CN104230759A - Preparation method of 3,4,4-trichlorocarbonylaniline - Google Patents
Preparation method of 3,4,4-trichlorocarbonylaniline Download PDFInfo
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- CN104230759A CN104230759A CN201410424387.3A CN201410424387A CN104230759A CN 104230759 A CN104230759 A CN 104230759A CN 201410424387 A CN201410424387 A CN 201410424387A CN 104230759 A CN104230759 A CN 104230759A
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- chlorophenyl isocyanate
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- trichlorocarbanilide
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- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- HFCNULUJRINLMK-UHFFFAOYSA-N 4-aminocyclohexa-3,5-diene-1,1,2-tricarbonyl chloride Chemical compound ClC(=O)C1C=C(N)C=CC1(C(=O)Cl)C(=O)Cl HFCNULUJRINLMK-UHFFFAOYSA-N 0.000 title abstract 4
- ADAKRBAJFHTIEW-UHFFFAOYSA-N 1-chloro-4-isocyanatobenzene Chemical compound ClC1=CC=C(N=C=O)C=C1 ADAKRBAJFHTIEW-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000007787 solid Substances 0.000 claims abstract description 29
- SDYWXFYBZPNOFX-UHFFFAOYSA-N 3,4-dichloroaniline Chemical compound NC1=CC=C(Cl)C(Cl)=C1 SDYWXFYBZPNOFX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 38
- ICUTUKXCWQYESQ-UHFFFAOYSA-N triclocarban Chemical compound C1=CC(Cl)=CC=C1NC(=O)NC1=CC=C(Cl)C(Cl)=C1 ICUTUKXCWQYESQ-UHFFFAOYSA-N 0.000 claims description 33
- 239000007921 spray Substances 0.000 claims description 13
- 238000005507 spraying Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 6
- 229960005081 diclofenamide Drugs 0.000 claims description 5
- 229960001325 triclocarban Drugs 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 238000002156 mixing Methods 0.000 abstract description 6
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 16
- 150000002148 esters Chemical class 0.000 description 7
- 125000006283 4-chlorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1Cl)C([H])([H])* 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000003912 environmental pollution Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 125000001475 halogen functional group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- BLNVISNJTIRAHF-UHFFFAOYSA-N 4-chlorobenzamide Chemical compound NC(=O)C1=CC=C(Cl)C=C1 BLNVISNJTIRAHF-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical class O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of basic chemical engineering, and particularly relates to a preparation method of 3,4,4-trichlorocarbonylaniline. According to the technical scheme, the preparation method comprises the following steps: under the condition of no solvent, adding 3,4-dichloroaniline and 4-chlorophenylisocyanate into a solid reactor for reacting at the temperature of 20-100DEG C, wherein the solid reactor is all equipment applicable to mixing and crushing of industrial solid powder. Particularly, the solid reactor is selected from one of a ball mill, an agravic mixer or a plough scraper type mixer. According to the preparation method of 3,4,4-trichlorocarbonylaniline, a solvent is not required during preparation, so that not only can the production cost of TCC be lowered, and the safety coefficient of the production process is improved, but also the environment pollution can be reduced, and the preparation method of 3,4,4-trichlorocarbonylaniline is an environmentally-friendly production method.
Description
Technical field
The present invention relates to basic chemical industry field, particularly a kind of preparation method of 3,4,4-Trichlorocarbanilide.
Background technology
3,4,4-Trichlorocarbanilide (TCC) is a kind of excellent antiseptic-germicide, and it is to bacterium, and particularly gram-positive microorganism has excellent restraining effect.Due to its low toxicity, high efficiency and higher thermostability and anti-discoloration, make it at light antimicrobial product, particularly widely apply in antibacterial and deodouring soap, following formula is the structural formula of TCC.
About the synthesis of TCC, early have report in the literature, the people such as David J.Beaver mention the method for synthesizing corresponding halogenated carbonyl aniline with halo aniline and halo isocyanic ester in diethyl ether in United States Patent (USP) 2846398.But very poor according to the product crystal shape of the method synthesis, product is very difficult with being separated of solvent.And product colour is poor, if the good product of colourity will be obtained, need recrystallization in ethanol, add difficulty and the cost of production.
Disclose one organic bases in CN101081822 as catalyzer, toluene is as the synthesis technique of solvent.Although this technique can obtain good transformation efficiency and product yield, use solvent toluene, add cost, reduce safety coefficient, and cause environmental pollution due to the volatilization of toluene.
A kind of toluene that uses is disclosed as solvent in CN100478330C, the technique of synthesis TCC, the toluene that this technique uses needs just can apply mechanically through complicated pickling, alkali cleaning and washing aftertreatment technology, not only add production cost and process complexity, and produce a large amount of waste water, cause environmental pollution.
CN102603574A discloses and is contacted with parachlorobenzyl isocyanic ester solution by 3,4-DCA solution, obtains Trichlorocarbanilide.Wherein, the concentration of described parachlorobenzyl isocyanic ester solution is no more than 20 % by weight, and with the weight of described parachlorobenzyl isocyanic ester for benchmark, in described parachlorobenzyl isocyanic ester solution, the content of impurity is lower than 1.0 % by weight.Need equally in this method with an organic solvent to dissolve parachlorobenzyl isocyanic ester, and higher to ingredient requirement.
As can be seen from above-mentioned document, not only will be with an organic solvent in the synthesis technique of TCC, and the organic solvent ratio used is very large, as in CN100478330C embodiment 1, calculating TCC output according to its yield is 196.8g, toluene for the synthesis of TCC is about 1025ml, can obtain thus, and products obtained therefrom reaches 1g: 5.2ml with using the mass volume ratio of solvent.Because these organic solvents not only have certain toxicity, and there is inflammable and explosive property.Not only add product cost, and its volatilization also can cause environmental pollution and the wasting of resources, does not meet the requirement of Green Chemistry.
Summary of the invention
The object of this invention is to provide a kind of applicable industrialized, in the absence of a solvent, the method for preparation 3,4,4-Trichlorocarbanilide.
In order to realize object of the present invention, the technical scheme that concrete employing is following: in the absence of a solvent, in solid reactor, by 3,4-DCA and 4-chlorophenyl isocyanate reaction preparation 3,4,4-Trichlorocarbanilide.Described solid reactor is allly be applicable to the mixing of industrialization solid powder, the equipment of damaged function.
What the present invention selected is applicable to the mixing of industrialization solid powder, the equipment of crushing function, is widely adopted in preparation process at industrial production mixture.Compared with mixture, the reaction conditions required in the preparation process of compound is more harsh, is therefore applicable to the mixing of industrialization solid powder, reactor that the equipment of crushing function is not used as the preparation process of compound.
Under the impact of intrinsic notion, people it is generally acknowledged, the reaction that the reaction producing solid prepares 3,4,4-Trichlorocarbanilide as the present invention just can must be carried out under solvent condition, or could handled easily.Instant invention overcomes the prejudice of prior art, prepare the reaction of 3,4,4-Trichlorocarbanilide in the absence of a solvent.The reaction of preparation 3,4,4-Trichlorocarbanilide provided by the invention does not use inflammable and explosive organic solvent, improves the safety coefficient of production process on the one hand, avoids the environmental pollution because solvent evaporates causes; Decrease the production process such as solid-liquid separation, solvent recuperation simultaneously, simplify technique.The preparation method that the invention provides 3,4,4-Trichlorocarbanilide has good environment friendly.
Concrete, the preparation method of the present invention 3,4,4-Trichlorocarbanilide comprises the following steps:
(1) with 3,4-DCA and 4-chlorophenyl isocyanate for reactant, the one of reactant is added solid reactor, material is warming up to 50 ~ 60 DEG C;
(2) by the another kind of reactant adopt in batches or spray pattern join in solid reactor, control temperature of reaction be 20 ~ 100 DEG C, stirring velocity is 30 ~ 130r/min, reacts 2 ~ 8 hours, obtains crude product 3,4,4-Trichlorocarbanilide;
(3) at 100 ~ 130 DEG C, under the condition of-0.085 ~ 0.1MPa, crude product 3,4, the 4-Trichlorocarbanilide of step (1) gained is toasted 4 ~ 8 hours, obtain 3,4,4-Trichlorocarbanilide.
Consider that this reaction process is more violent, liberated heat is higher instantaneously, the present invention first adds 3 in solid reactor, one in 4-dichlorphenamide bulk powder or 4-chlorophenyl isocyanate, another adopts the mode in batches added to add, such 3,4-DCA or 4-chlorophenyl isocyanate of making can fully contact, and is more conducive to controlling speed of response and temperature of reaction.
3 are prepared utilizing solid reactor, 4, during the reaction of 4-Trichlorocarbanilide, partial reaction raw material reaction is incomplete, unreacted part material, by under the condition of high temperature, high vacuum, is evaporated, reaches the object of purification by the present invention, method of purification provided by the invention does not need to use solvent wash, and operating process is simple.
4-chlorophenyl isocyanate in the present invention and 3,4-DCA can select arbitrary product of the prior art, and the present invention is not construed as limiting this.
Because the 4-chlorophenyl isocyanate (can be described as parachlorobenzyl isocyanic ester again) in the present invention is colourless to weak yellow liquid, add fashionable especially spraying adds fashionable more convenient in batches, preferably, step (1) is by 3,4-dichlorphenamide bulk powder joins in solid reactor, and step (2) is adopted in batches by 4-chlorophenyl isocyanate or spray pattern joins in solid reactor.
In order to make 3,4-DCA and 4-chlorophenyl isocyanate react completely, being beneficial to and controlling speed of response and temperature of reaction, step (2) adopts the mode that adds of spraying to add and is joined in solid reactor by 4-chlorophenyl isocyanate.The speed that sprays into of spraying can be determined according to the particular case of reaction, and generally, per minute sprays into 0.4 ~ 0.8% of 4-chlorophenyl isocyanate total amount.
In order to make 3,4-DCA and 4-chlorophenyl isocyanate react completely, be beneficial to and control speed of response and temperature of reaction, 4-chlorophenyl isocyanate is divided into 5 ~ 15 batches to join in solid reactor by step (2).Often criticize to join in reactor and all react for some time, the reaction times depends on the circumstances.
Preferably, 4-chlorophenyl isocyanate is divided into 10 batches to join in solid reactor.
The side reaction caused in order to avoid high temperature occurs, and affects the purity of reactant, and the preferred temperature of reaction of step (2) is 50 ~ 80 DEG C.
Concrete, solid reactor of the present invention is selected from the one in ball mill, Agravicmixer or coulter type mixer.Described ball mill is Horizontal cylindrical chuck swivel arrangement, by the major portion composition such as feed portion, discharging portion, rotating part, driving section (step-down gear, small transmission gear, motor, automatically controlled), can lead to cooling water and steam in chuck; Inner pottery or the stainless steel spheroid using different size, under the turning effort of urceolus, plays effect that is broken and mixing; For reducing spheroid to the gouging abrasion of cylindrical shell, in cylindrical shell, stud with abrasion-proof backing block.
Described Agravicmixer equipment is the equipment of horizontal cylinder shape with chuck, arranges the blade that difference turns to, cylindrical shell is distributed with fly knife device at cylinder distribution in vivo two; During work, material radial direction, hoop, axial three-dimensional shed motion, fly cutter on cylindrical shell plays crushing effect, material shape becomes cross-circulation, shears the multiple effects such as blending, as the WLZ Agravicmixer (increase fly knife device) that Shanghai Shengli Machinery Manufacturing Co., Ltd. produces.
The structure of described coulter type mixer and principle and Agravicmixer similar, difference is that inner agitating vane is colter, as the LDHS colter mixer (increase fly knife device) that Shanghai Shengli Machinery Manufacturing Co., Ltd. produces.
The present invention can carry out under temperature is the condition of 20-100 DEG C, and temperature of reaction is too low, and speed of response is too slow, and required time is long, is unfavorable for suitability for industrialized production; Temperature of reaction is too high, can produce by product, and reduce product content, preferably, temperature of reaction of the present invention is 50 ~ 80 DEG C.The present invention also can react when 20-40 DEG C.
The present invention is strict to the proportion requirement of reactant, when the mol ratio of 3,4-DCA and 4-chlorophenyl isocyanate is 1.1: 1 ~ 1: 1.1, all can make the productive rate that product keeps higher.
When the mol ratio of 3,4-DCA and 4-chlorophenyl isocyanate is 1: 1 ~ 1.05, there is certain help to the content reducing p-Chlorobenzoic acid amide, 3,4-DCA in product.
Preferably, if considered from cost angle, when the mol ratio of 3,4-DCA and 4-chlorophenyl isocyanate is 1: 1, can farthest reduce costs.
The preparation method of 3,4,4-Trichlorocarbanilides provided by the invention, does not need solvent in preparation process, can not only reduce TCC production cost, and improving the safety coefficient of production process, and can reduce environmental pollution, is a kind of environmentally friendly production method.And its color of 3,4,4-Trichlorocarbanilides to be prepared by preparation method of the present invention and crystal all can meet the needs in market, purity can reach more than 99%, and productive rate also can reach more than 90%.
Embodiment
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
The present embodiment is for adopting coulter type mixer uninanned platform TCC, and concrete preparation method comprises the following steps:
(1) in the 200L coulter type mixer (with fly knife device) being equipped with thermometer, sprinkler head, temperature control chuck, 40.5kg (0.25Kmol) 3 is added, 4-dichlorphenamide bulk powder, start coulter type mixer, rotating speed is 130r/min, material is warming up to 50 DEG C;
(2) at the uniform velocity spray into 4-chlorophenyl isocyanate with spraying head, the speed of spraying into is 0.32kg/min, sprays into 38.375kg (0.25Kmol) altogether, about 2 hours used times, and in the process, utilizing temperature control chuck to control temperature of reaction is 50 ~ 80 DEG C;
(3) controlling temperature of reaction is 50 DEG C, and stirring velocity is 130r/min, insulation reaction 1 hour, and then reaction product is at 110 DEG C, toasts 4 hours, release to obtain 3,4,4-Trichlorocarbanilides from the drain hole of coulter type mixer under the condition of-0.1MPa.
Sampling finds after detecting, and reacted product is white, and crystal is fine acicular, obtains product 77.5kg altogether, and know that the content of TCC in products therefrom is 99.53% with liquid-phase chromatographic analysis, productive rate is 98%.
Embodiment 2
The present embodiment is Agravicmixer uninanned platform TCC, and concrete preparation method comprises the following steps:
(1) in the 200L Agravicmixer being equipped with thermometer, sprinkler head, temperature control chuck, add 40.5kg (0.25Kmol) 3,4-DCA, start Agravicmixer, rotating speed is 60r/min, material is warming up to 50 DEG C;
(2) at the uniform velocity spray into 4-chlorophenyl isocyanate with spraying head, the speed of spraying into is 0.16kg/min, sprays into 38.375kg (0.25Kmol) altogether, about 4 hours used times, in the process, utilizes temperature control chuck to control temperature of reaction 80 DEG C;
(3) controlling temperature of reaction is 50 ~ 80 DEG C, and stirring velocity is 60r/min, insulation reaction 2 hours; Then reaction product is at 100 DEG C, toasts 6 hours, release to obtain 3,4,4-Trichlorocarbanilides from the drain hole of Agravicmixer under the condition of-0.1MPa.
Reacted product is white, and crystal is fine acicular, obtains product 73.8kg altogether, and know that the content of TCC in products therefrom is 99.21% with liquid-phase chromatographic analysis, productive rate is 93.57%.
Embodiment 3
The present embodiment is ball mill uninanned platform TCC, and concrete preparation method comprises the following steps:
(1) in the 200L ball mill being equipped with thermometer, temperature control chuck, 40.5kg (0.25Kmol) 3 is added, 4-dichlorphenamide bulk powder, add 3.84kg (0.025kmol) 4-chlorophenyl isocyanate simultaneously, material is warming up to 50 DEG C, at the uniform velocity stir, rotating speed is 30r/min, and controlling temperature of reaction by chuck is 60 DEG C, hybrid reaction 0.5 hour;
(2) 3.84kg (0.025kmol) 4-chlorophenyl isocyanate is added, when rotating speed is 30r/min, hybrid reaction 0.5 hour, in whole process, control temperature of reaction by chuck is 60 DEG C;
(3) step (2) repeats 8 times;
(4) control temperature is 60 DEG C, and stirring velocity is 30r/min, insulation reaction 2 hours.
(5) react after product at 130 DEG C, toast 6 hours under-0.085MPa vacuum condition, sampling detects.
Reacted product is white powder, and crystal is fine acicular, obtains product 74.3kg altogether, and know that the content of TCC in products therefrom is 99.02% with liquid-phase chromatographic analysis, productive rate is 94.2%.
Embodiment 4
The present embodiment is for adopting coulter type mixer uninanned platform TCC, and concrete preparation method comprises the following steps:
(1) in the 200L coulter type mixer being equipped with thermometer, sprinkler head, temperature control chuck, add 40.5kg (0.25Kmol) 3,4-DCA, start coulter type mixer, rotating speed is 130r/min, material is warming up to 30 DEG C;
(2) at the uniform velocity spray into 4-chlorophenyl isocyanate with spraying head, the speed of spraying into is 0.16kg/min, sprays into 38.375kg (0.25Kmol) altogether, about 4 hours used times, utilizes temperature control chuck to control temperature of reaction 20 ~ 40 DEG C;
(3) controlling temperature of reaction is 20 ~ 40 DEG C, and stirring velocity is 130r/min, insulation reaction 3 hours.
(4) react after product at 120 DEG C, toast 8 hours under-0.085MPa vacuum condition, sampling detects.
Reacted product is white, and crystal is fine acicular, obtains product 74.2kg altogether, and be 99.62% with the content of TCC in liquid-phase chromatographic analysis products therefrom, productive rate is 94.07%.
Reference examples
Temperature of reaction, with embodiment 1, just controls more than 120 DEG C by experimentation.
Reaction result cartogram
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (10)
1. the preparation method of a Trichlorocarbanilide, by 3,4-DCA and 4-chlorophenyl isocyanate reaction preparation 3,4,4-Trichlorocarbanilide, is characterized in that: in the absence of a solvent, reacts in solid reactor.
2. preparation method according to claim 1, is characterized in that, comprises the following steps:
(1) with 3,4-DCA and 4-chlorophenyl isocyanate for reactant, the one of reactant is added solid reactor, material is warming up to 50 ~ 60 DEG C;
(2) by the another kind of reactant adopt in batches or spray pattern join in solid reactor, control temperature of reaction be 20 ~ 100 DEG C, stirring velocity is 30 ~ 130r/min, reacts 2 ~ 8 hours, obtains crude product 3,4,4-Trichlorocarbanilide;
(3) at 100 ~ 130 DEG C, under the condition of-0.085 ~ 0.1MPa, crude product 3,4, the 4-Trichlorocarbanilide of step (1) gained is toasted 4 ~ 8 hours, obtain 3,4,4-Trichlorocarbanilide.
3. preparation method according to claim 2, it is characterized in that: step (1) is by 3,4-dichlorphenamide bulk powder joins in solid reactor, and step (2) is adopted in batches by 4-chlorophenyl isocyanate or spray pattern joins in solid reactor.
4. preparation method according to claim 3, is characterized in that: step (2) adopts the mode of spraying to add and join in solid reactor by 4-chlorophenyl isocyanate, and per minute sprays into 0.4 ~ 0.8% of 4-chlorophenyl isocyanate total amount.
5. preparation method according to claim 3, is characterized in that: be divided into 5 ~ 15 batches to join in solid reactor 4-chlorophenyl isocyanate.
6. preparation method according to claim 5, is characterized in that: be divided into 10 batches to join in solid reactor 4-chlorophenyl isocyanate.
7. preparation method according to claim 2, is characterized in that: step (2) temperature of reaction is 50 ~ 80 DEG C.
8. preparation method according to claim 1, is characterized in that: described solid reactor chooses the one in ball mill, Agravicmixer or coulter type mixer.
9. preparation method according to claim 1, is characterized in that: the mol ratio of 3,4-DCA and 4-chlorophenyl isocyanate is 1.1: 1 ~ 1: 1.1.
10. preparation method according to claim 1, is characterized in that: the mol ratio of 3,4-DCA and 4-chlorophenyl isocyanate is 1: 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110724057A (en) * | 2019-12-05 | 2020-01-24 | 山东省化工研究院 | Preparation method of carbasalate calcium |
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| CN101081822A (en) * | 2007-01-10 | 2007-12-05 | 胡汉忠 | Industrial preparation method of halogenated carbonyl aniline |
| CN102603574A (en) * | 2011-12-19 | 2012-07-25 | 中粮生物化学（安徽）股份有限公司 | Preparation method of trichlorocarbanilide (TCC) |
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- 2014-08-26 CN CN201410424387.3A patent/CN104230759B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1495219A (en) * | 2002-05-10 | 2004-05-12 | 1 | Solventless continuous preparation method of polyurea |
| CN101081822A (en) * | 2007-01-10 | 2007-12-05 | 胡汉忠 | Industrial preparation method of halogenated carbonyl aniline |
| CN101033203A (en) * | 2007-04-10 | 2007-09-12 | 宁波志华化学有限公司 | Method of preparing 1-(4-chloro-phenyl)-3-(3,4-dichloro-phenyl)-urea |
| CN102603574A (en) * | 2011-12-19 | 2012-07-25 | 中粮生物化学（安徽）股份有限公司 | Preparation method of trichlorocarbanilide (TCC) |
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| CN110724057A (en) * | 2019-12-05 | 2020-01-24 | 山东省化工研究院 | Preparation method of carbasalate calcium |
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