CN113402549A - Preparation method of glyphosate technical - Google Patents
Preparation method of glyphosate technical Download PDFInfo
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- CN113402549A CN113402549A CN202110795055.6A CN202110795055A CN113402549A CN 113402549 A CN113402549 A CN 113402549A CN 202110795055 A CN202110795055 A CN 202110795055A CN 113402549 A CN113402549 A CN 113402549A
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- amphoteric surfactant
- phosphate ester
- glyphosate technical
- glyphosate
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- 239000005562 Glyphosate Substances 0.000 title claims abstract description 31
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 42
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 36
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 26
- 239000010452 phosphate Substances 0.000 claims abstract description 26
- 239000002280 amphoteric surfactant Substances 0.000 claims abstract description 25
- -1 phosphate ester Chemical class 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000004471 Glycine Substances 0.000 claims abstract description 12
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 12
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 12
- 238000007259 addition reaction Methods 0.000 claims abstract description 7
- 238000006482 condensation reaction Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 23
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 19
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 19
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 19
- 239000013067 intermediate product Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 10
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 claims description 10
- 229930195729 fatty acid Natural products 0.000 claims description 10
- 239000000194 fatty acid Substances 0.000 claims description 10
- 150000004665 fatty acids Chemical class 0.000 claims description 10
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 239000004557 technical material Substances 0.000 claims 5
- 238000006243 chemical reaction Methods 0.000 abstract description 35
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 abstract description 24
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 16
- 230000007062 hydrolysis Effects 0.000 abstract description 14
- 230000015572 biosynthetic process Effects 0.000 abstract description 12
- 238000003786 synthesis reaction Methods 0.000 abstract description 12
- 239000007788 liquid Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 7
- 239000000498 cooling water Substances 0.000 abstract description 6
- 229940079593 drug Drugs 0.000 abstract description 6
- 239000003814 drug Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 206010024769 Local reaction Diseases 0.000 abstract description 3
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 229960002449 glycine Drugs 0.000 description 10
- 239000012043 crude product Substances 0.000 description 9
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- JXOHGGNKMLTUBP-HSUXUTPPSA-N shikimic acid Chemical compound O[C@@H]1CC(C(O)=O)=C[C@@H](O)[C@H]1O JXOHGGNKMLTUBP-HSUXUTPPSA-N 0.000 description 2
- JXOHGGNKMLTUBP-JKUQZMGJSA-N shikimic acid Natural products O[C@@H]1CC(C(O)=O)=C[C@H](O)[C@@H]1O JXOHGGNKMLTUBP-JKUQZMGJSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- CRFICXGOVSUJNA-UHFFFAOYSA-N 2-aminoacetic acid;phosphorous acid Chemical compound OP(O)O.NCC(O)=O CRFICXGOVSUJNA-UHFFFAOYSA-N 0.000 description 1
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 description 1
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 description 1
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 1
- 102000003960 Ligases Human genes 0.000 description 1
- 108090000364 Ligases Proteins 0.000 description 1
- 241000209510 Liliopsida Species 0.000 description 1
- 240000000249 Morus alba Species 0.000 description 1
- 235000008708 Morus alba Nutrition 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 241001233957 eudicotyledons Species 0.000 description 1
- 235000013905 glycine and its sodium salt Nutrition 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002420 orchard Substances 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- 230000005080 plant death Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000001243 protein synthesis Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 230000014616 translation Effects 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
- C07F9/3813—N-Phosphonomethylglycine; Salts or complexes thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a preparation method of glyphosate technical, belonging to the technical field of fine chemical product synthesis, wherein the synthesis process comprises the following steps: firstly, putting methanol, triethylamine, paraformaldehyde and glycine into a synthesis kettle to carry out addition reaction; secondly, adding dimethyl phosphite, and carrying out condensation reaction for 1-1.5h at 50-60 ℃; thirdly, after the reaction is finished, transferring the mixture into a hydrolysis kettle, filling cooling water into a jacket, dripping hydrochloric acid, adding phosphate ester amphoteric surfactant, preserving the temperature for 1h at 50-60 ℃ to prepare glyphosate raw drug, condensing the chloromethane generated in the hydrolysis process, then feeding the condensed liquid into a chloromethane production device, and feeding the condensed liquid into a methylal recovery process; according to the invention, the phosphate ester amphoteric surfactant is added in the synthesis of glyphosate, so that the reaction is milder, the phenomenon that the local reaction is too fast to form black materials to a certain extent, which causes side reactions is prevented, and the yield and the purity are further improved.
Description
Technical Field
The invention belongs to the technical field of fine chemical product synthesis, and relates to a preparation method of glyphosate technical.
Background
Glyphosate is a non-selective and residue-free biocidal herbicide, is very effective on perennial rooting weeds, and is widely used in rubber, mulberry, tea, orchards and sugarcane fields. Mainly inhibits enol pyruvyl shikimic acid phosphate synthetase in plants, thereby inhibiting the conversion of shikimic acid to phenylalanine, tyrosine and tryptophan, interfering protein synthesis and leading to plant death. Glyphosate is absorbed by stems and leaves and then transferred to various parts of plants, and can prevent and kill monocotyledons, dicotyledons, annual and perennial plants, herbaceous plants, shrubs and other plants of more than 40 families. After entering the soil, the glyphosate is combined with metal ions such as iron, aluminum and the like quickly to lose activity. The hydrolysis process of the glyphosate comprises the following steps: adding measured methanol, triethylamine and paraformaldehyde into a synthesis kettle, and adding into aminoacetic acid to perform addition reaction; then slowly adding dimethyl phosphite, carrying out condensation reaction at 50 ℃, and keeping for 1-1.5 h; after the reaction is finished, transferring the mixture into a hydrolysis kettle, introducing cooling water into a jacket, dropwise adding hydrochloric acid, keeping the temperature at 50 ℃ for 1h, condensing chloromethane generated in the hydrolysis process, removing a chloromethane production device, and recovering condensed liquid methylal; the process has low production efficiency and low product yield, and generates a large amount of wastewater in the production process, thereby having high labor intensity.
According to the thermochemical theory, the hydrolysis reaction of the glyphosate is an endothermic reaction, the concentration of hydrochloric acid participating in the hydrolysis reaction is not too high, and black materials are easily generated due to too high acid concentration, wherein the delta H is-296 KJ/mol; the acid concentration is increased, the reaction speed is doubled, a large amount of heat is instantaneously released, and the temperature and the pressure in the kettle are increased too fast to control.
Disclosure of Invention
The invention aims to provide a preparation method of glyphosate technical, which solves the problem of over-quick local reaction in the background technology.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of glyphosate technical comprises the following steps:
step A1, adding methanol, triethylamine, paraformaldehyde and glycine into a synthesis kettle for addition reaction, then adding dimethyl phosphite, and carrying out condensation reaction for 1-1.5h at 50 ℃ to obtain an intermediate product;
and step A2, after the reaction is finished, transferring the mixture into a hydrolysis kettle, introducing cooling water into a jacket, dropwise adding a hydrochloric acid solution with the mass fraction of 20% into the intermediate product, adding a phosphate ester amphoteric surfactant, keeping the temperature at 50 ℃ for 1h to obtain glyphosate raw drug, condensing the chloromethane generated in the hydrolysis process, then allowing the condensed methane to flow into a chloromethane production device, and allowing the condensed liquid to enter a methylal recovery process.
Further, in the step A1, the mass ratio of methanol, triethylamine, paraformaldehyde, glycine and dimethyl phosphite is 1: 4.3: 4.1: 4.9: 2.2.
further, the mass ratio of the intermediate product, the hydrochloric acid solution and the phosphate ester amphoteric surfactant in the step A2 is 1.2-1.5: 100: 9-11.
Wherein the phosphate ester amphoteric surfactant is prepared by the following steps:
step S11, weighing sodium dihydrogen phosphate aqueous solution which is prepared in advance and has the mass fraction of 40-50%, adding the sodium dihydrogen phosphate aqueous solution into a three-neck flask, placing epoxy chloropropane into a constant-pressure dropping funnel, adopting mechanical stirring, heating the epoxy chloropropane to 110 ℃ in an oil bath, dropping epichlorohydrin, controlling the dropping within 1h to be finished, reacting for 4h, removing solvent water by rotary evaporation after the reaction is finished, dissolving a product by ethanol, removing excessive sodium dihydrogen phosphate, recrystallizing a crude product by ethyl acetate and ethanol for 3-4 times, and drying the crude product in vacuum at 40 ℃ for 12h to obtain an intermediate 1;
the reaction process is as follows:
step S12, adding fatty acid into a three-neck flask, introducing nitrogen, heating to 120-130 ℃, slowly dripping N, N-dimethyl-1, 3-propanediamine by using a constant-pressure dropping funnel, controlling the dripping within half an hour to be finished, separating water generated by the reaction by using a water separator, continuing the reaction for 8 hours at 150 ℃, after the reaction is finished, carrying out reduced pressure distillation to obtain a light yellow crude product, recrystallizing for 3-4 times by using petroleum ether, and carrying out vacuum drying for 4 hours at 40-50 ℃ to obtain an intermediate 2;
the reaction process is as follows:
and step S13, adding the intermediate 1, the intermediate 2 and an ethanol solution with the mass fraction of 25% into a three-neck flask, and reacting at 85 ℃ for 8h to obtain the phosphate ester amphoteric surfactant.
The reaction process is as follows:
further, in the step S11, the molar ratio of sodium dihydrogen phosphate to epichlorohydrin is 1: 1.2.
further, in step S12, the molar ratio of N, N-dimethyl-1, 3-propanediamine to fatty acid is 1: 1.15.
further, in the step S13, the mass ratio of the intermediate 2 to the intermediate 1 to the ethanol solution is 1: 1: 15.4-20.2.
The invention has the beneficial effects that:
1) according to the invention, the phosphate ester amphoteric surfactant is added in the synthesis hydrolysis of glyphosate, and a relatively uniform environment can be formed after the phosphate ester amphoteric surfactant is added, so that the reaction is milder, and the occurrence of side reactions caused by over-quick local reaction can be prevented to a certain extent; in addition, bubbles generated in the reaction process form a small reaction environment, so that the reaction efficiency is improved, and the yield and the purity are further improved.
2) The phosphate ester amphoteric surfactant prepared by the invention contains a phosphoric acid structure in the structure, has good thermal stability and good temperature resistance in the later use process, contains a phosphoric acid group in the structure and has excellent alkali resistance, has good solubilization performance under the high-temperature and alkaline conditions of the synthesis process, has good biodegradability, and can be used for easily treating generated wastewater.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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
Preparation of phosphate ester amphoteric surfactant:
step S11, weighing sodium dihydrogen phosphate aqueous solution prepared in advance with mass fraction of 40%, adding the sodium dihydrogen phosphate aqueous solution into a three-neck flask, placing epoxy chloropropane into a constant-pressure dropping funnel, mechanically stirring, heating in an oil bath to 105 ℃, dropping epichlorohydrin, controlling the completion of dropping within 1h, reacting for 4h, removing solvent water after the reaction is finished, performing rotary evaporation, dissolving the product with ethanol, removing excessive sodium dihydrogen phosphate, recrystallizing the crude product with ethyl acetate and ethanol for 3 times, and performing vacuum drying at 40 ℃ for 12h to obtain an intermediate 1, wherein the molar ratio of the sodium dihydrogen phosphate to the epichlorohydrin is 1: 1.2;
step S12, adding fatty acid into a three-neck flask, introducing nitrogen, heating to 120 ℃, slowly dripping N, N-dimethyl-1, 3-propanediamine by using a constant-pressure dropping funnel, controlling the dripping within half an hour to be finished, separating water generated by the reaction by using a water separator, continuing the reaction for 8 hours at 150 ℃, after the reaction is finished, carrying out reduced pressure distillation to obtain a light yellow crude product, recrystallizing for 3 times by using petroleum ether, and carrying out vacuum drying for 4 hours at 40 ℃ to obtain an intermediate 2, wherein the molar ratio of the N, N-dimethyl-1, 3-propanediamine to the fatty acid is 1: 1.15;
step S13, adding the intermediate 1, the intermediate 2 and an ethanol solution with the mass fraction of 25% into a three-neck flask, and reacting at 85 ℃ for 8h to obtain the phosphate ester amphoteric surfactant, wherein the mass ratio of the intermediate 2 to the intermediate 1 to the ethanol solution is 1: 1: 15.4.
example 2
Preparation of phosphate ester amphoteric surfactant:
step S11, weighing a sodium dihydrogen phosphate aqueous solution prepared in advance with a mass fraction of 45%, adding the sodium dihydrogen phosphate aqueous solution into a three-neck flask, placing epoxy chloropropane into a constant-pressure dropping funnel, mechanically stirring, heating in an oil bath to 108 ℃, dropping epichlorohydrin, controlling the completion of dropping within 1h, reacting for 4h, after the reaction is finished, removing solvent water by rotary evaporation, dissolving the product with ethanol, removing excessive sodium dihydrogen phosphate, recrystallizing the crude product with ethyl acetate and ethanol for 3 times, and drying in vacuum at 40 ℃ for 12h to obtain an intermediate 1, wherein the molar ratio of the sodium dihydrogen phosphate to the epoxy chloropropane is 1: 1.2;
step S12, adding fatty acid into a three-neck flask, introducing nitrogen, heating to 125 ℃, slowly dripping N, N-dimethyl-1, 3-propanediamine by using a constant-pressure dropping funnel, controlling the dripping within half an hour to be finished, separating water generated by the reaction by using a water separator, continuing the reaction for 8 hours at 150 ℃, after the reaction is finished, carrying out reduced pressure distillation to obtain a light yellow crude product, recrystallizing for 3 times by using petroleum ether, and carrying out vacuum drying for 4 hours at 45 ℃ to obtain an intermediate 2, wherein the molar ratio of the N, N-dimethyl-1, 3-propanediamine to the fatty acid is 1: 1.15;
step S13, adding the intermediate 1, the intermediate 2 and an ethanol solution with the mass fraction of 25% into a three-neck flask, and reacting at 85 ℃ for 8h to obtain the phosphate ester amphoteric surfactant, wherein the mass ratio of the intermediate 2 to the intermediate 1 to the ethanol solution is 1: 1: 18.2.
example 3
Preparation of phosphate ester amphoteric surfactant:
step S11, weighing sodium dihydrogen phosphate aqueous solution which is prepared in advance and has the mass fraction of 50%, adding the sodium dihydrogen phosphate aqueous solution into a three-neck flask, placing epoxy chloropropane into a constant-pressure dropping funnel, mechanically stirring, heating the mixture to 110 ℃ in an oil bath, dropping epichlorohydrin, controlling the completion of dropping within 1h, reacting for 4h, removing solvent water after the reaction is finished, performing rotary evaporation, dissolving the product with ethanol, removing excessive sodium dihydrogen phosphate, recrystallizing the crude product with ethyl acetate and ethanol for 4 times, and performing vacuum drying at 40 ℃ for 12h to obtain an intermediate 1, wherein the molar ratio of the sodium dihydrogen phosphate to the epichlorohydrin is 1: 1.2;
step S12, adding fatty acid into a three-neck flask, introducing nitrogen, heating to 130 ℃, slowly dripping N, N-dimethyl-1, 3-propanediamine by using a constant-pressure dropping funnel, controlling the dripping within half an hour to be finished, separating water generated by the reaction by using a water separator, continuing the reaction for 8 hours at 150 ℃, after the reaction is finished, carrying out reduced pressure distillation to obtain a light yellow crude product, recrystallizing for 4 times by using petroleum ether, and carrying out vacuum drying for 4 hours at 50 ℃ to obtain an intermediate 2, wherein the molar ratio of the N, N-dimethyl-1, 3-propanediamine to the fatty acid is 1: 1.15;
step S13, adding the intermediate 1, the intermediate 2 and an ethanol solution with the mass fraction of 25% into a three-neck flask, and reacting at 85 ℃ for 8h to obtain the phosphate ester amphoteric surfactant, wherein the mass ratio of the intermediate 2 to the intermediate 1 to the ethanol solution is 1: 1: 20.2.
example 4
A preparation method of glyphosate technical comprises the following steps:
step A1, adding methanol, triethylamine, paraformaldehyde and glycine into a synthesis kettle for addition reaction, then adding dimethyl phosphite, and carrying out condensation reaction at 50 ℃ for 1h to obtain an intermediate product, wherein the mass ratio of methanol, triethylamine, paraformaldehyde, glycine and dimethyl phosphite is 1: 4.3: 4.1: 4.9: 2.2;
step A2, after the reaction is finished, transferring the mixture into a hydrolysis kettle, introducing cooling water into a jacket, dropwise adding a hydrochloric acid solution with the mass fraction of 20% into the intermediate product, adding the phosphate ester amphoteric surfactant prepared in example 1, keeping the temperature at 50 ℃ for 1h to obtain glyphosate raw drug, condensing chloromethane generated in the hydrolysis process, removing a chloromethane production device, and recovering condensed liquid noracetal, wherein the mass ratio of the intermediate product, the hydrochloric acid solution and the phosphate ester amphoteric surfactant is 1.2: 100: 9.
example 5
A preparation method of glyphosate technical comprises the following steps:
step A1, adding methanol, triethylamine, paraformaldehyde and glycine into a synthesis kettle for addition reaction, then adding dimethyl phosphite, and carrying out condensation reaction at 50 ℃ for 1h to obtain an intermediate product, wherein the mass ratio of methanol, triethylamine, paraformaldehyde, glycine and dimethyl phosphite is 1: 4.3: 4.1: 4.9: 2.2;
step A2, after the reaction is finished, transferring the mixture into a hydrolysis kettle, introducing cooling water into a jacket, dropwise adding a hydrochloric acid solution with the mass fraction of 20% into the intermediate product, adding the phosphate ester amphoteric surfactant prepared in example 2, keeping the temperature at 50 ℃ for 1h to obtain glyphosate raw drug, condensing chloromethane generated in the hydrolysis process, removing a chloromethane production device, and recovering condensed liquid noracetal, wherein the mass ratio of the intermediate product, the hydrochloric acid solution and the phosphate ester amphoteric surfactant is 1.3: 100: 10.
example 6
A preparation method of glyphosate technical comprises the following steps:
step A1, adding methanol, triethylamine, paraformaldehyde and glycine into a synthesis kettle for addition reaction, then adding dimethyl phosphite, and carrying out condensation reaction at 50 ℃ for 1.5h to obtain an intermediate product, wherein the mass ratio of the methanol to the triethylamine to the paraformaldehyde to the glycine to the dimethyl phosphite is 1: 4.3: 4.1: 4.9: 2.2;
step A2, after the reaction is finished, transferring the mixture into a hydrolysis kettle, introducing cooling water into a jacket, dropwise adding a hydrochloric acid solution with the mass fraction of 20% into the intermediate product, adding the phosphate ester amphoteric surfactant prepared in example 3, keeping the temperature at 50 ℃ for 1h to obtain glyphosate raw drug, condensing chloromethane generated in the hydrolysis process, removing a chloromethane production device, and recovering condensed liquid noracetal, wherein the mass ratio of the intermediate product, the hydrochloric acid solution and the phosphate ester amphoteric surfactant is 1.5: 100: 11.
comparative example 1
75g of glycine and 160g of phosphorous acid are dissolved in 400g of methanol and stirred for 60min at normal temperature for later use. Putting 246g of 36.5 mass percent formaldehyde, 98g of 50 mass percent sulfuric acid and 600g of methanol into a high-pressure reaction kettle, heating to 70-75 ℃ while stirring, slowly adding glycine phosphorous acid solution, sealing the reaction kettle after adding, slowly heating to 180 ℃, controlling the pressure to be 10MPa, reacting for 10 hours, cooling after finishing heat preservation, adding a small amount of liquid alkali, adjusting the pH value of the system to 1-1.5, and separating out a large amount of solids during the reaction to obtain 138.1g of glyphosate raw drug.
The glyphosate technical obtained in examples 4-6 and comparative example 1 is tested for yield and purity, and the test results are shown in table 1:
TABLE 1
| Item | Example 4 | Example 5 | Example 6 | Comparative example 1 |
| Yield% | 93.21 | 93.91 | 92.86 | 78.8 |
| Purity% | 99.46 | 99.65 | 99.57 | 95.1 |
As can be seen from table 1, the glyphosate technical prepared in examples 4 to 6 has a yield of 92.86 to 93.91% and a purity of 99% compared with comparative example 1.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (6)
1. A preparation method of glyphosate technical is characterized by comprising the following preparation steps:
carrying out addition reaction on methanol, triethylamine, paraformaldehyde and glycine, then adding dimethyl phosphite for condensation reaction to obtain an intermediate product, dropwise adding a hydrochloric acid solution into the intermediate product, adding a phosphate ester amphoteric surfactant, and reacting to obtain a glyphosate technical product;
wherein the phosphate ester amphoteric surfactant is prepared by the following steps:
step S11, reacting sodium dihydrogen phosphate water solution with epichlorohydrin at the temperature of 105-110 ℃ for 4h, removing solvent water by rotary evaporation, dissolving the product with ethanol, and then recrystallizing and drying to obtain an intermediate 1;
step S12, adding fatty acid into a three-neck flask, introducing nitrogen, heating to 120-130 ℃, adding N, N-dimethyl-1, 3-propanediamine, reacting for 8h at 150 ℃, performing reduced pressure distillation, recrystallizing for 3-4 times by using petroleum ether, and drying to obtain an intermediate 2;
and step S13, adding the intermediate 1, the intermediate 2 and an ethanol solution into a three-neck flask, and reacting for 8 hours at 85 ℃ to obtain the phosphate ester amphoteric surfactant.
2. The method for preparing glyphosate technical material according to claim 1, which is characterized in that: the mass ratio of methanol, triethylamine, paraformaldehyde, glycine and dimethyl phosphite is 1: 4.3: 4.1: 4.9: 2.2.
3. the method for preparing glyphosate technical material according to claim 1, which is characterized in that: the mass ratio of the intermediate product to the hydrochloric acid solution to the phosphate ester amphoteric surfactant is 1.2-1.5: 100: 9-11.
4. The method for preparing glyphosate technical material according to claim 1, which is characterized in that: in the step S11, the mass fraction of the sodium dihydrogen phosphate aqueous solution is 40 to 50%, and the molar ratio of the sodium dihydrogen phosphate to the epichlorohydrin is 1: 1.2.
5. the method for preparing glyphosate technical material according to claim 1, which is characterized in that: in step S12, the molar ratio of N, N-dimethyl-1, 3-propanediamine to fatty acid is 1: 1.15.
6. the method for preparing glyphosate technical material according to claim 1, which is characterized in that: in the step S13, the mass ratio of the intermediate 2 to the intermediate 1 to the ethanol solution is 1: 1: 15.4-20.2.
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