CN112521312A - Synthesis method of isoproturon herbicide - Google Patents
Synthesis method of isoproturon herbicide Download PDFInfo
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- CN112521312A CN112521312A CN202011410422.8A CN202011410422A CN112521312A CN 112521312 A CN112521312 A CN 112521312A CN 202011410422 A CN202011410422 A CN 202011410422A CN 112521312 A CN112521312 A CN 112521312A
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- water diversion
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- toluene
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- PUIYMUZLKQOUOZ-UHFFFAOYSA-N isoproturon Chemical compound CC(C)C1=CC=C(NC(=O)N(C)C)C=C1 PUIYMUZLKQOUOZ-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000004009 herbicide Substances 0.000 title claims abstract description 19
- 230000002363 herbicidal effect Effects 0.000 title claims abstract description 17
- 238000001308 synthesis method Methods 0.000 title abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 125
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000010438 heat treatment Methods 0.000 claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 25
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 230000018044 dehydration Effects 0.000 claims abstract description 22
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims description 29
- 238000010992 reflux Methods 0.000 claims description 28
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 24
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 24
- XEDSKXUZIQDPLO-UHFFFAOYSA-N CC1=CC=CC=C1.C(C)(C)C1=CC=C(N)C=C1 Chemical compound CC1=CC=CC=C1.C(C)(C)C1=CC=C(N)C=C1 XEDSKXUZIQDPLO-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 16
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 13
- MTMNJFGEKOYMIV-UHFFFAOYSA-N carbonyl dichloride;toluene Chemical compound ClC(Cl)=O.CC1=CC=CC=C1 MTMNJFGEKOYMIV-UHFFFAOYSA-N 0.000 claims description 13
- 239000011521 glass Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000008234 soft water Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- LRTFPLFDLJYEKT-UHFFFAOYSA-N para-isopropylaniline Chemical compound CC(C)C1=CC=C(N)C=C1 LRTFPLFDLJYEKT-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 238000005086 pumping Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 230000001502 supplementing effect Effects 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 238000010189 synthetic method Methods 0.000 claims description 6
- 239000012780 transparent material Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 239000004202 carbamide Substances 0.000 abstract description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 10
- -1 cumene isocyanate toluene Chemical compound 0.000 abstract description 10
- 208000012839 conversion disease Diseases 0.000 abstract description 4
- 238000007792 addition Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- ZDGLQYKCZMGQMP-UHFFFAOYSA-N aniline toluene Chemical compound CC1=CC=CC=C1.NC1=CC=CC=C1.NC1=CC=CC=C1 ZDGLQYKCZMGQMP-UHFFFAOYSA-N 0.000 description 3
- ZPSNFVVCGMSWID-UHFFFAOYSA-N 2-isocyanatopropan-2-ylbenzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1 ZPSNFVVCGMSWID-UHFFFAOYSA-N 0.000 description 2
- 235000006760 Acer pensylvanicum Nutrition 0.000 description 1
- 240000002245 Acer pensylvanicum Species 0.000 description 1
- 241000234282 Allium Species 0.000 description 1
- 235000002732 Allium cepa var. cepa Nutrition 0.000 description 1
- 244000000383 Allium odorum Species 0.000 description 1
- 235000018645 Allium odorum Nutrition 0.000 description 1
- 235000005338 Allium tuberosum Nutrition 0.000 description 1
- 235000001602 Digitaria X umfolozi Nutrition 0.000 description 1
- 235000017898 Digitaria ciliaris Nutrition 0.000 description 1
- 235000005476 Digitaria cruciata Nutrition 0.000 description 1
- 235000006830 Digitaria didactyla Nutrition 0.000 description 1
- 235000005804 Digitaria eriantha ssp. eriantha Nutrition 0.000 description 1
- 235000010823 Digitaria sanguinalis Nutrition 0.000 description 1
- 244000025670 Eleusine indica Species 0.000 description 1
- 235000014716 Eleusine indica Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- 240000004713 Pisum sativum Species 0.000 description 1
- 235000010582 Pisum sativum Nutrition 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 244000152045 Themeda triandra Species 0.000 description 1
- 240000006677 Vicia faba Species 0.000 description 1
- 235000010749 Vicia faba Nutrition 0.000 description 1
- 235000002098 Vicia faba var. major Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000012015 potatoes Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
- C07C273/1809—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
- C07C273/189—Purification, separation, stabilisation, use of additives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method of isoproturon herbicide, which comprises the following steps of firstly, putting measured toluene into a dehydration kettle, opening steam to heat up, carrying out backflow water diversion, observing front and rear water diversion mirrors to notice backflow conditions when the temperature in the kettle reaches a first temperature interval, observing the front and rear water diversion mirrors when the temperature of materials in the kettle reaches a second temperature interval, continuing heating until no water drops exist in distillate in the front water diversion mirrors, continuing heating when effluent liquid of the rear water diversion mirrors is clear and transparent, and stopping water diversion after maintaining backflow dehydration for two hours; the cumene isocyanate toluene liquid is dropwise added, so that the temperature in the synthesis process can be effectively controlled, the generation of urea in the process is reduced, the reaction conversion rate, the product quality and the yield are improved, the operation process and the temperature are easy to control, meanwhile, the cold synthesis conversion rate is improved by 8 percent on average, the yield of isoproturon is improved by 1 percent, and the original yield is improved to 98 percent from 97 percent.
Description
Technical Field
The invention relates to the technical field of isoproturon herbicide synthesis, and particularly relates to a synthesis method of isoproturon herbicide.
Background
Isoproturon, chemical name is N- (4-isopropylphenyl) -N ', N' dimethyl urea, high-efficient low-toxicity substituted urea herbicide. The herbicide has the characteristics of wide herbicide controlling spectrum, long applicable period and the like, can prevent and kill annual weeds such as crab grass, goosefoots, bluegrass and the like, is suitable for weeding in partial vegetable fields such as tomatoes, potatoes, seedlings growing Chinese chives, eggplants, broad beans, peas, onion and the like, can be used before and after germination, is compounded with other herbicides, has a synergistic effect, and is one of more ideal dry-land herbicides.
However, in the existing isoproturon production process, the content of the by-product urea is high, the unit consumption of raw material phosgene is high, the temperature change of the cumyl isocyanate toluene liquid is large when the cumyl isocyanate toluene liquid is added, the temperature in the synthesis process cannot be effectively controlled, and the product quality and the yield are reduced.
Disclosure of Invention
In order to overcome the technical problems, the invention aims to provide a synthesis method of isoproturon herbicide, which improves the dehydration efficiency of isoproturon aniline toluene solution, reduces the water content to below 50ppm, improves the content of isoproturon reaction isopropyl ester, reduces the content of byproduct urea, and reduces the unit consumption of raw material phosgene;
the cold light kettle is introduced with light and dripped at the same time, the reaction temperature can be effectively controlled not to exceed 20 ℃, and the generation of urea in the process is reduced;
the synthesis cooling kettle adopts a isopropyl ester dropping method, and the cumene isocyanate toluene liquid is dropped, so that the temperature in the synthesis process can be effectively controlled, the reaction conversion rate, the product quality and the yield are improved, the method obtains good evidence in actual production, the process is easy to control, meanwhile, the cold-synthesis conversion rate is improved by 8 percent on average, the yield of isoproturon is improved by 1 percent, and the original 97 percent is improved to 98 percent.
The purpose of the invention can be realized by the following technical scheme:
a synthetic method of isoproturon herbicide comprises the following steps:
step one, adding measured methylbenzene into a dehydration kettle, opening steam to heat, carrying out backflow water diversion, observing front and rear water diversion sight glasses to notice backflow when the temperature in the kettle reaches a first temperature interval, observing the front and rear water diversion sight glasses when the temperature of materials in the kettle reaches a second temperature interval, continuing heating until distillate in the front water diversion sight glasses has no water drops, continuing heating when the effluent of the rear water diversion sight glasses is clear and transparent, and stopping water diversion after maintaining backflow dehydration for 1.5-2.5 hours;
step two, cooling the toluene subjected to water diversion to 35-40 ℃, pumping 1200kg of p-isopropylaniline through a pneumatic diaphragm pump, and completely dissolving to obtain p-isopropylaniline toluene solution;
step three, adding another certain amount of toluene solution into a cold light kettle, introducing light gas at 0 ℃ for saturation to prepare phosgene toluene solution, then dropwise adding p-isopropylaniline toluene solution while introducing light, controlling the reaction temperature not to exceed 20 ℃, placing the mixture into a hot light kettle after the reaction is finished, and raising the reaction temperature to 58-62 ℃ at the speed of raising the temperature by 4-10 ℃ per hour to ensure that the material becomes transparent;
step four, continuously heating the transparent material at the speed of heating to 10-15 ℃ per hour, simultaneously keeping refluxing for 1.5-2.5 hours, then switching a reflux valve, and removing phosgene toluene liquid to a light methyl kettle;
step five, after the desolventizing is finished, heating and introducing nitrogen gas at the same time, and removing excessive phosgene and hydrochloric acid gas to obtain p-cumyl isocyanate toluene liquid;
step six, transferring 300-400kg of dimethylamine and 1200-1600kg of front cut toluene into a synthesis cold kettle, dropwise adding the toluene solution of p-isopropyl isocyanate into the synthesis cold kettle for synthesis, measuring the pH value of the material at the later stage of the reaction to ensure that the pH value is 8, and supplementing the dimethylamine if the pH value is less than 8, wherein the front cut refers to the dehydration in the step one;
seventhly, after the reaction in the sixth step is finished, transferring the mixture into a heat seal kettle, opening steam to start heating, heating to 82-85 ℃ at the speed of heating to 15-20 ℃ per hour, keeping the temperature for 0.5-1 hour at constant temperature, heating to 86-90 ℃, and keeping the temperature for 1.5-2.5 hours;
step eight, after the heat preservation in the step seven is finished, naturally cooling to below 70 ℃, opening a soft water valve to store 300 liters of soft water, continuously cooling, cooling the material to 35-40 ℃, and centrifuging;
and step nine, recovering the solvent separated in the centrifugal process, and drying the wet material to obtain isoproturon.
Furthermore, in the first step, 3400 plus 3800kg of toluene is put into a dehydration kettle, steam is opened for heating up, reflux water diversion is carried out, when the temperature in the kettle reaches 80-83 ℃ in a first temperature interval, the reflux condition is noticed through observing front and rear water diversion sight glasses, when the temperature of materials in the kettle reaches 105 plus 115 ℃ in a second temperature interval, the front and rear water diversion sight glasses are observed for continuously heating up until no water drops exist in distillate in the front water diversion sight glass, the heating is continued when effluent liquid of the rear water diversion sight glass is clear and transparent, and the water diversion is stopped after the reflux dehydration is maintained for 1.5-2.5 hours.
Furthermore, the number of the cold light kettles in the third step is two, 1500-2500L toluene solution is added into each cold light kettle, phosgene and toluene solution is obtained by introducing gas at 0 ℃ and saturation, the p-isopropylaniline toluene solution obtained in the second step is equally divided into two batches, the two batches are respectively transferred into two aniline elevated tanks to be dripped into the cold light kettles, and one aniline elevated tank corresponds to one cold light kettle.
Further, in the fifth step, during the process of expelling the excess phosgene and hydrochloric acid gas, the temperature is controlled to be kept at 100 ℃ and 110 ℃.
Further, in the sixth step, the dropwise addition is one-time dropwise addition, and the temperature does not exceed 20 ℃ after the dropwise addition.
Further, in the ninth step, the drying temperature is 90-100 ℃.
The invention has the beneficial effects that:
the dehydration efficiency of the isoproturon aniline toluene solution is improved, the water content is reduced to be below 50ppm, the content of isoproturon reaction isopropyl ester is improved, the content of a by-product urea is reduced, and the unit consumption of raw material phosgene is reduced;
the cold light kettle is introduced with light and dripped at the same time, the reaction temperature can be effectively controlled not to exceed 20 ℃, and the generation of urea in the process is reduced;
the synthesis cold kettle adopts a isopropyl ester dropping method, and the cumene isocyanate toluene liquid is dropped, so that the temperature in the synthesis process can be effectively controlled, the generation of urea in the process is reduced, the reaction conversion rate, the product quality and the yield are improved, the method obtains good evidence in the actual production, the process is easy to control, meanwhile, the cold conversion rate is improved by 8 percent on average, the yield of isoproturon is improved by 1 percent, and the yield is improved to 98 percent from the original 97 percent.
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:
a synthetic method of isoproturon herbicide comprises the following steps:
step one, throwing 3400kg of measured toluene into a dehydration kettle, opening steam to heat, carrying out reflux and water diversion, observing front and rear water diversion mirrors to notice the reflux condition when the temperature in the kettle reaches a first temperature interval of 80-83 ℃, observing the front and rear water diversion mirrors when the temperature of materials in the kettle reaches a second temperature interval of 105-115 ℃, continuously heating until no water drops exist in distillate in the front water diversion mirror, continuously heating when effluent liquid of the rear water diversion mirror is clear and transparent, and stopping water diversion after maintaining reflux and dehydration for 1.5 hours;
step two, cooling the toluene subjected to water diversion to 35-40 ℃, pumping 1200kg of p-isopropylaniline through a pneumatic diaphragm pump, obtaining a p-isopropylaniline toluene solution after complete dissolution, equally dividing the p-isopropylaniline toluene solution into two batches, respectively transferring the two batches of p-isopropylaniline toluene solution into two aniline elevated tanks to be dripped into a cold light kettle, wherein one aniline elevated tank corresponds to one cold light kettle;
step three, adding 1500-2500L toluene solution into each cold light kettle, introducing light gas at 0 ℃ for saturation to obtain phosgene toluene solution, then dropwise adding p-isopropylaniline toluene solution while introducing light, controlling the reaction temperature to be not more than 20 ℃, putting the mixture into the hot light kettle after the reaction is finished, and raising the reaction temperature to 58 ℃ at the speed of raising the temperature per hour by 4-10 ℃ to ensure that the material becomes transparent;
step four, continuously heating the transparent material at the speed of heating to 10-15 ℃ per hour, simultaneously keeping refluxing for 1.5 hours, then switching a reflux valve, and removing phosgene toluene liquid to a light first kettle;
step five, after the desolventizing is finished, heating and introducing nitrogen gas at the same time, removing excessive phosgene and hydrochloric acid gas, and controlling the temperature to be kept at 100 ℃ and 110 ℃ to obtain the p-cumyl isocyanate toluene liquid;
step six, transferring 300kg of dimethylamine and 1200kg of toluene of front cut fraction into a synthesis cold kettle, dropwise adding the toluene solution of the p-isopropyl isocyanate into the synthesis cold kettle, dropwise adding for one time, wherein the temperature does not exceed 20 ℃ after dropwise adding, synthesizing, and frequently measuring the pH value of the material in the later reaction period to ensure that the pH value is 8, and supplementing the dimethylamine if the pH value is less than 8;
seventhly, after the reaction in the sixth step is finished, transferring the mixture into a heat seal kettle, opening steam to start heating, heating to 82 ℃ at the speed of heating to 15-20 ℃ per hour, keeping the temperature for 0.5 hour at constant temperature, heating to 86 ℃, and keeping the temperature for 1.5 hours;
step eight, after the heat preservation in the step seven is finished, naturally cooling to below 70 ℃, opening a soft water valve to store 300 liters of soft water, continuously cooling, cooling the material to 35-40 ℃, and centrifuging;
and step nine, recovering the solvent separated in the centrifugal process, and drying the wet material at the drying temperature of 90-100 ℃, wherein isoproturon is obtained after drying is completed.
Example 2:
a synthetic method of isoproturon herbicide comprises the following steps:
step one, adding 3500kg of measured toluene into a dehydration kettle, opening steam to heat, carrying out reflux and water diversion, observing front and rear water diversion mirrors to notice the reflux condition when the temperature in the kettle reaches a first temperature interval of 80-83 ℃, observing the front and rear water diversion mirrors when the temperature of materials in the kettle reaches a second temperature interval of 105-115 ℃, continuously heating until no water drops exist in distillate in the front water diversion mirror, continuously heating when effluent liquid of the rear water diversion mirror is clear and transparent, and stopping water diversion after maintaining reflux and dehydration for 1.8 hours;
step two, cooling the toluene subjected to water diversion to 35-40 ℃, pumping 1200kg of p-isopropylaniline through a pneumatic diaphragm pump, obtaining a p-isopropylaniline toluene solution after complete dissolution, equally dividing the p-isopropylaniline toluene solution into two batches, respectively transferring the two batches of p-isopropylaniline toluene solution into two aniline elevated tanks to be dripped into a cold light kettle, wherein one aniline elevated tank corresponds to one cold light kettle;
step three, adding 1500-2500L toluene solution into each cold light kettle, introducing light gas at 0 ℃ for saturation to obtain phosgene toluene solution, then dropwise adding p-isopropylaniline toluene solution while introducing light, controlling the reaction temperature to be not more than 20 ℃, putting the mixture into the hot light kettle after the reaction is finished, and raising the reaction temperature to 60 ℃ at the speed of raising the temperature per hour by 4-10 ℃ to ensure that the material becomes transparent;
step four, continuously heating the transparent material at the speed of heating to 10-15 ℃ per hour, simultaneously keeping refluxing for 1.8 hours, then switching a reflux valve, and removing phosgene toluene liquid to a light first kettle;
step five, after the desolventizing is finished, heating and introducing nitrogen gas at the same time, removing excessive phosgene and hydrochloric acid gas, and controlling the temperature to be kept at 100 ℃ and 110 ℃ to obtain the p-cumyl isocyanate toluene liquid;
step six, transferring 350kg of dimethylamine and 1350kg of toluene as a front fraction into a synthesis cooling kettle, dropwise adding the toluene solution of the p-isopropyl isocyanate into the synthesis cooling kettle for one time, wherein the temperature does not exceed 20 ℃ after dropwise adding, synthesizing, and frequently measuring the pH value of the material in the later period of reaction to ensure that the pH value is 8, and supplementing the dimethylamine if the pH value is less than 8;
step seven, after the reaction in the step six is finished, transferring the mixture into a heat seal kettle, opening steam to start heating, heating to 83 ℃ at the speed of heating to 15-20 ℃ per hour, keeping the temperature for 0.8 hour at constant temperature, heating to 87 ℃, and keeping the temperature for 1.7 hours;
step eight, after the heat preservation in the step seven is finished, naturally cooling to below 70 ℃, opening a soft water valve to store 300 liters of soft water, continuously cooling, cooling the material to 35-40 ℃, and centrifuging;
and step nine, recovering the solvent separated in the centrifugal process, and drying the wet material at the drying temperature of 90-100 ℃, wherein isoproturon is obtained after drying is completed.
Example 3:
a synthetic method of isoproturon herbicide comprises the following steps:
step one, putting 3700kg of measured toluene into a dehydration kettle, opening steam to heat, carrying out backflow and water diversion, observing front and rear water diversion mirrors to pay attention to backflow when the temperature in the kettle reaches a first temperature interval of 80-83 ℃, observing the front and rear water diversion mirrors when the temperature of materials in the kettle reaches a second temperature interval of 105-115 ℃, continuously heating until no water drops exist in distillate in the front water diversion mirror, continuously heating when effluent liquid of the rear water diversion mirror is clear and transparent, and stopping water diversion after maintaining backflow and dehydration for 2.0 hours;
step two, cooling the toluene subjected to water diversion to 35-40 ℃, pumping 1200kg of p-isopropylaniline through a pneumatic diaphragm pump, obtaining a p-isopropylaniline toluene solution after complete dissolution, equally dividing the p-isopropylaniline toluene solution into two batches, respectively transferring the two batches of p-isopropylaniline toluene solution into two aniline elevated tanks to be dripped into a cold light kettle, wherein one aniline elevated tank corresponds to one cold light kettle;
step three, adding 1500-2500L toluene solution into each cold light kettle, introducing light gas at 0 ℃ for saturation to obtain phosgene toluene solution, then dropwise adding p-isopropylaniline toluene solution while introducing light, controlling the reaction temperature to be not more than 20 ℃, putting the mixture into the hot light kettle after the reaction is finished, and raising the reaction temperature to 60 ℃ at the speed of raising the temperature per hour by 4-10 ℃ to ensure that the material becomes transparent;
step four, continuously heating the transparent material at the speed of heating to 10-15 ℃ per hour, simultaneously keeping refluxing for 2.0 hours, then switching a reflux valve, and removing phosgene toluene liquid to a light first kettle;
step five, after the desolventizing is finished, heating and introducing nitrogen gas at the same time, removing excessive phosgene and hydrochloric acid gas, and controlling the temperature to be kept at 100 ℃ and 110 ℃ to obtain the p-cumyl isocyanate toluene liquid;
step six, transferring 380kg of dimethylamine and 1500kg of toluene of a front fraction into a synthesis cold kettle, dropwise adding the toluene solution of the p-isopropyl isocyanate into the synthesis cold kettle, dropwise adding for one time, wherein the temperature does not exceed 20 ℃ after dropwise adding, synthesizing, and frequently measuring the pH value of the material in the later reaction period to ensure that the pH value is 8, and supplementing the dimethylamine if the pH value is less than 8;
step seven, after the reaction in the step six is finished, transferring the mixture into a heat seal kettle, opening steam to start heating, heating to 84 ℃ at the speed of heating to 15-20 ℃ per hour, keeping the temperature for 0.8 hour at constant temperature, heating to 88 ℃, and keeping the temperature for 2.2 hours;
step eight, after the heat preservation in the step seven is finished, naturally cooling to below 70 ℃, opening a soft water valve to store 300 liters of soft water, continuously cooling, cooling the material to 35-40 ℃, and centrifuging;
and step nine, recovering the solvent separated in the centrifugal process, and drying the wet material at the drying temperature of 90-100 ℃, wherein isoproturon is obtained after drying is completed.
Example 4:
a synthetic method of isoproturon herbicide comprises the following steps:
step one, putting 3800kg of measured toluene into a dehydration kettle, starting steam to heat, carrying out reflux and water diversion, observing front and rear water diversion mirrors to pay attention to the reflux condition when the temperature in the kettle reaches a first temperature interval of 80-83 ℃, observing the front and rear water diversion mirrors when the temperature of materials in the kettle reaches a second temperature interval of 105-115 ℃, continuously heating until no water drops exist in distillate in the front water diversion mirror, continuously heating when effluent liquid of the rear water diversion mirror is clear and transparent, and stopping water diversion after maintaining reflux and dehydration for 2.5 hours;
step two, cooling the toluene subjected to water diversion to 35-40 ℃, pumping 1200kg of p-isopropylaniline through a pneumatic diaphragm pump, obtaining a p-isopropylaniline toluene solution after complete dissolution, equally dividing the p-isopropylaniline toluene solution into two batches, respectively transferring the two batches of p-isopropylaniline toluene solution into two aniline elevated tanks to be dripped into a cold light kettle, wherein one aniline elevated tank corresponds to one cold light kettle;
step three, adding 1500-2500L toluene solution into each cold light kettle, introducing light gas at 0 ℃ for saturation to obtain phosgene toluene solution, then dropwise adding p-isopropylaniline toluene solution while introducing light, controlling the reaction temperature to be not more than 20 ℃, putting the mixture into the hot light kettle after the reaction is finished, and raising the reaction temperature to 62 ℃ at the speed of raising the temperature per hour by 4-10 ℃ to ensure that the material becomes transparent;
step four, continuously heating the transparent material at the speed of heating to 10-15 ℃ per hour, simultaneously keeping refluxing for 2.5 hours, then switching a reflux valve, and removing phosgene toluene liquid to a light first kettle;
step five, after the desolventizing is finished, heating and introducing nitrogen gas at the same time, removing excessive phosgene and hydrochloric acid gas, and controlling the temperature to be kept at 100 ℃ and 110 ℃ to obtain the p-cumyl isocyanate toluene liquid;
step six, transferring 400kg of dimethylamine and 1600kg of toluene as a front fraction into a synthesis cooling kettle, dropwise adding the toluene solution of the p-isopropyl isocyanate into the synthesis cooling kettle, dropwise adding at one time, wherein the temperature does not exceed 20 ℃ after dropwise adding, synthesizing, and frequently measuring the pH value of the material in the later reaction period to ensure that the pH value is 8, and supplementing the dimethylamine if the pH value is less than 8;
step seven, after the reaction in the step six is finished, transferring the mixture into a heat seal kettle, opening steam to start heating, heating to 85 ℃ at the speed of heating to 15-20 ℃ per hour, keeping the temperature for 1 hour at constant temperature, heating to 90 ℃, and keeping the temperature for 2.5 hours;
step eight, after the heat preservation in the step seven is finished, naturally cooling to below 70 ℃, opening a soft water valve to store 300 liters of soft water, continuously cooling, cooling the material to 35-40 ℃, and centrifuging;
and step nine, recovering the solvent separated in the centrifugal process, and drying the wet material at the drying temperature of 90-100 ℃, wherein isoproturon is obtained after drying is completed.
The working principle of the invention is as follows:
1000kg of p-isopropylaniline in 5 to 10 months, 1200kg of the rest months, and 84 ℃ of the boiling point of a toluene and water azeotrope, so when the temperature in the kettle reaches the first temperature of 84 ℃, the reflux condition is noticed through observing the front and rear water diversion mirrors to prevent flushing, when the temperature of the materials in the kettle reaches the second temperature interval of 105-115 ℃, the reaction end point is approached, the front and rear water diversion mirrors are observed, the temperature is continuously increased until the distillate in the front water diversion mirror has no water drops, and the effluent of the rear water diversion mirror is continuously heated when the effluent is clear and transparent;
the dehydration efficiency of the isoproturon aniline toluene solution is improved, the water content is reduced to be below 50ppm, the content of isoproturon reaction isopropyl ester is improved, the content of a by-product urea is reduced, and the unit consumption of raw material phosgene is reduced;
the cold light kettle is introduced with light and dripped at the same time, the reaction temperature can be effectively controlled not to exceed 20 ℃, and the generation of urea in the process is reduced;
the synthesis cold kettle adopts a isopropyl ester dropping method, and the cumene isocyanate toluene liquid is dropped, so that the temperature in the synthesis process can be effectively controlled, the generation of urea in the process is reduced, the reaction conversion rate, the product quality and the yield are improved, the method obtains good evidence in the actual production, the process is easy to control, meanwhile, the cold conversion rate is improved by 8 percent on average, the yield of isoproturon is improved by 1 percent, and the yield is improved to 98 percent from the original 97 percent.
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 synthetic method of isoproturon herbicide is characterized by comprising the following steps:
step one, adding measured methylbenzene into a dehydration kettle, opening steam to heat, carrying out backflow water diversion, observing front and rear water diversion sight glasses to notice backflow when the temperature in the kettle reaches a first temperature interval, observing the front and rear water diversion sight glasses when the temperature of materials in the kettle reaches a second temperature interval, continuing heating until distillate in the front water diversion sight glasses has no water drops, continuing heating when the effluent of the rear water diversion sight glasses is clear and transparent, and stopping water diversion after maintaining backflow dehydration for 1.5-2.5 hours;
step two, cooling the toluene subjected to water diversion to 35-40 ℃, pumping 1200kg of p-isopropylaniline through a pneumatic diaphragm pump, and completely dissolving to obtain p-isopropylaniline toluene solution;
step three, adding another certain amount of toluene solution into a cold light kettle, introducing light gas at 0 ℃ for saturation to prepare phosgene toluene solution, then dropwise adding p-isopropylaniline toluene solution while introducing light, controlling the reaction temperature not to exceed 20 ℃, placing the mixture into a hot light kettle after the reaction is finished, and raising the reaction temperature to 58-62 ℃ at the speed of raising the temperature by 4-10 ℃ per hour to ensure that the material becomes transparent;
step four, continuously heating the transparent material at the speed of heating to 10-15 ℃ per hour, simultaneously keeping refluxing for 1.5-2.5 hours, then switching a reflux valve, and removing phosgene toluene liquid to a light methyl kettle;
step five, after the desolventizing is finished, heating and introducing nitrogen gas at the same time, and removing excessive phosgene and hydrochloric acid gas to obtain p-cumyl isocyanate toluene liquid;
step six, transferring 300-400kg of dimethylamine and 1200-1600kg of toluene as a front fraction into a synthesis cold kettle, dropwise adding the toluene solution of the p-isopropyl isocyanate into the synthesis cold kettle for synthesis, and periodically measuring the pH value of the material in the later reaction period to ensure that the pH value is 8, and supplementing the dimethylamine if the pH value is less than 8;
seventhly, after the reaction in the sixth step is finished, transferring the mixture into a heat seal kettle, opening steam to start heating, heating to 82-85 ℃ at the speed of heating to 15-20 ℃ per hour, keeping the temperature for 0.5-1 hour at constant temperature, heating to 86-90 ℃, and keeping the temperature for 1.5-2.5 hours;
step eight, after the heat preservation in the step seven is finished, naturally cooling to below 70 ℃, opening a soft water valve to store 300 liters of soft water, continuously cooling, cooling the material to 35-40 ℃, and centrifuging;
and step nine, recovering the solvent separated in the centrifugal process, and drying the wet material to obtain isoproturon.
2. The method as claimed in claim 1, wherein step one, 3800kg of toluene is charged into a dehydration kettle, steam is turned on to raise the temperature for reflux and water diversion, when the temperature in the kettle reaches 80-83 ℃, the reflux condition is noticed through observing the front and rear water diversion mirrors, when the temperature of the materials in the kettle reaches 105-115 ℃ of the second temperature interval, the front and rear water diversion mirrors are observed to continue to raise the temperature until the distillate in the front water diversion mirror has no water drops, when the effluent of the rear water diversion mirror is clear and transparent, the water diversion is stopped after the reflux and dehydration are maintained for 1.5-2.5 hours.
3. The method as claimed in claim 1, wherein the number of said luminescent kettles is two, each luminescent kettle is filled with 1500-2500L toluene solution and saturated with light at 0 ℃ to obtain phosgene toluene solution, the p-isopropylaniline toluene solution obtained in step two is divided into two batches, which are transferred into two aniline overhead tanks for dropwise adding into the luminescent kettle, one aniline overhead tank corresponds to one luminescent kettle.
4. The method as claimed in claim 1, wherein the temperature is controlled to be at 100-110 ℃ during the process of driving off excess phosgene and hydrochloric acid gas in step five.
5. The method for synthesizing an isoproturon herbicide as claimed in claim 1, wherein the dropwise addition in step six is one dropwise addition, and the temperature at the end of the dropwise addition does not exceed 20 ℃.
6. The method for synthesizing isoproturon herbicide as claimed in claim 1, wherein the drying temperature in the ninth step is 90-100 ℃.
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| CN101709041A (en) * | 2009-11-13 | 2010-05-19 | 安徽广信集团铜陵化工有限公司 | Process for producing diuron |
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| CN107162937A (en) * | 2017-07-12 | 2017-09-15 | 安徽广信农化股份有限公司 | A kind of synthesis technique of high-quality diuron |
| CN110938019A (en) * | 2019-12-10 | 2020-03-31 | 江苏快达农化股份有限公司 | Continuous synthesis method of isoproturon |
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| CN101709041A (en) * | 2009-11-13 | 2010-05-19 | 安徽广信集团铜陵化工有限公司 | Process for producing diuron |
| WO2012054093A2 (en) * | 2010-01-29 | 2012-04-26 | The Regents Of The University Of California | Acyl piperidine inhibitors of soluble epoxide hydrolase |
| CN105254536A (en) * | 2015-10-20 | 2016-01-20 | 安徽广信农化股份有限公司 | Diuron esterification synthesis process |
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