4-, the acetaldehyde that 1. prepare, heating
To 70 DEG C -80 DEG C, then heat preservation to reaction is completed, and obtains reaction solution；
2. using the stage 1) for the toluene that 2. prepares of step as extracting solution, extracting liquid volume is the 40%-60% of reaction solution volume, it will
Extracting solution is added drop-wise to stirring in 4. reaction solution that step obtains and removes aqueous solution part to natural layering, retain organic solvent
Part, then using deionized water oscillation cleaning organic solvent to pH value neutrality, then vacuum distillation recycling design, collects 155
DEG C/100Pa-165 DEG C/100Pa evaporates the fraction in area, obtain fraction to be processed；
3. by 2. fraction to be processed that step obtains and stage 1) the step ethyl alcohol, the nickel powder that 2. prepare successively put into and add in hydrogen kettle,
It is disposably filled with hydrogen with the pressure of kettle pressure 3MPa-4MPa, the middle control after kettle pressure drop to 1.5MPa, when fraction residual volume to be processed
Solid content is filtered out after lower than 1.5%, then vacuum distillation recycling design, obtain stand-by solvent；
4. 3. stand-by solvent that step obtains is put into the stage 1) in the toluene solvant that 2. prepares of step, then press 15%/min-
The stage 1 is added dropwise in the quality drop rate of 20%/min) 1. phosphorus tribromide that step prepares, 2.5h-3h is stood after being added dropwise to complete, is obtained
Miscible agent is obtained, neutral to miscible agent pH value using deionized water oscillation cleaning, vacuum distillation recycling design collects main fraction, i.e.,
Obtain the second pre product；
4) synthesis and modification of component A
1. using toluene as solvent, by the stage 1) the step remaining magnesium powder, residue 2- methyltetrahydrofuran and the remaining iodine that 1. prepare is brilliant
Successively put into the stage 1) in the third reaction vessel that 3. prepares of step, carries out causing hair by heating reaction vessel and answer, to reacting
After, the stage 3 is added dropwise with the quality drop rate of 40%/min-50%/min immediately) the second pre product for obtaining, it is added dropwise
Stand 2.5h-3h after the completion, the dropwise addition stage 2 be then added dropwise with the quality drop rate of 10%/min-12%/min) obtain the
One pre product stands 10h-12h after being added dropwise to complete, and obtains end solution to be processed；
2. successively use the stage 1) hydrochloric acid of 5% mass concentration that 2. prepares of step and deionized water to step 1. obtain wait locate
Solution processed is washed reason eventually, is then used organic phase vacuum distillation, is obtained product of distillation, which is prefabricated pyrethrins；
3. using deionized water by the stage 1) sodium hydrate aqueous solution of mass concentration 20% that 2. prepares of step is diluted to quality
After the sodium hydrate aqueous solution of concentration 1%, using dilution as the medium prefabricated pyrethrins that repeatedly 2. Washing obtains to PH
Value no longer changes, that is, component A needed for obtaining；
5) manufacture of component B
1. by the stage 1) fresh liver that 1. prepares of step machine barking and is chopped into the cell grain of partial size 1mm-2mm after cleaning,
It is then immersed in the stage 1) 2. step shakes degreasing using 200W-250W power ultrasonic in ethyl alcohol, obtain defatted cells grain；
2. -70 DEG C are put into after 1. defatted cells grain that step obtains is mixed with 5 times of its quality of deionized water immediately -- 100 DEG C
It is quick-frozen in household freezer, until taking out simultaneously mechanical grinding grinds after fully charge, rupture of membranes mixing ice slag is obtained, has been dissolved naturally to ice slag
Bi Hou carries out centrifugal treating using the rate of 9000rpm/min-12000rpm/min, intercepts supernatant, obtain prefabricated B component
Solution；
3. 2. prefabricated B component solution injection stage 1 that step is obtained) in the ammonium sulfate that 2. prepares of step, it is shaken to mixed uniformly
Centrifugal treating is carried out with the rate of 6000rpm/min-8000rpm/min again afterwards, takes supernatant, obtains purifying B component solution；
4. use the stage 1) polyacrylamide-sodium dodecyl sulfate gel for 2. preparing of step 3. purifying B that step is obtained
Component solution carries out purifying electrophoretic process, obtains powder after separation product dehydration, which fills B component needed for object is；
6) whole pyrethrins processed
1. by the stage 5) obtain B component and the stage 4) obtain component A after mixing, that is, obtain needed for pyrethrins, should
Pyrethrins is pyrethroids organic solution and the mixed uniformly dirty solution of powdered curing object.
2. a kind of less toxic Gao Minyi for confined space decomposes pyrethrins, it is characterised in that: the pyrethrins is divided into A, B two
Kind component, component A is with 2.5 parts -3 parts of magnesium powder by weight, 16 parts -18 parts of 2- methyltetrahydrofuran, 7 part -8 of Bromoethyl phenyl ether
Part, 120 parts -150 parts of trishydroxymethylaminomethane, iodine is 0.1 part -0.2 part brilliant, 22 parts -24 parts of the fluoro- 3- phenoxy benzaldehyde of 4-,
5 parts -6 parts of acetaldehyde, 7 parts -8 parts of phosphorus tribromide be raw material, with ethyl alcohol, nickel powder, the sodium hydrate aqueous solution of mass concentration 20%, first
Benzene, deionized water, 5% mass concentration hydrochloric acid be technique auxiliary material, through aldol polycondensation, grignard reaction, plus hydrogen, bromo hydrogen, coupling,
Degradable modification and finally obtain；B component be using fresh liver as raw material, through degreasing, rupture of membranes, purification, Purified in electrophoresis, dusting,
Preservation is made.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2097971C1 (en) * | 1990-09-12 | 1997-12-10 | Перюкут-Хеми Аг | Pyrethroid-containing insecticide agent |
| CN103688986A (en) * | 2013-12-13 | 2014-04-02 | 广西田园生化股份有限公司 | Ultra low volume concentrate containing silafluofen and chloronicotinyl insecticide |
| CN106973941A (en) * | 2017-05-03 | 2017-07-25 | 明光市飞洲新材料有限公司 | A kind of attapulgite modified efficient mosquito lures agent and preparation method thereof of going out |
| US20180235230A1 (en) * | 2017-02-13 | 2018-08-23 | Clarke Mosquito Control Products, Inc. | Insecticidal composition |
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2018
- 2018-10-31 CN CN201811284972.2A patent/CN109293604A/en not_active Withdrawn
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2097971C1 (en) * | 1990-09-12 | 1997-12-10 | Перюкут-Хеми Аг | Pyrethroid-containing insecticide agent |
| CN103688986A (en) * | 2013-12-13 | 2014-04-02 | 广西田园生化股份有限公司 | Ultra low volume concentrate containing silafluofen and chloronicotinyl insecticide |
| US20180235230A1 (en) * | 2017-02-13 | 2018-08-23 | Clarke Mosquito Control Products, Inc. | Insecticidal composition |
| CN106973941A (en) * | 2017-05-03 | 2017-07-25 | 明光市飞洲新材料有限公司 | A kind of attapulgite modified efficient mosquito lures agent and preparation method thereof of going out |
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| Title |
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| 丛杉等: "广谱杀虫杀螨剂氟硅菊酯的合成综述", 《现代农药》 * |
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