CN101796963B - Preparation method of glyphosate composition containing sulfate radical or bisulfate radical ions - Google Patents
Preparation method of glyphosate composition containing sulfate radical or bisulfate radical ions Download PDFInfo
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- CN101796963B CN101796963B CN2010101133233A CN201010113323A CN101796963B CN 101796963 B CN101796963 B CN 101796963B CN 2010101133233 A CN2010101133233 A CN 2010101133233A CN 201010113323 A CN201010113323 A CN 201010113323A CN 101796963 B CN101796963 B CN 101796963B
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- glyphosate
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- mixed liquor
- bisulfate
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- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000005562 Glyphosate Substances 0.000 title claims abstract description 87
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- -1 sulfate radical Chemical class 0.000 title claims abstract description 30
- 239000000203 mixture Substances 0.000 title abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- AZIHIQIVLANVKD-UHFFFAOYSA-N N-(phosphonomethyl)iminodiacetic acid Chemical compound OC(=O)CN(CC(O)=O)CP(O)(O)=O AZIHIQIVLANVKD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 12
- 239000002585 base Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 229930182470 glycoside Natural products 0.000 claims description 8
- 239000000375 suspending agent Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 claims description 5
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 229940110456 cocoa butter Drugs 0.000 claims description 3
- 235000019868 cocoa butter Nutrition 0.000 claims description 3
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 3
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000343 potassium bisulfate Inorganic materials 0.000 claims description 3
- NIAGBSSWEZDNMT-UHFFFAOYSA-M tetraoxidosulfate(.1-) Chemical compound [O]S([O-])(=O)=O NIAGBSSWEZDNMT-UHFFFAOYSA-M 0.000 claims description 3
- CDMGNVWZXRKJNS-UHFFFAOYSA-N 2-benzylphenol Chemical compound OC1=CC=CC=C1CC1=CC=CC=C1 CDMGNVWZXRKJNS-UHFFFAOYSA-N 0.000 claims description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- JJEJDZONIFQNHG-UHFFFAOYSA-N [C+4].N Chemical compound [C+4].N JJEJDZONIFQNHG-UHFFFAOYSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043237 diethanolamine Drugs 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 239000001397 quillaja saponaria molina bark Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229930182490 saponin Natural products 0.000 claims description 2
- 150000007949 saponins Chemical class 0.000 claims description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 2
- 239000003760 tallow Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000000857 drug effect Effects 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000012266 salt solution Substances 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 abstract 1
- 241000196324 Embryophyta Species 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 8
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 8
- 235000011130 ammonium sulphate Nutrition 0.000 description 8
- 238000009472 formulation Methods 0.000 description 8
- 239000010413 mother solution Substances 0.000 description 8
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 229910021653 sulphate ion Inorganic materials 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- ZEKANFGSDXODPD-UHFFFAOYSA-N glyphosate-isopropylammonium Chemical compound CC(C)N.OC(=O)CNCP(O)(O)=O ZEKANFGSDXODPD-UHFFFAOYSA-N 0.000 description 4
- 239000004009 herbicide Substances 0.000 description 4
- 230000002528 anti-freeze Effects 0.000 description 3
- 239000013530 defoamer Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 230000002363 herbicidal effect Effects 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- 229920001285 xanthan gum Polymers 0.000 description 3
- 244000026873 Alternanthera philoxeroides Species 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 241000234646 Cyperaceae Species 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- PDYXIVPKOMYDOK-UHFFFAOYSA-N Glyphosate-monoammonium Chemical compound [NH4+].OC(=O)CNCP(O)([O-])=O PDYXIVPKOMYDOK-UHFFFAOYSA-N 0.000 description 1
- IAVLFFCDBNJEFG-UHFFFAOYSA-N P(=O)(O)(O)CN=CC(=O)O.C(C)(=O)O Chemical compound P(=O)(O)(O)CN=CC(=O)O.C(C)(=O)O IAVLFFCDBNJEFG-UHFFFAOYSA-N 0.000 description 1
- 241000209504 Poaceae Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008485 antagonism Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001175 calcium sulphate Substances 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000000762 glandular Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000000361 pesticidal effect Effects 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- YZHUMGUJCQRKBT-UHFFFAOYSA-M sodium chlorate Chemical compound [Na+].[O-]Cl(=O)=O YZHUMGUJCQRKBT-UHFFFAOYSA-M 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to a preparation method of glyphosate water-based preparation containing sulfate radical or bisulfate radical ions. The glyphosate is mixed glyphosate liquid prepared by carrying out a sulfuric acid oxidization method on PMIDA, or mixed glyphosate salt solution is formed by continuously adding alkali. Then, the obtained mixed liquid is added with surface active agent to prepare the glyphosate composition water-based preparation containing the sulfate radical or bisulfate radical ions; and in the preparation, the glyphosate has the mass percent (based on glyphosate acid) more than or equal to 20%, the sulfate radical or bisulfate radical ions more than or equal to 20% and the mass percent ratio between the glyphosate and the sulfate radical or bisulfate radical ions is 1:2-2:1. The preparation technique of the glyphosate needs not to separate glyphosate technical in advance, thus greatly reducing the input of production equipment and manpower, reducing the emission of waste water in the production process, saving resources and being beneficial to environmental protection; furthermore, the preparation contains more sulfate radical or bisulfate radical ions, thus greatly improving the drug effect, reducing the dosage of the glyphosate and saving the resources.
Description
Technical field
The present invention relates to a kind of preparation method of glyphosate formulation, relate in particular to a kind of preparation method who contains the water base chemical preparation of glyphosate of sulfate ion or hydrogen sulfate ion.
Background technology
Glyphosate (glyphosate), formal name used at school N-((phosphonomethyl)) glycine, N-((phosphonomethyl)) amion acetic acid (Phosphonomethyl Imino Acetic Acid) is a kind of organophosphorus herbicide.Glyphosate absorbs by plant leaf blade and non-woody cauline leaf as non-selective, noresidue herbicide after seedling, conducts to the plant corpus each several part, and is very effective to dark root perennial weed and annual and biennial grass family, sedge family and broad leaved weed.The most outstanding characteristics of glyphosate are in can being conducted to underground rhizome downwards and be tillered by the cauline leaf absorption, and are extremely strong to weeds underground organization destructive power.In China, glyphosate is used widely, is the weed killer herbicide of China's usage amount maximum.Yet, glyphosate in use, the medicament availability is low, fails to obtain due control efficiency as a rule.Agricultural chemicals in developed country annual nearly 25% is wasted because of improper use, in China then up to 60%.The bioavailability that how to improve pesticidal preparations is most important to agricultural sustainable development.
Studies show that in a large number ammonium sulfate can play synergistic effect to the activity of weeding of glyphosate.Its main mechanism be can eliminate spray in the water, on the plant stem-leaf and even the cations such as Ca2+, Mg2+ that exist in inside plants tissue and the glandular secretion thing antagonism that glyphosate is played, sulfate radical wherein can be combined into water-soluble little calcium sulphate with cations such as Ca2+, Mg2+, magnesium sulfate is separated out.Simultaneously, the transporting in weeds has significant facilitation to ammonium sulfate to glyphosate.
But because the solvability of ammonium sulfate in water is limited, the amount of adding ammonium sulfate in the glyphosate more than 30% (calculating with the glyphosate) waterborne preparation is smaller or equal to 15%, and the easy crystallization of formulation products.The ammonium sulfate concentrations that can add in the disclosed glyphosate formulation of Chinese invention patent application CN1649494 is up to 180g/L.After yet 15% ammonium sulfate diluted 150 times in use, concentration had only one thousandth, and synergistic effect is limited.Up to the present, also do not have sulfate ion or hydrogen sulfate ion content more than or equal to 20% water baseization glyphosate formulation research report, do not contain sulfate radical or bisulfate ion as glyphosate potentiating compounds research report yet about beyond the ammonium sulfate all the other.
The 1980s to the nineties, China once adopted monoxone etc. to be the feedstock production PMIDA, utilized the sulfuric acid oxidation legal system to be equipped with 10% ammonium glyphosate then.Because ammonium sulfate solvability is limited, can't prepare the glyphosate formulation of high-load.So far also do not utilize PMIDA sulfuric acid oxidation legal system to be equipped with the research report of glyphosate (in glyphosate) more than or equal to 20% high concentrate formulation.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method who contains the water base chemical preparation of glyphosate of high-concentration sulfuric acid radical ion or hydrogen sulfate ion.The technical solution used in the present invention feature is: PMIDA is got glyphosate mixed liquor or its salt with the sulfuric acid oxidation legal system, add auxiliary agent and water such as surfactant again in the mixed liquor, be prepared into water base chemical preparation.Through the water base chemical preparation of glyphosate of the present invention's preparation, wherein glyphosate (in glyphosate) weight percentage is more than or equal to 20%, and sulfate ion or hydrogen sulfate ion weight percentage are more than or equal to 20%.
Preparation method of the present invention comprises the steps: PMIDA, catalyzer and sulfuric acid in 1: 0.001: 0.5---ratio was mixed in 1: 0.05: 1.5, and---stirring reaction 1 under 135 ℃ the condition---obtained the glyphosate mixed liquor in 4 hours 75 ℃ of reaction temperatures; Add alkali toward the glyphosate mixed liquor, make the glyphosate mixed liquor be converted into the glyphosate salt mixed liquor; Add auxiliary agents such as surfactant again in the glyphosate salt mixed liquor of gained, make the water base chemical preparation of the glyphosate that contains sulfate ion or hydrogen sulfate ion.
Described catalyzer is one or more in hydrogen peroxide, polyphosphoric acid, niter cake, potassium acid sulfate, cobalt nitrate, cerous nitrate, the lanthanum nitrate; Described alkali is one or more in ammonia, isopropylamine, methylamine, ethamine, ethylenediamine, ethylene glycol amine, diethanol amine, urea, carbon ammonium, sodium hydroxide, the potassium hydroxide; Described surfactant is one or more in benzylphenol APEO, alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether, alkyl glycoside, tallow amine ethyl group thing, Tea Saponin, cocoa butter amide compound, organosilicon, the naphthalene sulfonate.
A kind of main advantage of preparation method that contains the water base chemical preparation of glyphosate of sulfate ion or hydrogen sulfate ion provided by the present invention has:
(1) preparation process need not to separate glyphosate technicals, and the glyphosate composition that contains sulfate ion or hydrogen sulfate ion that directly will synthesize is used for water base chemical preparation preparation, has significantly reduced production equipment and artificial the input.
(2) production process does not have the glyphosate discharging of waste liquid, and no glyphosate technicals waste has been saved resource and has been beneficial to environmental protection.
(3) the concentration height of preparation glyphosate suspending agent or aqua sulphate-containing ion or hydrogen sulfate ion, the drug effect brilliance has reduced the mu consumption of glyphosate technicals, provides cost savings, and has saved resource.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, the present invention describes with following specific embodiment, but the present invention is limited to these examples absolutely not.The following stated only is the present invention embodiment preferably, only is used to explain the present invention, can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that all any modifications of being made within the spirit and principles in the present invention, be equal to replacement and improvement etc., all should be included within protection scope of the present invention.
One, the preparation of 30% glyphosate (in the glyphosate) suspending agent of sulfur acid hydrogen radical ion:
Embodiment 1 gets PMIDA (content 96%) 425g in the flask that band stirs, and adds sulfuric acid (content 98%) 260g, lanthanum nitrate 0.5g, is warming up to 95 ℃ ± 5 ℃, reaction 3---obtained mixing glyphosate mother solution to there not being the bubble generation in 4 hours.In mixing glyphosate mother solution, add isopropyl amine salt 150g, and add alkyl glycoside 30g, naphthalene sulfonate 25g, thickener xanthans 1g, antifreeze glycol 30g, defoamer silicone 0.01g simultaneously, the surplus water is mended to 1000g, promptly makes 30% glyphosate (in the glyphosate) suspending agent of sulfur acid hydrogen radical ion.
Embodiment 2 gets PMIDA (content 96%) 425g in the flask that band stirs, and adds sulfuric acid (content 98%) 630g, and cerous nitrate 0.5g is warming up to 75 ℃ ± 5 ℃, reaction 3---obtained mixing glyphosate mother solution to there not being the bubble generation in 4 hours.Add ammonia 25g toward mixing glyphosate mother solution, and add alkyl glycoside 30g, naphthalene sulfonate 25g, thickener xanthans 1g, antifreeze glycol 30g, defoamer silicone 0.01g simultaneously, the surplus water is mended to 1500g, promptly makes 20% glyphosate (in the glyphosate) suspending agent of sulfur acid hydrogen radical ion.
Embodiment 3 gets PMIDA (content 96%) 425g in the flask that band stirs, and adds sulfuric acid (content 98%) 260g, polyphosphoric acid 20g, is warming up to 130 ℃ ± 5 ℃, reaction 1---obtained mixing glyphosate mother solution to there not being the bubble generation in 2 hours.In mixing glyphosate mother solution, add potassium hydroxide 150g, and add alkyl glycoside 30g, naphthalene sulfonate 25g, thickener xanthans 1g, antifreeze glycol 30g, defoamer silicone 0.01g simultaneously, the surplus water is mended to 1000g, promptly makes 30% glyphosate (in the glyphosate) suspending agent of sulfur acid hydrogen radical ion.
Two, the preparation of 30% glyphosate (in the glyphosate) aqua of sulphate-containing ion:
Embodiment 4 gets PMIDA (content 96%) 425g in being with the flask that stirs, and adds sulfuric acid (content 98%) 260g, lanthanum nitrate 0.5g, hydrogen peroxide 10 grams, is warming up to 95 ℃ ± 5 ℃, reaction 3---obtained mixing glyphosate mother solution to there not being the bubble generation in 4 hours.Feed methylamine gas 215g in glyphosate mixing mother liquor, add alkyl glycoside 50g, organosilicon 20g again, water is mended 30% glyphosate (in the glyphosate) aqua that promptly gets sulphate-containing ion to 1000g.
Embodiment 5 gets PMIDA (content 96%) 425g in the flask that band stirs, add sulfuric acid (content 98%) 260g, cobalt nitrate 0.5g, potassium acid sulfate 10 grams, be warming up to 120 ℃ ± 5 ℃, reaction 1---obtained mixing glyphosate mother solution to there not being the bubble generation in 2 hours.Add urea 95g in glyphosate mixing mother liquor, add alkyl glycoside 50g, organosilicon 20g again, water is mended 30% glyphosate (in the glyphosate) aqua that promptly gets sulphate-containing ion to 1000g.
This is than the preparation of example 141% glyphosate isopropyl amine salt aqua
Get 95% glyphosate technicals, 32 mass parts in the four-hole boiling flask that band stirs, the water that adds 49 mass parts, drip the isopropylamine of 11 mass parts then, in mixed liquor, add the alkyl glycoside of 5 mass parts, the cocoa butter diacetayl amide of 3 mass parts again, promptly make 41% glyphosate isopropyl amine salt aqua through stirring, its glyphosate content is 30.4%.
Embodiment 6 glyphosate formulation drug effects this
(1) reagent agent
A: by 30% glyphosate (in the glyphosate) suspending agent of embodiment 1 resulting sulfur acid hydrogen radical ion
B: by 30% glyphosate (in the glyphosate) aqua of embodiment 4 resultant sulphate-containing ions
C: by comparative example 1 resulting 41% glyphosate isopropyl amine salt aqua
(2) experimental design and method
Experiment is divided into A, B, 4 processing of C, D, handles medicament with using automatic sprayer to the alternanthera philoxeroides processing of spraying after 300 times of the ordinary tap water dilutions.D is the ordinary tap water control treatment.Each handles 3 repetitions.Behind the medicine 15 days, take by weighing the above-ground plant parts fresh weight, rhizome is continued to cultivate take by weighing the regeneration plant fresh weight after 30 days.
(3) experimental result and analysis
Experimental result such as following table
According to interpretation, by the glyphosate formulation of the inventive method preparation under the situation of identical active ingredient using dosage, to the control efficiency of alternanthera philoxeroides apparently higher than 41% common glyphosate isopropyl amine salt aqua.
Claims (4)
1. a preparation method who contains the water base chemical preparation of glyphosate of sulfate radical or hydrogen sulfate ion is characterized in that, obtains glyphosate mixed liquor or its salt with PMIDA through sulfuric acid oxidation, adds auxiliary agent and water such as surfactant again, is prepared into water base chemical preparation; Glyphosate in the gained preparation (in glyphosate) weight percentage more than or equal to 20%, sulfate ion or hydrogen sulfate ion weight percentage be more than or equal to 20%, comprise the steps: PMIDA, catalyzer and sulfuric acid by 1: 0.001: 0.5---mix at 1: 0.05: 1.5,---stirring reaction 1 under 135 ℃ the condition---obtained the glyphosate mixed liquor in 4 hours 75 ℃ of reaction temperatures; Add alkali toward the glyphosate mixed liquor, make the glyphosate mixed liquor be converted into the glyphosate salt mixed liquor; Add auxiliary agent again in the glyphosate salt mixed liquor of gained, preparation contains the water base chemical preparation of glyphosate of sulfate radical or hydrogen sulfate ion; Described catalyzer is one or more in polyphosphoric acid, niter cake, potassium acid sulfate, cobalt nitrate, cerous nitrate, the lanthanum nitrate.
2. according to claim 1, it is characterized in that described alkali is one or more in ammonia, isopropylamine, methylamine, ethamine, ethylenediamine, ethylene glycol amine, diethanol amine, urea, carbon ammonium, sodium hydroxide, the potassium hydroxide.
3. according to claim 1, it is characterized in that described auxiliary agent comprises surfactant, surfactant be in benzylphenol APEO, alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether, alkyl glycoside, tallow amine ethyl group thing, Tea Saponin, cocoa butter amide compound, organosilicon, the naphthalene sulfonate one or more.
4. according to claim 1, it is characterized in that described waterborne preparation comprises suspending agent and aqua.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101133233A CN101796963B (en) | 2010-01-29 | 2010-01-29 | Preparation method of glyphosate composition containing sulfate radical or bisulfate radical ions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101133233A CN101796963B (en) | 2010-01-29 | 2010-01-29 | Preparation method of glyphosate composition containing sulfate radical or bisulfate radical ions |
Publications (2)
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| CN104145953B (en) * | 2014-07-21 | 2016-06-08 | 宁德师范学院 | A kind of suspension agent of being applied in seed coat agent and using method thereof |
| CN109221243A (en) * | 2018-10-17 | 2019-01-18 | 浙江金帆达生化股份有限公司 | A kind of glyphosate liquid preparation continuous production technology |
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| 华乃震.草甘膦活性和助剂.《农药》.2002,第41卷(第2期),1-5. * |
| 陆阳 等.草甘膦合成工艺研究.《化工中间体》.2009,(第8期),47-50. * |
| 高德霖.硫铵对草甘膦的增效作用.《精细化工化纤信息通讯》.2001,(第3期),2-5. * |
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