CN112390944A - Synthetic method and application of bacillus thuringiensis auxiliary agent - Google Patents
Synthetic method and application of bacillus thuringiensis auxiliary agent Download PDFInfo
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- bacillus thuringiensis
- polyoxyethylene ether
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- 241000193388 Bacillus thuringiensis Species 0.000 title claims abstract description 32
- 229940097012 bacillus thuringiensis Drugs 0.000 title claims abstract description 32
- 239000012752 auxiliary agent Substances 0.000 title claims abstract description 9
- 238000010189 synthetic method Methods 0.000 title abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 38
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 37
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 37
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000004562 water dispersible granule Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- TVFWYUWNQVRQRG-UHFFFAOYSA-N 2,3,4-tris(2-phenylethenyl)phenol Chemical compound C=1C=CC=CC=1C=CC1=C(C=CC=2C=CC=CC=2)C(O)=CC=C1C=CC1=CC=CC=C1 TVFWYUWNQVRQRG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 12
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 12
- 238000004321 preservation Methods 0.000 claims abstract description 11
- 239000002671 adjuvant Substances 0.000 claims abstract description 9
- 230000007062 hydrolysis Effects 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000001308 synthesis method Methods 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims abstract description 4
- 230000032050 esterification Effects 0.000 claims abstract description 3
- 238000005886 esterification reaction Methods 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 14
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- KLIIGADLHUOXPS-UHFFFAOYSA-N 2-(1,2,2-triphenylethenyl)phenol Chemical compound OC1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 KLIIGADLHUOXPS-UHFFFAOYSA-N 0.000 claims description 4
- BOLQUPOXTWHXIX-UHFFFAOYSA-N OC1=CC=CC=C1.C=1C=CC=CC=1C=C(C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound OC1=CC=CC=C1.C=1C=CC=CC=1C=C(C=1C=CC=CC=1)C1=CC=CC=C1 BOLQUPOXTWHXIX-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 abstract description 25
- 239000010452 phosphate Substances 0.000 abstract description 25
- -1 styryl phenol Chemical compound 0.000 abstract description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 18
- 150000005690 diesters Chemical class 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000000725 suspension Substances 0.000 abstract description 4
- 238000005338 heat storage Methods 0.000 abstract description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 abstract description 3
- 230000001018 virulence Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 14
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- 239000012263 liquid product Substances 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920001732 Lignosulfonate Polymers 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- HLPHHOLZSKWDAK-UHFFFAOYSA-M sodium;formaldehyde;naphthalene-1-sulfonate Chemical compound [Na+].O=C.C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HLPHHOLZSKWDAK-UHFFFAOYSA-M 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 239000004135 Bone phosphate Substances 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000000853 biopesticidal effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical class OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 229940042880 natural phospholipid Drugs 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004563 wettable powder Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/338—Polymers modified by chemical after-treatment with inorganic and organic compounds
-
- 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
- A01N25/12—Powders or granules
- A01N25/14—Powders or granules wettable
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- 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
- A01N63/20—Bacteria; Substances produced thereby or obtained therefrom
- A01N63/22—Bacillus
- A01N63/23—B. thuringiensis
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/327—Polymers modified by chemical after-treatment with inorganic compounds containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33396—Polymers modified by chemical after-treatment with organic compounds containing nitrogen having oxygen in addition to nitrogen
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Zoology (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Dentistry (AREA)
- Inorganic Chemistry (AREA)
- Toxicology (AREA)
- Virology (AREA)
- Microbiology (AREA)
- Biotechnology (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention discloses a synthesis method and application of a bacillus thuringiensis auxiliary agent, which comprises the following steps: 1) mixing: adding a certain amount of tristyrylphenol polyoxyethylene ether into a four-neck flask provided with a heating circulation device, a thermometer and a mechanical stirrer, controlling the temperature at 40 ℃, adding P while stirring2O5Powder, then heating to 50 ℃, mixing and stirring; 2) esterification: stirring the mixed solution for 0.5h, heating to 70 ℃, and reacting for 3-5h under heat preservation; 3) hydrolysis: adding deionized water, and reacting for 0.5 h; 4) neutralizing: adding triethanolamine, heating to 75 deg.C, and reacting for 1 h. The synthetic method provided by the invention has the advantages that the styryl phenol polyoxyethylene ether phosphate salt as the bacillus thuringiensis adjuvant has good repeatability of monoester and diester, and the monoester content in the product is high, thus being beneficial to the stability of the water dispersible granules; in addition, the bacillus thuringiensis water dispersible granules prepared by the phosphate are high in virulence titer, high in suspension rate, good in dispersibility and stable in performance after heat storage.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a synthesis method and application of a bacillus thuringiensis auxiliary agent.
Background
As a biopesticide complementing chemical pesticides, bacillus thuringiensis plays an important role in the prevention and control of plant diseases and insect pests, and also plays an important role in organic agriculture. Bacillus thuringiensis is highly selective and safe to human, livestock, natural enemies and plants, so that the Bacillus thuringiensis is accepted by more and more people in recent years. At present, more than 100 commercial preparations of bacillus thuringiensis are used as microbial insecticides with wide application, dosage and effect in the world, so that the bacillus thuringiensis is concerned by people.
The water dispersible granule is characterized in that: good fluidity and easy metering, and avoids dust pollution caused by pouring the wettable powder from a packaging container.
The water dispersible granule is a granular preparation prepared by mixing, crushing and granulating active ingredients of pesticide, various auxiliary agents and fillers. When diluted with water, the composition can be quickly disintegrated and dispersed to form a stable suspension for spray application. The bacillus thuringiensis is a product obtained by fermenting agricultural and sideline products, wherein high sugar content is a great difficulty, which can cause the granules to have strong viscosity and difficult disintegration and dispersion, and a proper dispersant is needed to achieve the expected effect.
Phosphate esters are an important class of surfactants, and phosphorus-containing surfactants represented by phosphate ester series have excellent characteristics. Since phosphoric acid is a tribasic acid, phosphate esters generally consist of monophosphate esters, diphosphate esters and a small amount of phosphoric acid. The phosphate ester surfactant has performance similar to natural phospholipid, is easy to biodegrade, has lower irritation than common alkyl sulfonate and alkyl sulfate anionic surfactants, wherein, the diester has good smoothness and lipophilicity, and the monoester has stronger hydrophilic ability and foaming ability. The difference of the application performance and the difference of the substituent groups of the mono-ester and the diester determine that phosphate products with different mono-ester and diester ratios have different functions.
Common dispersants for bacillus thuringiensis water dispersible granules include lignosulfonate and sodium naphthalene sulfonate formaldehyde condensate. The lignosulfonate is dissolved in water most quickly, is favorable for disintegration of granules, and has poor dispersion durability. The sodium naphthalenesulfonate formaldehyde condensate has strong dispersivity, but the dispersivity is reduced after being wetted. The styryl phenol polyoxyethylene ether phosphate ester salt is used as an anionic surfactant, is a class of phosphorus-containing surfactants, has an excellent dispersing effect, is used as a bacillus thuringiensis water dispersible granule dispersing agent, and is extremely strong in dispersibility and good in stability.
Disclosure of Invention
The invention aims to provide a synthesis method and application of a bacillus thuringiensis auxiliary agent, so as to solve the technical problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: a method for synthesizing a bacillus thuringiensis adjuvant comprises the following steps:
s1: mixing: adding a certain amount of tristyrylphenol polyoxyethylene ether into a four-neck flask provided with a heating circulation device, a thermometer and a mechanical stirrer, controlling the temperature at 40 ℃, adding P while stirring2O5Powder, then heating to 50 ℃, mixing and stirring;
s2: esterification: stirring the mixed solution for 0.5h, heating to 70 ℃, and reacting for 3-5h under heat preservation;
s3: hydrolysis: adding deionized water, and reacting for 0.5 h;
s4: neutralizing: adding triethanolamine, heating to 75 deg.C, and reacting for 1 h.
As a further improvement of the technical solution of the present invention, P in the step S12O5The ratio of the amount of the triphenylvinylphenol polyoxyethylene ether to the amount of the triphenylvinylphenol polyoxyethylene ether is arbitrary.
As a further improvement of the technical solution of the present invention, P in the step S12O5The mass ratio of the triphenylethylene phenol polyoxyethylene ether to the triphenylethylene phenol polyoxyethylene ether is 1: 2-4.
As a further improvement of the technical scheme of the invention, the moisture content of the tristyrylphenol polyoxyethylene ether in the step S1 cannot be higher than 2%.
As a further improvement of the technical scheme of the invention, the deionized water in the step S3 accounts for 3% of the feeding amount.
As a further improvement of the technical scheme of the invention, the triethanolamine content and P in the step S42O5The mass of (A) is 3: 1.
The invention also provides an application of the bacillus thuringiensis auxiliary agent synthesized by the synthesis method in preparing water dispersible granules from bacillus thuringiensis.
Compared with the prior art, the invention has the beneficial effects that: the synthetic method provided by the invention has the advantages that the styryl phenol polyoxyethylene ether phosphate salt as the bacillus thuringiensis adjuvant has good repeatability of monoester and diester, and the monoester content in the product is high, thus being beneficial to the stability of the water dispersible granules; in addition, the bacillus thuringiensis water dispersible granules prepared by the phosphate are high in virulence titer, high in suspension rate, good in dispersibility and stable in performance after heat storage.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
440g of tristyrylphenol polyoxyethylene ether was charged into a four-necked flask equipped with a heating apparatus, a mechanical stirrer, and a thermometer. After the stirrer was started, the temperature was raised to 40 ℃ and P was added2O528 g. Stirring at 50 deg.C for 0.5h, and uniformly heatingAnd keeping the temperature to 70 ℃ for reaction for 3 h. 14g of deionized water was added, the hydrolysis reaction was carried out for 0.5h, and 160g of the sample was taken. Adding 53g of triethanolamine, heating to 75 ℃, and neutralizing for 1 h. The obtained yellow liquid product is styryl phenol polyoxyethylene ether phosphate, and the molecular structural formula of the target product is (C)30H24O(C2H4O)17)2POONH4、C30H24O(C2H4O)17OPO(ONH4)2。
Example 2
440g of tristyrylphenol polyoxyethylene ether was charged into a four-necked flask equipped with a heating apparatus, a mechanical stirrer, and a thermometer. After the stirrer was started, the temperature was raised to 40 ℃ and P was added2O521 g. Keeping the temperature at 50 ℃, stirring for 0.5h, uniformly heating to 70 ℃, and reacting for 3h under the condition of heat preservation. 13.6g of deionized water was added, and 155g of the mixture was sampled after 0.5 hour of hydrolysis. Adding 40g of triethanolamine, heating to 75 ℃, and neutralizing for 1 h. The obtained yellow liquid product is styryl phenol polyoxyethylene ether phosphate, and the molecular structural formula of the target product is (C)30H24O(C2H4O)17)2POONH4、C30H24O(C2H4O)17OPO(ONH4)2。
Example 3
440g of tristyrylphenol polyoxyethylene ether was charged into a four-necked flask equipped with a heating apparatus, a mechanical stirrer, and a thermometer. After the stirrer was started, the temperature was raised to 40 ℃ and P was added2O514 g. Keeping the temperature at 50 ℃, stirring for 0.5h, uniformly heating to 70 ℃, and reacting for 3h under the condition of heat preservation. 13.4g of deionized water was added, hydrolysis was carried out for 0.5 hour, and 150g of sample was taken. Adding 26.5g of triethanolamine, heating to 75 ℃, and neutralizing for 1 h. The obtained yellow liquid product is styryl phenol polyoxyethylene ether phosphate, and the molecular structural formula of the target product is (C)30H24O(C2H4O)17)2POONH4、C30H24O(C2H4O)17OPO(ONH4)2。
Example 4
440g of tristyrylphenol polyoxyethylene ether was charged into a four-necked flask equipped with a heating apparatus, a mechanical stirrer, and a thermometer. After the stirrer was started, the temperature was raised to 40 ℃ and P was added2O528 g. Keeping the temperature at 50 ℃, stirring for 0.5h, uniformly heating to 70 ℃, and reacting for 4h under the condition of heat preservation. 14g of deionized water was added, the hydrolysis reaction was carried out for 0.5h, and 160g of the sample was taken. Adding 53g of triethanolamine, heating to 75 ℃, and neutralizing for 1 h. The obtained yellow liquid product is styryl phenol polyoxyethylene ether phosphate, and the molecular structural formula of the target product is (C)30H24O(C2H4O)17)2POONH4、C30H24O(C2H4O)17OPO(ONH4)2。
Example 5
440g of tristyrylphenol polyoxyethylene ether was charged into a four-necked flask equipped with a heating apparatus, a mechanical stirrer, and a thermometer. After the stirrer was started, the temperature was raised to 40 ℃ and P was added2O521 g. Keeping the temperature at 50 ℃, stirring for 0.5h, uniformly heating to 70 ℃, and reacting for 4h under the condition of heat preservation. 13.6g of deionized water was added, and 155g of the mixture was sampled after 0.5 hour of hydrolysis. Adding 40g of triethanolamine, heating to 75 ℃, and neutralizing for 1 h. The obtained yellow liquid product is styryl phenol polyoxyethylene ether phosphate, and the molecular structural formula of the target product is (C)30H24O(C2H4O)17)2POONH4、C30H24O(C2H4O)17OPO(ONH4)2。
Example 6
440g of tristyrylphenol polyoxyethylene ether was charged into a four-necked flask equipped with a heating apparatus, a mechanical stirrer, and a thermometer. After the stirrer was started, the temperature was raised to 40 ℃ and P was added2O514 g. Keeping the temperature at 50 ℃, stirring for 0.5h, uniformly heating to 70 ℃, and reacting for 4h under the condition of heat preservation. 13.4g of deionized water was added, hydrolysis was carried out for 0.5 hour, and 150g of sample was taken. Adding triethanolamine26.5g, heating to 75 ℃, and neutralizing for 1 h. The obtained yellow liquid product is styryl phenol polyoxyethylene ether phosphate, and the molecular structural formula of the target product is (C)30H24O(C2H4O)17)2POONH4、C30H24O(C2H4O)17OPO(ONH4)2。
Example 7
440g of tristyrylphenol polyoxyethylene ether was charged into a four-necked flask equipped with a heating apparatus, a mechanical stirrer, and a thermometer. After the stirrer was started, the temperature was raised to 40 ℃ and P was added2O528 g. Keeping the temperature at 50 ℃, stirring for 0.5h, uniformly heating to 70 ℃, and carrying out heat preservation reaction for 5 h. 14g of deionized water was added, the hydrolysis reaction was carried out for 0.5h, and 160g of the sample was taken. Adding 53g of triethanolamine, heating to 75 ℃, and neutralizing for 1 h. The obtained yellow liquid product is styryl phenol polyoxyethylene ether phosphate, and the molecular structural formula of the target product is (C)30H24O(C2H4O)17)2POONH4、C30H24O(C2H4O)17OPO(ONH4)2。
Example 8
440g of tristyrylphenol polyoxyethylene ether was charged into a four-necked flask equipped with a heating apparatus, a mechanical stirrer, and a thermometer. After the stirrer was started, the temperature was raised to 40 ℃ and P was added2O521 g. Keeping the temperature at 50 ℃, stirring for 0.5h, uniformly heating to 70 ℃, and carrying out heat preservation reaction for 5 h. 13.6g of deionized water was added, and 155g of the mixture was sampled after 0.5 hour of hydrolysis. Adding 40g of triethanolamine, heating to 75 ℃, and neutralizing for 1 h. The obtained yellow liquid product is styryl phenol polyoxyethylene ether phosphate, and the molecular structural formula of the target product is (C)30H24O(C2H4O)17)2POONH4、C30H24O(C2H4O)17OPO(ONH4)2。
Example 9
In-suit clothes440g of tristyrylphenol polyoxyethylene ether was charged into a four-necked flask equipped with a heating device, a mechanical stirrer and a thermometer. After the stirrer was started, the temperature was raised to 40 ℃ and P was added2O514 g. Keeping the temperature at 50 ℃, stirring for 0.5h, uniformly heating to 70 ℃, and carrying out heat preservation reaction for 5 h. 13.4g of deionized water was added, hydrolysis was carried out for 0.5 hour, and 150g of sample was taken. Adding 26.5g of triethanolamine, heating to 75 ℃, and neutralizing for 1 h. The obtained yellow liquid product is styryl phenol polyoxyethylene ether phosphate, and the molecular structural formula of the target product is (C)30H24O(C2H4O)17)2POONH4、C30H24O(C2H4O)17OPO(ONH4)2。
The phosphoric acid monoesters, phosphoric acid diesters and pH values of the styrylphenol polyoxyethylene ether phosphate ester salt auxiliaries prepared in examples 1 to 9 are shown in the following tables:
TABLE 1 phosphoric monoester and phosphoric diester of styrylphenol polyoxyethylene ether phosphate ester salt adjuvant and pH value
| Phosphoric acid diester/%) | Phosphoric monoester/%) | pH value | |
| Example 1 | 21.05 | 78.49 | 6.60 |
| Example 2 | 23.03 | 76.43 | 6.74 |
| Example 3 | 22.76 | 76.78 | 6.89 |
| Example 4 | 21.49 | 78.01 | 6.63 |
| Example 5 | 22.12 | 77.32 | 6.81 |
| Example 6 | 22.69 | 76.82 | 6.93 |
| Example 7 | 20.75 | 78.82 | 6.54 |
| Example 8 | 22.64 | 76.86 | 6.62 |
| Example 9 | 22.83 | 76.63 | 6.87 |
As can be seen from the experimental data of the above examples 1-9, the content of the phosphoric monoester is between 76-79%, the content of the phosphoric diester is between 20-23%, and the experimental reproducibility is good. The phosphate monoester has strong hydrophilicity, good dispersion performance and good stability. Therefore, in the styrylphenol polyoxyethylene ether phosphate, the high content of the phosphate monoester is preferably controlled. The prepared phosphate can be used for preparing water dispersible granules.
Verification test
The phosphate prepared in the embodiment is applied to bacillus thuringiensis to prepare water dispersible granules.
60 percent of raw powder of the bacillus thuringiensis with the content of 50000IU/mg, 5 percent of phosphate salt, 5 percent of wetting agent, 0.3 percent of disintegrating agent and ammonium sulfate are taken for complement, evenly mixed in a stirring tank, crushed by a crusher and homogenized; granulating by adopting an extrusion granulation method, and preparing uniform granules by using a forced extrusion mode through a pore plate with a certain size and pore diameter.
Examples 1 to 9 are applied to bacillus thuringiensis to prepare water dispersible granules, and the indexes corresponding to the water dispersible granules 1 to 9 are shown in the following table:
TABLE 2 indexes of water dispersible granule 1-9
Table 3 indexes of commercially available auxiliaries NNO and K12 corresponding to water dispersible granules
The above examples and the results of the verification experiments show that: the phosphate monoester and phosphate diester synthesized by the method have good repeatability; the high content of monoester in the product is beneficial to the stability of the water dispersible granule. The bacillus thuringiensis water dispersible granules prepared by the phosphate ester have high virulence titer, high suspension rate, good dispersibility and stable performance after heat storage.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (7)
1. A method for synthesizing a bacillus thuringiensis auxiliary agent is characterized by comprising the following steps: the method comprises the following steps:
s1: mixing: adding a certain amount of tristyrylphenol polyoxyethylene ether into a four-neck flask provided with a heating circulation device, a thermometer and a mechanical stirrer, controlling the temperature at 40 ℃, adding P while stirring2O5Powder, then heating to 50 ℃, mixing and stirring;
s2: esterification: stirring the mixed solution for 0.5h, heating to 70 ℃, and reacting for 3-5h under heat preservation;
s3: hydrolysis: adding deionized water, and reacting for 0.5 h;
s4: neutralizing: adding triethanolamine, heating to 75 deg.C, and reacting for 1 h.
2. A method of synthesizing a bacillus thuringiensis adjuvant according to claim 1, wherein said method comprises: p in said step S12O5The ratio of the amount of the triphenylvinylphenol polyoxyethylene ether to the amount of the triphenylvinylphenol polyoxyethylene ether is arbitrary.
3. A method of synthesizing a bacillus thuringiensis adjuvant according to claim 2, wherein: p in said step S12O5The mass ratio of the triphenylethylene phenol polyoxyethylene ether to the triphenylethylene phenol polyoxyethylene ether is 1: 2-4.
4. A method of synthesizing a bacillus thuringiensis adjuvant according to claim 1, wherein said method comprises: the moisture content of the tristyrylphenol polyoxyethylene ether in the step S1 cannot be higher than 2%.
5. A method of synthesizing a bacillus thuringiensis adjuvant according to claim 1, wherein said method comprises: the deionized water in the step S3 accounts for 3% of the feeding amount.
6. A method of synthesizing a bacillus thuringiensis adjuvant according to claim 1, wherein said method comprises: the amount of triethanolamine and P in the step S42O5The mass of (A) is 3: 1.
7. The application of the bacillus thuringiensis auxiliary agent synthesized by the synthesis method of any one of claims 1 to 6 in preparing water dispersible granules from bacillus thuringiensis.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4912245A (en) * | 1986-07-11 | 1990-03-27 | Rhone-Poulenc Chimie | Phosphoric acid ester-based compositions, process for the preparation thereof |
| CN105854728A (en) * | 2016-04-21 | 2016-08-17 | 允发化工（上海）有限公司 | Synthesis method of non-ionic surfactant |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4912245A (en) * | 1986-07-11 | 1990-03-27 | Rhone-Poulenc Chimie | Phosphoric acid ester-based compositions, process for the preparation thereof |
| CN105854728A (en) * | 2016-04-21 | 2016-08-17 | 允发化工（上海）有限公司 | Synthesis method of non-ionic surfactant |
Non-Patent Citations (1)
| Title |
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| 陶贤平: "多芳基酚聚氧乙烯醚磷酸酯盐的合成", 《河南化工》 * |
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