CN113264852A - Method for preparing tetrabutyl urea by oil-water two-phase reaction system - Google Patents
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- CN113264852A CN113264852A CN202110531617.6A CN202110531617A CN113264852A CN 113264852 A CN113264852 A CN 113264852A CN 202110531617 A CN202110531617 A CN 202110531617A CN 113264852 A CN113264852 A CN 113264852A
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 113
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 55
- SNDGLCYYBKJSOT-UHFFFAOYSA-N 1,1,3,3-tetrabutylurea Chemical compound CCCCN(CCCC)C(=O)N(CCCC)CCCC SNDGLCYYBKJSOT-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 31
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims abstract description 78
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000243 solution Substances 0.000 claims abstract description 21
- 238000000520 microinjection Methods 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 7
- 238000007670 refining Methods 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000002347 injection Methods 0.000 claims description 9
- 239000007924 injection Substances 0.000 claims description 9
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 10
- 239000007788 liquid Substances 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 7
- 238000007789 sealing Methods 0.000 abstract description 4
- 239000007789 gas Substances 0.000 abstract description 2
- 238000005303 weighing Methods 0.000 description 14
- 239000012071 phase Substances 0.000 description 13
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 12
- 239000012043 crude product Substances 0.000 description 10
- 239000012074 organic phase Substances 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- -1 however Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- FVRDYQYEVDDKCR-DBRKOABJSA-N tiazofurine Chemical compound NC(=O)C1=CSC([C@H]2[C@@H]([C@H](O)[C@@H](CO)O2)O)=N1 FVRDYQYEVDDKCR-DBRKOABJSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 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 method for preparing tetrabutyl urea by an oil-water two-phase reaction system, which takes bis (trichloromethyl) carbonate and dibutylamine as raw materials, designs and provides the oil-water two-phase reaction system, adopts a solvent capable of effectively dissolving the bis (trichloromethyl) carbonate and the dibutylamine, simultaneously adds a water phase into the reaction system, can absorb hydrogen chloride gas generated by the reaction while sealing the reaction system in a liquid state, promotes the forward progress of the whole reaction, and has the characteristics of high conversion rate, high selectivity and the like. The method for preparing the tetrabutyl urea by the oil-water two-phase reaction system comprises the following steps: dissolving bis (trichloromethyl) carbonate in an organic solvent, placing the solution in a reactor, and simultaneously adding water into the reactor to seal a reaction system; then the dibutylamine is dissolved in the organic solvent and is slowly injected into the organic solution of the bis (trichloromethyl) carbonate by a micro-injection pump to carry out chemical reaction, and the product tetrabutyl urea is obtained after refining treatment.
Description
Technical Field
The invention relates to a method for preparing high-purity tetrabutyl urea, in particular to a method for preparing tetrabutyl urea by an oil-water two-phase reaction system.
Background
Tetrabutyl urea (1,1,3, 3-tetrabutyllurea, CAS 4559-86-8) is transparent or slightly yellowish liquid, has a relative density of 0.887 at 25 ℃, a melting point of-51 ℃/760mm mercury, a flash point of 93 ℃, a boiling point of 379.8 ℃/760mmHg, a viscosity slightly higher than that of water, and a solubility similar to that of tetramethylurea, is miscible with most organic reagents such as petroleum ether and the like, is a widely used organic synthesis intermediate, and can also be used as a solvent, an extractant and a catalyst for organic synthesis. In addition, the solubility of the hydrogenated anthraquinone in the tetrabutyl urea is higher than that of trioctyl phosphate, so that the hydrogenation efficiency in the hydrogen peroxide production process is improved, and the distribution coefficient in the extraction process is increased, so that the hydrogenated anthraquinone can be used as a solvent in the hydrogen peroxide production instead of the trioctyl phosphate and is an important carrier in the new hydrogen peroxide production process.
The widely used technology for industrially producing tetrabutyl urea at present is to use phosgene and dibutylamine to react in an organic solvent, however, phosgene is a substance with high toxicity and high reaction activity and has strong corrosivity, Chinese patent with publication No. CN102702029A discloses a method which adopts phosgene as a raw material and a fully-closed reaction device, has extremely high requirements on equipment, adopts gas-liquid contact reaction in the reactor, has low reaction efficiency, has unreacted phosgene in the reactor after the reaction is finished, needs inert gas replacement, and has high operation difficulty. In order to further improve the phosgene conversion rate, patent CN201210103230.1 discloses a method for absorbing unreacted phosgene by reacting phosgene with di-n-butylamine in an alkaline organic solvent and using the alkaline solvent, which basically realizes the reaction process without toxicity, three wastes and harsh process flow operating conditions. In view of the severe toxicity of the reaction raw material phosgene, chinese patent publication No. CN105837473A discloses that bis (trichloromethyl) carbonate (bis (trichloromethyl) carbonate) is used instead of phosgene, the bis (trichloromethyl) carbonate is crushed and then mixed with a strong alkali aqueous solution, after sufficient stirring, dibutylamine is added dropwise for reaction, basically realizing the non-toxicity and harmlessness of the reaction raw materials, but the bis (trichloromethyl) carbonate has poor water solubility, the reaction contact surface is a liquid-solid reaction, and the reaction rate is slow. Chinese patent publication No. CN106478461A discloses that the problem of poor water solubility of bis (trichloromethyl) carbonate is solved by using ethanol as a solvent instead of water, and bis (trichloromethyl) carbonate is dissolved in ethanol and slowly dropped into dibutylamine through a constant pressure funnel, so that the reaction rate is improved, but the reaction selectivity is poor and the yield is not high. Therefore, it is necessary to develop a method for preparing tetrabutyl urea, which avoids using phosgene which is a highly toxic raw material, has low requirement on equipment, has no corrosion to equipment, does not produce three wastes, and has high yield, aiming at the problems.
Disclosure of Invention
The invention provides a method for preparing tetrabutyl urea by an oil-water two-phase reaction system, which aims at the problems and the defects of the prior art, the method takes bis (trichloromethyl) carbonate and dibutylamine as raw materials, the oil-water two-phase reaction system is designed and provided, a solvent capable of effectively dissolving the bis (trichloromethyl) carbonate and the dibutylamine is adopted, simultaneously, a water phase is added into the reaction system, the hydrogen chloride gas generated by the reaction can be absorbed while the reaction system is sealed by liquid, the forward progress of the whole reaction is promoted, and the product tetrabutyl urea can be obtained after the reaction product is subjected to reduced pressure distillation. The whole reaction process is normal temperature and normal pressure, the process flow is simple, and the method has the characteristics of high conversion rate, high selectivity and the like.
The invention is realized by the following technical scheme:
the method for preparing the tetrabutyl urea by the oil-water two-phase reaction system comprises the following steps: dissolving bis (trichloromethyl) carbonate in an organic solvent, placing the solution in a reactor, and simultaneously adding water into the reactor to seal a reaction system; then the dibutylamine is dissolved in the organic solvent and is slowly injected into the organic solution of the bis (trichloromethyl) carbonate by a micro-injection pump to carry out chemical reaction, and the product tetrabutyl urea is obtained after refining treatment.
The invention relates to a method for preparing tetrabutyl urea by an oil-water two-phase reaction system, which adopts the further technical scheme that the molar ratio of the reaction raw materials of bis (trichloromethyl) carbonate to dibutylamine is 1: 6-48; the added water is deionized water, and the added amount of the water can completely absorb the byproduct hydrogen chloride generated by the reaction. The further technical proposal is that the mol ratio of the reaction raw material bis (trichloromethyl) carbonate to dibutylamine is preferably 1: 24-36.
The method for preparing the tetrabutyl urea by the oil-water two-phase reaction system has the further technical scheme that the organic solvent can be cyclohexane, n-octanol, carbon tetrachloride, dichloromethane, dichloroethane or a combination thereof; still further, dichloroethane is preferred as the solvent.
The method for preparing the tetrabutyl urea by the oil-water two-phase reaction system has the further technical scheme that the concentration of the bis (trichloromethyl) carbonate organic solution is 2-50 percent; the concentration of the dibutylamine organic solution is 15% -100%. The concentration of the bis (trichloromethyl) carbonate organic solution is preferably 5 to 10 percent; the concentration of the dibutylamine organic solution is preferably 40-60%.
The further technical scheme of the method for preparing the tetrabutyl urea by the oil-water two-phase reaction system can be that the feeding injection rate of the micro-injection pump is 1-15 mL/h. Still further technical proposal is that the feeding injection rate of the micro-injection pump is preferably 6-9 mL/h.
The method for preparing the tetrabutyl urea by the oil-water two-phase reaction system has the further technical scheme that the temperature of the reaction system is 20-60 ℃, the reaction pressure is normal pressure, and the reaction time is 2-10 h. The further technical proposal is that the reaction temperature is preferably 35-45 ℃ and the reaction time is preferably 6-8 h. .
After the reaction is finished, the organic phase and the water phase are separated, the organic phase is washed by water, dried and distilled under reduced pressure to obtain the tetrabutyl urea, and the water phase is recycled after the byproduct hydrogen chloride is removed.
Compared with the prior art, the invention has the following beneficial effects:
compared with the traditional preparation method, the preparation method disclosed by the invention has the advantages that the reaction system is carried out in an organic solvent, and the bis (trichloromethyl) carbonate is used for replacing phosgene, so that the transportation difficulty of reaction raw materials is solved, the corrosion of phosgene to equipment is reduced, the service life of the whole period of the device is prolonged, the reaction materials are basically nontoxic and harmless, the operation difficulty is reduced, and the process cost is reduced. The reaction system is carried out in an organic solvent, so that the mass transfer area in the reaction process is increased, the conversion rate of raw materials and the selectivity of products are improved, and the high yield of reaction products is realized. And meanwhile, deionized water is added into the reaction system, so that hydrogen chloride generated in the reaction process can be absorbed while the reaction system is sealed in a liquid state, the forward progress of the reaction is promoted, and the conversion rate of the reaction is further improved. The preparation method basically realizes the aims of no toxicity and pollution in the reaction process, high reaction conversion rate and good selectivity of target products. The conversion rate of the bis (trichloromethyl) carbonate in the invention can reach 99.1%, and the selectivity of the tetrabutyl urea can also reach 99.2%.
Detailed Description
Example 1
Weighing 1.68 g of bis (trichloromethyl) carbonate, dissolving the bis (trichloromethyl) carbonate in 31.68 g of dichloroethane, adding the solution into a 250mL three-neck flask, weighing 30mL of deionized water, and adding the deionized water into the three-neck flask to form a liquid seal; weighing 27.43 g of dibutylamine, dissolving the dibutylamine in 15.02 g of dichloroethane, placing the dibutylamine in a 50mL micro-injection pump, setting the sample injection rate of the micro-injection pump to be 9mL/h, starting stirring, controlling the reaction temperature to be 45 ℃, sealing the reactor after the feeding is finished, and continuing the reaction, wherein the feeding time is about 5h, and the reaction retention time is about 3 h. After the reaction is finished, separating the reaction solution by using a separating funnel, washing an organic phase by using water, and then distilling under reduced pressure to obtain a crude product of the tetrabutyl urea, and distilling the crude product under reduced pressure to obtain a product of the tetrabutyl urea. Meanwhile, the unreacted dibutylamine can be recycled after being recovered. The analysis shows that the conversion rate of the bis (trichloromethyl) carbonate can reach 99.10 percent, and the selectivity of the tetrabutyl urea can also reach 99.20 percent.
Example 2
Weighing 1.62 g of bis (trichloromethyl) carbonate, dissolving the bis (trichloromethyl) carbonate in 32.38 g of dichloroethane, adding the solution into a 250mL three-neck flask, weighing about 30mL of deionized water, and adding the deionized water into the three-neck flask to form a liquid seal; weighing 16.9 g of dibutylamine, dissolving the dibutylamine in 25 g of dichloroethane, placing the dibutylamine in a 50mL micro-injection pump, setting the sample injection rate of the micro-injection pump to be 9mL/h, starting stirring, controlling the reaction temperature to be 45 ℃, and after the feeding is finished, continuously reacting in a closed reactor, wherein the feeding time is about 5h, and the reaction retention time is about 3 h. After the reaction is finished, separating the reaction solution by using a separating funnel, washing an organic phase by using water, and then distilling under reduced pressure to obtain a crude product of the tetrabutyl urea, and distilling the crude product under reduced pressure to obtain a product of the tetrabutyl urea. Meanwhile, the unreacted dibutylamine can be recycled after being recovered, and the conversion rate of the bis (trichloromethyl) carbonate can reach 99.00 percent and the selectivity of the tetrabutyl urea can also reach 88.96 percent through analysis.
Example 3
Weighing 1.66 g of bis (trichloromethyl) carbonate, dissolving in 35.80 g of cyclohexane, adding into a 250mL three-neck flask, weighing 30mL of deionized water, and adding into the three-neck flask; weighing 16.91 g of dibutylamine, dissolving the dibutylamine in 10 g of cyclohexane, placing the dibutylamine in a 50mL micro-injection pump, setting the injection rate of the micro-injection pump to be 3mL/h, starting stirring, and controlling the reaction temperature to be about 35 ℃. The reaction feeding time is about 8h, after the reaction is finished, the reaction solution is separated by a separating funnel, the organic phase is washed by water and then is subjected to reduced pressure distillation and refining to obtain a crude product of the tetrabutyl urea, and the crude product is subjected to reduced pressure distillation to obtain a product of the tetrabutyl urea. Meanwhile, the unreacted dibutylamine can be recycled, and the conversion rate of the bis (trichloromethyl) carbonate can reach 99.09% and the selectivity of the tetrabutyl urea can reach 70.05% through analysis.
Example 4
Weighing 1.67 g of bis (trichloromethyl) carbonate, dissolving in 34.97 g of n-octanol, adding into a 250mL three-neck flask, weighing 30mL of deionized water, and adding into the three-neck flask; weighing 37.29 g of dibutylamine, placing the dibutylamine in a 50mL micro-injection pump, setting the sample injection rate of the micro-injection pump to be 9mL/h, starting stirring, controlling the reaction temperature to be about 25 ℃, and sealing the reactor to continue the reaction after the feeding is finished. Wherein the reaction feeding time is about 4h, the reaction retention time is about 4h, after the reaction is finished, the reaction liquid is separated by a separating funnel, the organic phase is washed by water and then is subjected to reduced pressure distillation and refining to obtain a crude product of the tetrabutyl urea, and the crude product is subjected to reduced pressure distillation to obtain a product of the tetrabutyl urea. Meanwhile, the unreacted dibutylamine can be recycled after being recovered, and the conversion rate of the bis (trichloromethyl) carbonate can reach 97.65 percent and the selectivity of the tetrabutyl urea is only 51.98 percent.
Comparative example 1 (No Water seal)
Weighing 1.66 g of bis (trichloromethyl) carbonate, dissolving the bis (trichloromethyl) carbonate in 30.26 g of dichloroethane, and adding the solution into a 250mL three-neck flask; weighing 36.26 g of dibutylamine, placing the dibutylamine in a 50mL micro-injection pump, setting the sample injection rate of the micro-injection pump to be 6mL/h, starting stirring, controlling the reaction temperature to be about 35 ℃, and after the feeding is finished, sealing the reactor to continue the reaction, wherein the feeding time is about 6.5h, and the reaction retention time is about 1.5 h. After the reaction is finished, separating the reaction solution by using a separating funnel, washing an organic phase by using water, and then distilling under reduced pressure to obtain a crude product of the tetrabutyl urea, and distilling the crude product under reduced pressure to obtain a product of the tetrabutyl urea. Meanwhile, the unreacted dibutylamine can be recycled after being recovered, and analysis shows that the conversion rate of the bis (trichloromethyl) carbonate can reach 99.03%, and the selectivity of the tetrabutyl urea can also reach 82.65%. As can be seen from comparative example 1, the addition of the aqueous phase is eliminated, and the reaction by-product hydrogen chloride reacts with the starting material dibutylamine to form dibutylamine hydrochloride, which hinders the reaction and reduces the selectivity of the product. Meanwhile, due to the reduction of the reaction temperature and the reduction of the dibutylamine feeding rate, certain influence is also generated on the forward progress of the reaction, and finally, the selectivity of the target product is reduced.
Claims (10)
1. A method for preparing tetrabutyl urea by an oil-water two-phase reaction system is characterized by comprising the following steps: dissolving bis (trichloromethyl) carbonate in an organic solvent, placing the solution in a reactor, and simultaneously adding water into the reactor to seal a reaction system; then the dibutylamine is dissolved in the organic solvent and is slowly injected into the organic solution of the bis (trichloromethyl) carbonate by a micro-injection pump to carry out chemical reaction, and the product tetrabutyl urea is obtained after refining treatment.
2. The method for preparing tetrabutyl urea by using an oil-water two-phase reaction system according to claim 1, wherein the molar ratio of the bis (trichloromethyl) carbonate to dibutylamine is 1: 6-48; the added water is deionized water, and the added amount of the water can completely absorb the byproduct hydrogen chloride generated by the reaction.
3. The method for preparing tetrabutyl urea by using an oil-water two-phase reaction system according to claim 2, wherein the molar ratio of the bis (trichloromethyl) carbonate to dibutylamine is 1: 24-36.
4. The method for preparing tetrabutyl urea with the oil-water two-phase reaction system according to claim 1, wherein the organic solvent is cyclohexane, n-octanol, carbon tetrachloride, dichloromethane, dichloroethane or a combination thereof.
5. The method for preparing tetrabutyl urea by using an oil-water two-phase reaction system according to claim 1, wherein the concentration of the bis (trichloromethyl) carbonate organic solution is 2% -50%; the concentration of the dibutylamine organic solution is 15% -100%.
6. The method for preparing tetrabutyl urea with the oil-water two-phase reaction system according to claim 5, wherein the concentration of the bis (trichloromethyl) carbonate organic solution is 5% -10%; the concentration of the dibutylamine organic solution is 40-60%.
7. The method for preparing tetrabutyl urea with the oil-water two-phase reaction system as claimed in claim 1, wherein the micro-injection pump has a feed injection rate of 1-15 mL/h.
8. The method for preparing tetrabutyl urea with the oil-water two-phase reaction system as claimed in claim 7, wherein the micro-injection pump has a feed injection rate of 6-9 mL/h.
9. The method for preparing tetrabutyl urea by using the oil-water two-phase reaction system according to claim 1, wherein the temperature of the reaction system is 20-60 ℃, the reaction pressure is normal pressure, and the reaction time is 2-10 h.
10. The method for preparing tetrabutyl urea with the oil-water two-phase reaction system according to claim 9, wherein the reaction temperature is 35-45 ℃ and the reaction time is 6-8 h.
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| CN101333176A (en) * | 2008-05-30 | 2008-12-31 | 浙江工业大学 | Method for preparing substituent urea and co-producing hydrochloride of corresponding amines |
| CN103193680A (en) * | 2013-04-03 | 2013-07-10 | 北京石油化工学院 | Preparation method of tetrabutyl urea |
| CN108558706A (en) * | 2018-03-28 | 2018-09-21 | 苏州昊帆生物股份有限公司 | Tetramethylurea and preparation method thereof |
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2021
- 2021-05-17 CN CN202110531617.6A patent/CN113264852A/en active Pending
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