[go: up one dir, main page]

WO2016039466A1 - Nouveau procédé de production d'azodicarbonamide - Google Patents

Nouveau procédé de production d'azodicarbonamide Download PDF

Info

Publication number
WO2016039466A1
WO2016039466A1 PCT/JP2015/075926 JP2015075926W WO2016039466A1 WO 2016039466 A1 WO2016039466 A1 WO 2016039466A1 JP 2015075926 W JP2015075926 W JP 2015075926W WO 2016039466 A1 WO2016039466 A1 WO 2016039466A1
Authority
WO
WIPO (PCT)
Prior art keywords
formula
urea
water
organic solvent
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2015/075926
Other languages
English (en)
Japanese (ja)
Inventor
谷口　正俊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
I&c Chemtech Co Ltd
Original Assignee
I&c Chemtech Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by I&c Chemtech Co Ltd filed Critical I&c Chemtech Co Ltd
Priority to CN201580049311.XA priority Critical patent/CN106795105B/zh
Priority to JP2016547809A priority patent/JP6165349B2/ja
Publication of WO2016039466A1 publication Critical patent/WO2016039466A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C281/00—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
    • C07C281/20—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group the two nitrogen atoms of the functional groups being doubly-bound to each other, e.g. azoformamide

Definitions

  • the present invention relates to a production method for obtaining azodicarbonamide using a urea active derivative and a structure.
  • Azodicarbonamide is a useful compound widely used as a foaming agent from the viewpoint of its decomposition behavior, physical properties, and chemical properties.
  • the most commonly practiced conventional production method involves reacting hydrazine hydrate produced from urea or ammonia with 2 moles of urea.
  • This is a method for producing azodicarbonamide by several stages of reaction including the above (Patent Document 1).
  • This conventional production method causes wasteful consumption of raw materials that do not contribute to the molecular structure of the target product azodicarbonamide, which causes an increase in cost.
  • Another problem is the generation of a large amount of ammonia as a by-product and carbon dioxide that causes global warming.
  • this method uses a chlorinating agent, an oxidizing agent, a strong acid, a heavy metal catalyst, or the like, a large amount of waste water containing a large amount of salts, acids, heavy metals, ammonia nitrogen, and the like is generated as waste. Since disposal is required to dispose of these, it costs a large amount of processing costs, increases product costs, and may cause pollution. Sometimes it is possible.
  • Patent Document 4 the structural formula of urea and the structural formula of azodicarbonamide (ADCA) are completely different by using a special apparatus in a special method called organic electrolytic synthesis from urea. Nevertheless, it is described that ADCA is suddenly generated from urea. It is illogical if it reacts with other raw materials from urea to produce various reaction intermediates and the desired ADCA is not obtained. Also in the energy yield, if the electric energy required for the direct reaction is calculated, there is a problem that a large amount of electric energy having a very low electric energy yield is wasted. Details will be given in later sections.
  • Patent Document 3 The production method of chlorourea and bromourea used as raw materials or intermediates used in the present invention is described in (Patent Document 3) in addition to (Patent Document 1).
  • Patent Document 4 In a recently published document (Patent Document 4), the actual state of the reaction has not been elucidated at all using a special method and a special apparatus called an organic electrolytic synthesis method from urea.
  • Various general problems and drawbacks have already been pointed out in the background section. It is a patent that the object that is completely different from the raw material can be unknown at once, special equipment, special technology is necessary, and if you do not perform continuous recycling reaction with raw materials with complicated composition, you can obtain the object I can't. Furthermore, since the raw material is used in a large excess, it is essential to recycle the raw material. Prediction of side reactions and impurities from the side reactions can be predicted, but there is no explanation for these exclusions and purification.
  • An object of the present invention is to provide an epoch-making production method of azodicarbonamide that is simple, safe and has a reduced environmental burden.
  • the present inventors have conducted intensive research on a simple and efficient method of reacting urea with an active urea derivative and an active structure of urea.
  • active urea under normal pressure is analyzed.
  • Urea represented by formula (1) is represented by formula (10) in a homogeneous system or a heterogeneous mixed system of water or an organic solvent or ionic liquid, and an organic solvent or ionic liquid and water. Since the compound represented by the formula (10) is chemically very active, a de-HBr reaction is immediately generated and converted into the compound of the formula (7). A novel process for producing azodicarbonamide formula (7).
  • Urea represented by the formula (1) is converted into water or an organic solvent or ionic liquid and an organic solvent or a homogeneous system or a heterogeneous mixed system of ionic liquid and water under the acidic condition (9)
  • a compound of formula (10) is obtained by reacting a urea molecule with a bromourea active transition intermediate represented by the formula:
  • Urea represented by the formula (1) can be converted from urea to acidic conditions in a homogeneous or heterogeneous mixed system of water or an organic solvent or ionic liquid, and an organic solvent or ionic liquid and water.
  • N-bromourea represented by the formula (8) is generated by an agent or a bromination method, and then brominated by electrophilic oxidation with an active bromo compound of NH group to which a bromo atom is bonded or a hydrogen peroxide-derived activator.
  • a urea active transition intermediate formula (9) is obtained and at the same time urea molecules react to obtain a compound of formula (10).
  • Urea represented by formula (1) is subjected to chlorination reaction under acidic conditions in a homogeneous or heterogeneous mixed system of water or an organic solvent or ionic liquid, and an organic solvent or ionic liquid and water.
  • the compound of formula (11) is obtained.
  • Monochlorourea of formula (11) (including N-chlorourea Na salt) is subjected to bromination or bromination to obtain N-bromourea represented by formula (8).
  • the bromourea active transition intermediate formula (9) is obtained by electrophilic oxidation with the active bromo compound of NH group to which the bromo atom is bonded or the hydrogen peroxide-derived activator, and at the same time, the urea molecule reacts and the formula (10) A compound is obtained.
  • Urea represented by the formula (1) can be converted from urea to acidic bromine under acidic conditions in a homogeneous or heterogeneous mixed system of water or organic solvent or ionic liquid and organic solvent or ionic liquid and water.
  • N-bromourea represented by the formula (8) is produced by an agent or bromination method, and then electrophilic oxidation of the NH group to which the bromine atom is bonded is electrolyzed and desorbed as a proton by electrolysis, Bromourea active transition intermediate Formula (9).
  • urea molecules react to obtain a compound of formula (10).
  • Item 6 When an electrolytic reaction is used for urea represented by formula (1) in water or an organic solvent or ionic liquid, and an organic solvent or a homogeneous system or a heterogeneous mixed system of ionic liquid and water.
  • a mixture of hydrogen bromide, bromo salt and hydrogen chloride, chloride salt as a supporting electrolyte, two-electron oxidation under acidic conditions to generate a bromo cation to produce N-bromourea represented by formula (8)
  • electrophilic oxidation of the NH group to which the bromo atom is bonded is subjected to two-electron oxidation by an electrolytic reaction and eliminated as a proton to obtain a bromourea active transition intermediate formula (9).
  • urea molecules react to obtain a compound of formula (10).
  • Item 7 The urea represented by the formula (1) is converted from urea to a bromine under acidic conditions in a homogeneous or heterogeneous mixed system of water or an organic solvent or ionic liquid, and an organic solvent or ionic liquid and water.
  • An N-bromourea represented by the formula (8) is produced by a chlorinating agent or a bromination method, or, if necessary, it is represented by the formula (11) from urea by a chlorinating agent or a chlorination method under acidic conditions.
  • Chlorourea (including N-chlorourea Na salt) is produced, then N-bromourea represented by the formula (8) is produced by a brominating agent or bromination method, and then supported using an electrolytic reaction.
  • Urea represented by the formula (1) is hydrogen bromide under acidic conditions in water or an organic solvent or ionic liquid, and an organic solvent or a homogeneous or heterogeneous mixture of ionic liquid and water. Then, bromine is generated by adding a peroxide such as hydrogen peroxide dropwise to a mixture of bromo salt, hydrogen chloride and chloride salt.
  • the urea represented by the formula (1) is generated by the generated bromine, hypobromite, and hypobromite, and the N-bromourea represented by the formula (8) is generated by the two-electron oxidation by the brom cation.
  • the bromourea active transition intermediate formula (9) is obtained by electrophilic oxidation with an active bromo compound of NH group to which a bromo atom is bonded or an active substance derived from hydrogen peroxide, and at the same time, a urea molecule reacts with the formula (10 ) Is obtained.
  • Item 9 The urea represented by the formula (1) is converted into an organic bromide under acidic conditions in a homogeneous system or a heterogeneous mixed system of water, an organic solvent or an ionic liquid, and an organic solvent or an ionic liquid and water.
  • urea is two-electron-oxidized by a brom cation to produce N-bromourea represented by the formula (8), and then a bromine atom is bonded.
  • Bromourea active transition intermediate formula (9) is obtained by electrophilic oxidation with an active bromine compound of NH group or an active substance derived from hydrogen peroxide, and at the same time, urea molecules react to obtain a compound of formula (10).
  • Item 10 In a homogeneous system or heterogeneous mixed system of water or an organic solvent or ionic liquid, and an organic solvent or ionic liquid and water, a halogen acid salt such as hydrogen bromide or hydrogen chloride of urea is used as a raw material Then, chlorine or bromine is generated by dropping a peroxide such as hydrogen peroxide under acidic conditions. Generated and converted chlorine, hypochlorous acid, hypochlorite, bromine, hypobromite, hypobromite, chlorinated and brominated urea represented by formula (1) A novel process for producing an azodicarbonamide according to any one of Items 1 to 9
  • Item 11 A novel method for producing azodicarbonamide formula (7), wherein the method of the corresponding item is taken from the method of Item 1 to Item 10 using a mixture of urea and urea salt as a raw material.
  • Item 13 When a halogen or a halogen compound is used with a peroxide such as hydrogen peroxide as an oxidizing agent, it is stable to water such as cerium compound, vanadium compound, selenium compound, tellurium compound, transition metal compound and aluminum fluoride. 13. A novel process for producing an azodicarbonamide formula (7) according to items 1 to 12, wherein a strong Lewis acid is used as a catalyst and an acid such as formic acid or acetic acid is used.
  • a peroxide such as hydrogen peroxide as an oxidizing agent
  • M represents hydrogen and a monovalent to tetravalent metal selected from the group consisting of Li, Na, K, Mg, Ca, Mn, Fe, Ni, Cu, Ag, Zn, and Sn.
  • X represents a chlorine atom and a bromine atom.
  • m represents an integer of 1 to 4.
  • M is hydrogen, Li, Na, K, Mg, Ca, Ti, Zr, Mn, Fe, Ni, Cu, Ag, Zn, Al, Si, Sn, or other metal ions, in formula (13)
  • the cation portion of the represented compound represents H and ammonium ion, primary ammonium ion, secondary ammonium ion, tertiary ammonium ion, and X is a halogen anion and an organic brominating agent anion.
  • iodine Molecule bromine molecule, chlorine molecule, chlorobromine.
  • the present invention is an efficient production method for directly obtaining the azodicarbonamide represented by the formula (7) from the urea represented by the formula (1) in one step. Since it is carried out in a homogeneous or heterogeneous mixed system of water or an organic solvent or ionic liquid, and an organic solvent or ionic liquid and water, it is a simple, safe and inexpensive production method with a low environmental load. Moreover, since the produced azodicarbonamide is precipitated as a solid, separation and purification are easy. Further, since the aqueous solution containing the compounds represented by formulas (12) to (13), hydrogen halide, or halogen and unreacted urea used in the reaction can be circulated and reused as it is, almost no waste is removed from the system.
  • the urea of formula (1) may be urea hydrochloride, bromate or other salts, and the hydrogen halide or halogen salt used for the halogenation is in an amount relative to the urea to be reacted. is there.
  • the peroxide etc. which are used as an oxidizing agent can be used, since hydrogen peroxide becomes final water, there is no generation of by-products and waste.
  • an electrolysis method if a gas diffusion electrode is used, hydrogen is not generated and power consumption can be suppressed.
  • the present invention relates to a homogeneous or heterogeneous mixture of water or an organic solvent or ionic liquid, and an organic solvent or ionic liquid and water, with or under active conditions of urea or urea salts under acidic conditions.
  • oxidation reaction of bromide compounds and hydrogen peroxide-derived active substances, or by electrolytically oxidizing intermediates of chlorourea and bromourea, by-produced hydrogen halide and halogen salts are recycled and discarded.
  • This is a method for producing an azodicarbonamide having no product, and is represented by the following reaction formula.
  • the chemical reaction is a homogeneous or heterogeneous mixed system of water or an organic solvent or ionic liquid, and an organic solvent or ionic liquid and water.
  • Urea or a salt thereof represented by formula (1) A compound represented by formula (12) under acidic conditions, a chlorinating agent or a brominating agent prepared from the compound represented by formula (13), and replicated hydrogen chloride or chloride salt and hydrogen bromide Alternatively, the hydrogen bromide salt is recycled using an oxidizing agent such as hydrogen peroxide that does not produce by-products.
  • the compound (11) or compound (8) proceeds with an active bromide compound and a hydrogen peroxide-derived activator or by electrolyzing two molecules of urea theoretically by four-electron oxidation.
  • the active bromide compound and the hydrogen peroxide-derived activator include compounds and chemical species known in the art, but are not limited to specific compounds and chemical species.
  • hydrogen chloride, hydrogen bromide, chlorine, bromine, hypochlorous acid, hypochlorous acid and hydrogen peroxide undergo a correlation reaction with each other, resulting in a competitive reaction. These compounds also coordinate with urea to form complexes, complicating the reaction.
  • an active bromine compound is produced.
  • the halogen compound acts on hydrogen peroxide and its active substance under acidic conditions, an active substance derived from hydrogen peroxide is generated.
  • the active bromide compound and / or the hydrogen peroxide-derived activator may be any compound or chemical species that oxidizes bromourea to form a bromourea active transition intermediate, and there are many compounds and chemical species belonging to them. However, it is not particularly limited to a specific compound or chemical species.
  • M represents hydrogen and a monovalent to tetravalent metal selected from the group consisting of Li, Na, K, Mg, Ca, Mn, Fe, Ni, Cu, Ag, Zn, and Sn.
  • X represents a chlorine atom, a bromine atom, or an iodine atom.
  • m represents an integer of 1 to 4.
  • Examples of the compound represented by the formula (12) include hypochlorous acid, lithium hypochlorite, chlorous acid, lithium chlorite, chloric acid, lithium chlorate, perchloric acid, lithium perchlorate, Sodium hypochlorite, sodium chlorite, sodium chlorate, sodium perchlorate, potassium hypochlorite, potassium chlorite, potassium chlorate, potassium perchlorate, calcium hypochlorite, calcium chlorite , Calcium chlorate, calcium perchlorate, magnesium hypochlorite, magnesium chlorite, magnesium chlorate, magnesium perchlorate, hypobromite, lithium hypobromite, bromite, lithium bromite, Bromate, lithium bromate, perbromate, lithium perbromate, sodium hypobromite, sodium bromate, sodium bromate, sodium perbromate , Potassium hypobromite, potassium bromite, potassium bromate, potassium perbromate, calcium hypobromite, calcium bromate, calcium bromate, calcium perbromate, magnesium hypobromite, hypoiodide Acid, lithium
  • the compound represented by the formula (12) can be used for generating an active bromide compound and / or an active form derived from hydrogen peroxide.
  • the active bromide compound includes a compound generated in the reaction system, and examples thereof include a brom cation, a brom cation radical, a brom radical, bromine chloride, a bromine complex (for example, dioxane complex) and the like.
  • the hydrogen peroxide-derived active substance includes compounds generated in the reaction system, such as OH cation, OH radical, OOH radical, singlet oxygen, OOH anion, OOH cation, superoxide, superoxide anion. , Superoxide anion radical, peroxy radical, hydroperoxyl radical and the like.
  • the compound represented by the formula (12) is preferably hypochlorous acid, hypobromite, sodium hypochlorite, sodium chlorate, potassium hypochlorite, potassium chlorate, calcium hypochlorite.
  • M represents a monovalent to tetravalent metal selected from the group consisting of hydrogen, Li, Na, K, Mg, Ca, Mn, Fe, Ni, Cu, Ag, Zn, and Sn. And H And an ammonium ion, a primary ammonium ion, a secondary ammonium ion, a tertiary ammonium ion and a halogen cation, X is a halogen anion and an organic brominating agent anion component, and a bromine molecule, a chlorine molecule, a chloro molecule. Indicates bromine.
  • halogen in X in the formula (13) examples include chlorine, bromine and iodine.
  • Examples of the compound represented by the formula (13) include hydrogen chloride, hydrogen bromide, hydrogen iodide, lithium chloride, sodium chloride, potassium chloride, calcium chloride, copper chloride, magnesium chloride, iron chloride, zinc chloride, and chloride.
  • the compound represented by the formula (13) can be used to generate an active bromide compound and / or an active form derived from hydrogen peroxide. It can be used to generate active bromide compounds and / or hydrogen peroxide derived activators.
  • the active bromide compound includes a compound generated in the reaction system, and examples thereof include a brom cation, a brom cation radical, a brom radical, bromine chloride, a bromine complex (for example, dioxane complex) and the like.
  • the hydrogen peroxide-derived active substance includes compounds generated in the reaction system, such as OH cation, OH radical, OOH radical, singlet oxygen, OOH anion, OOH cation, superoxide anion, superoxide. Anion radical, peroxy radical, hydroperoxyl radical and the like can be mentioned.
  • the compound represented by the formula (13) is preferably hydrogen chloride, hydrogen bromide, lithium chloride, sodium chloride, potassium chloride, calcium chloride, magnesium chloride, zinc chloride, iron chloride, copper chloride, lithium bromide, Sodium bromide, potassium bromide, calcium bromide, magnesium bromide, zinc bromide, copper bromide, lithium iodide, sodium iodide, potassium iodide, copper iodide, ammonium chloride, ammonium bromide, chlorine, bromine , Iodine, chlorobromine, dibromoisocyanuric acid, N-bromosuccinimide and the like, but are not particularly limited to these compounds.
  • halogen in X in the formula (13) examples include fluorine, chlorine, bromine and iodine.
  • examples of the hydrogen halide include hydrogen chloride, hydrogen bromide, and hydrogen iodide.
  • examples of the halogen include chlorine, bromine, and iodine.
  • highly stable strong Lewis acids as catalysts and the use of acids such as formic acid and acetic acid are effective.
  • the invention is not particularly limited to this.
  • urea as a raw material is contained at a concentration of 0.5 to 50 mol / L in a homogeneous system or a heterogeneous mixed system with water or an organic solvent or ionic liquid, and an organic solvent or ionic liquid.
  • concentration is preferably 2 to 30 mol / L.
  • the invention is not particularly limited to this.
  • the concentration of urea is influenced by the solubility with respect to temperature and the ratio of bromine-based oxidant, but basically, the presence of a high concentration and a large amount of urea is preferable.
  • the molar ratio of a compound such as a halogen-based oxidant to urea is preferably such that when the active intermediate transition compound bromourea cation (compound 9) is formed, its surroundings are enveloped with urea.
  • the compound such as halogen-based oxidizing agent is 0.01 to 0.45 molar ratio, but preferably 0.05 to 0.3 molar ratio. Hydrogen peroxide, a substantial oxidant, corresponds to these numbers. However, it is not particularly limited to this.
  • the series of reactions of the present invention does not require separation of intermediates. If necessary, the compounds represented by the formulas (8) and (11) can be separated and stored, and can be used as raw materials for other derivatives.
  • the temperature of the series of reactions of the present invention is too low for converting halogen anions to halogen molecules, halogen cations, active halogen species with an oxidizing agent such as hydrogen peroxide, and for the production of hydrogen peroxide active substances.
  • an oxidizing agent such as hydrogen peroxide
  • the reaction is carried out at ⁇ 200 to 100 ° C., preferably ⁇ 10 to 70 ° C. It is desirable to adjust the temperature according to the reaction conditions in view of the stability and reactivity of the reaction intermediate and reaction active intermediate.
  • an aqueous solution of urea has a significantly reduced freezing point.
  • the electrolytic method When the electrolytic method is applied to the intermediate, it is desirable to react at a low temperature in order to decompose the active intermediate and suppress side reactions from the heat generated during electrolysis.
  • the reaction is carried out at ⁇ 50 to 100 ° C., preferably ⁇ 20 to 40 ° C. It is also possible to carry out the reaction at a low temperature.
  • the reaction can be performed at a low temperature even in a homogeneous mixed system with an organic solvent or an ionic liquid.
  • the invention is not particularly limited to this.
  • organic solvent examples include halogen solvents such as dichloroethane, carbon tetrachloride, and chlorobenzene, and chain or cyclic alkanes such as n-pentane, n-hexane, cyclopentane, and cyclohexane, Ethers such as tetrahydrofuran, 1,2-dimethoxyethane, dioxane, methyl-t-butyl ether and methylcyclopentyl ether, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, cyclopentanone and cyclohexanone, methyl
  • halogen solvents such as dichloroethane, carbon tetrachloride, and chlorobenzene
  • chain or cyclic alkanes such as n-pentane, n-hexane, cyclopentane, and cycl
  • an ionic liquid you may have imidazolium which may have a substituent, quaternary ammonium, pyridinium which may have a substituent, phosphonium, and a substituent as a cation component.
  • Pyrrolidiniums, sulfoniums, anion components such as boron tetrafluoride, phosphorus hexafluoride, trifluoroacetic acid, trifluoromethanesulfonic acid, bistrifluoromethanesulfonimide, alkylsulfonic acid, acetic acid, nitric acid, chlorine, bromine
  • the ionic liquid include salts of these cationic components and anionic components.
  • the use of water, an organic solvent, or an ionic liquid alone may be used. A combination of these may also be used.
  • the solution containing urea may be a homogeneous phase or a heterogeneous phase (liquid phase separation state).
  • a mixed solvent of water and an organic solvent in the case of a heterogeneous system, the raw materials and various reagents are mainly dissolved in the aqueous layer. In addition, various reagents are mainly dissolved.
  • urea and salts do not dissolve at all, it is important that urea and salts are dispersed in the solvent as fine particles as possible.
  • the halogenating agent is a hydrogen halide or halogen salt after the reaction, but it is regenerated to a halogen with a peroxide such as hydrogen peroxide, so when using hydrogen peroxide in particular,
  • a peroxide such as hydrogen peroxide
  • the oxidation by-product is a small amount of water, and it is not necessary to adjust the liquid composition from the accumulation of by-products generated in minute amounts to the limit of recycling.
  • this electrolytic reaction may be constant voltage electrolysis or constant current electrolysis.
  • any method of a non-diaphragm, a diaphragm, and an ion exchange membrane is possible as an electrolysis method.
  • a metal electrode, a carbon electrode, and a composite electrode thereof can be used as the anode in the electrolysis of the present invention.
  • noble metals such as gold, silver, platinum and ruthenium and minor metals such as titanium, chromium, nickel and manganese, and electrodes coated with noble metals other than noble metals such as titanium, stainless steel, iron and hastelloy And electrodes coated with precious metals on substrates other than metals such as olefin resins, engineering resins, carbon-based substrates, composite coated electrodes of metal oxides such as iridium oxide and ruthenium oxide and platinum, and coatings similar to the above with minor metals An electrode etc. are mentioned.
  • examples of the carbon-based electrode include carbon-based electrodes such as carbon, glassy carbon, graphite, graphene, carbon sheet, carbon fiber sheet, carbon fiber cloth, diamond-like coated electrode, and composite electrodes thereof.
  • the anode is an electrode in which platinum is coated on a metal substrate other than a noble metal such as platinum, titanium, titanium, stainless steel, iron, or hastelloy, and a substrate other than a metal such as an olefin resin, an engineering resin, or a carbon-based substrate.
  • Electrode coated with platinum composite electrode of platinum with metal oxide such as iridium oxide and ruthenium oxide, and carbon, glassy carbon, graphite, graphene, carbon sheet, carbon fiber sheet, carbon fiber cloth, diamond-like coated electrode Carbon-based electrodes such as these, and composite electrodes thereof, but are not particularly limited thereto.
  • the cathode is not particularly limited, and the materials exemplified as the anode electrode and general-purpose metals such as iron, copper, and aluminum, and stainless steel, hastelloy, various alloys, and composite electrodes thereof can be used.
  • Preferred as the cathode are platinum, stainless steel, titanium, stainless steel, hastelloy, iron, and electrodes in which platinum is coated on a metal base other than noble metal such as titanium, stainless steel, iron, hastelloy, olefin resin, engineering resin, carbon-based group Electrode with platinum coated on base material other than metal such as metal, and composite coated electrode of metal oxide such as iridium oxide and ruthenium oxide and platinum and carbon, glassy carbon, graphite, carbon sheet, carbon fiber sheet, carbon fiber Although it is carbon-type electrodes, such as cloth, these composite electrodes, etc., it is not specifically limited to these.
  • the shape of the electrode a plate shape, a cloth shape, a comb shape, a pipe shape, a nonwoven fabric shape, a shape obtained by a paper-making method, a felt shape, etc. can be used. Processed products can be used.
  • the anode has a shape without a gap and the cathode has a shape with a hole or a gap.
  • the shape of the cathode is not limited. In particular, it is not limited to these.
  • the electrolysis of the present invention is carried out in a state where the current density is kept constant at 1 to 20,000 mA / cm 2 , preferably 10 to 5000 mA / cm 2 .
  • the electrode potential is set to 0.5 to 100 V vs. Ag / AgCl, preferably 1 to 70 V vs. Although it can hold
  • the reaction temperature is preferably ⁇ 40 to 100 ° C.
  • the temperature is preferably ⁇ 20 to 70 ° C., but is not particularly limited thereto. It is desirable to adjust the temperature according to the reaction conditions in view of the stability and reactivity of the reaction intermediate and reaction active intermediate. In a homogeneous mixed system with an organic solvent or ionic liquid, the reaction can be performed at a lower temperature.
  • Reactivity in this reaction ease of formation of active intermediate, promotion of reactivity of active intermediate with urea, suppression of decomposition of active intermediate, generation of oxidized active species for formation of intermediate, 2 electrons Reactions under acidic conditions are desirable for promoting oxidation and suppressing side reactions such as Hoffman transition.
  • the acid added for the acidic condition may be mineral products such as hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, and organic acids such as acetic acid, propionic acid, citric acid.
  • the buffer solution which is a mixture with those salts may be sufficient.
  • Reference example 1 In a reaction vessel equipped with a stirrer and a thermometer, 75 g (1.25 mol) of urea is dissolved in 150 ml of water, and 321 ml (1.25 mol) of a 29% sodium hypochlorite aqueous solution is added dropwise at 10 ° C. over 1 hour with stirring. A sample is taken, potassium iodide and acetic acid (1: 1) are added, and 0.1N-sodium thiosulfate titration is immediately performed. As a result of titration analysis, it was confirmed that the yield of monochlorourea was 98.4%. When ultraviolet analysis was performed, absorption at 244 nm peculiar to monochlorourea was observed.
  • Reference example 3 Monochlorourea produced in Reference Example 1 is separated by crystals when concentrated under reduced pressure. Dissolve 31.5 g (0.33 mol) of monochlorourea in 100 ml of water, add 80 ml of 8% hydrochloric acid, add 34 g (0.33 mol) of sodium bromide, and add 30 ml of 30% hydrogen peroxide at 50 ° C. with stirring. (0.33 mol) is added dropwise over 1 hour. After completion of the dropwise addition, the reaction is terminated by stirring for another 30 minutes. When the sample was collected and subjected to ultraviolet analysis, the absorption at 275 nm characteristic of monobromourea was shown.
  • Example 1-1 In a 500 ml round bottom flask equipped with a magnetic stir bar, dropping funnel and thermometer, 90 g (1.5 mol) of urea was dissolved in 100 ml of water, followed by cooling to 5 ° C. under cooling at 5 ° C. 17 .1 g of 32% HCl (0.15 mol) was added with stirring. Adjust the addition amount of 32% HCl so that the pH of the solution is 1. To the solution was added 133 g of 10.7% NaOCl aqueous solution (wt% as active Cl 2 , 0.2 mol) over 14 minutes upon cooling. After stirring for 1 hour after completion of the addition, 20.5 g of NaBr (0.2 mol) was added to the solution.
  • the temperature of the reaction solution is raised to 35 ° C. and stirred for 1 hour, then 79.3 g (0.7 mol) of 30% hydrogen peroxide is divided into two, and the first half is added dropwise over 30 minutes. Stir for 1 hour, then drop the remaining half in 30 minutes.
  • the reaction is terminated by stirring for 5 hours. As the reaction progresses, a yellow solid is formed and becomes suspended in the reaction solution. After completion of the reaction, the solid is separated by filtration, washed with water and dried.
  • the obtained azodicarbonamide was identified by infrared absorption spectrum (IR) and proton nuclear magnetic resonance spectrum ( 1 H-NMR).
  • Example 1-2 In a 500 ml round bottom flask equipped with a magnetic stir bar, dropping funnel and thermometer, 90 g (1.5 mol) of urea was dissolved in 300 ml of water, followed by cooling to 0 ° C. under cooling at 0 ° C. 22 0.5 g of 35% hydrochloric acid (0.22 mol) was added with stirring. Further, the solution was adjusted with 35% hydrochloric acid so that the pH was 1. To the solution was added 19.6 g ammonium bromide (0.2 mol) and 23.5 g NaCl (0.4 mol).
  • Example 1-5 In a 500 ml round bottom flask equipped with a magnetic stir bar, dropping funnel and thermometer, 90 g (1.5 mol) of urea was dissolved in 300 ml of water, followed by cooling to 0 ° C. under cooling at 0 ° C. 22 0.5 g of 35% hydrochloric acid (0.22 mol) was added with stirring. Further, the solution was adjusted with 35% hydrochloric acid so that the pH was 1. To the solution were added 1.96 g ammonium bromide (0.02 mol) and 23.5 g NaCl (0.4 mol).
  • azodicarbonamide was identified by infrared absorption spectrum (IR) and proton nuclear magnetic resonance spectrum ( 1 H-NMR). The yield of azodicarbonamide from the consumed urea was 94.1%.
  • IR KBr
  • 3337,3187cm -1 N-H stretching
  • 1637cm -1 N-H bending
  • 1 H-NMR (D6-DMSO) ⁇ 8.02 (s, 2H, NH), 7.97 (s, 2H, NH).
  • Example 15-26 The first oxidant is converted from sodium hypochlorite to bromine, bromide and bromate in amounts considerably smaller than the theoretical amount, and reacted first, and then hydrogen peroxide is added to form hydrogen bromide. Except for using 2 times the amount of hydrogen peroxide corresponding to recycling reaction of bromine, bromide or bromate after converting the product to bromine or bromic acid or bromate, the same as Example 1-3 The reaction and treatment were carried out.
  • Example 1-1 an oxidizing agent such as sodium hypochlorite that is the first oxidizing agent is not used, but a small amount of NaBr is added first, and the amount is equivalent to twice the number of moles of dissolved total chloranion.
  • the hydrogen peroxide to be added is reacted and treated to separate the produced azodicarbonamide, the mother liquor and the washing solution of the azodicarbonamide isolate are combined, the consumed urea is added, and NaBr is
  • the recycling reaction is performed while adjusting the composition by adding these.
  • water is removed using a membrane or the like. Other reactions and treatments are carried out in the same manner as in Example 1-1.
  • Example 32 Urea (1.2 g, 20 mmol), sodium bromide (41 mg, 0.4 mmol), cooled to 5 ° C. in a beaker-type electrolytic cell equipped with two platinum plate electrodes (1.5 ⁇ 1.0 cm 2 ). 0.34 mg of 32% HCl (0.3 mmol) and water (2.0 g) were weighed and stirred to obtain a homogeneous solution. While the electrolytic cell was immersed in an ice-water bath and cooled, electrolysis was performed for 10.7 hours while keeping the current constant at 100 mA, and 5778 coulombs of electricity was applied.
  • Example 33 Electrolysis was carried out in the same manner as described in Example 32 using the monobromourea produced in Reference Example 3 as a raw material instead of the urea in Example 32.
  • 213 mg of azodicarbonamide was obtained.
  • the yield is 92.0%.
  • the electrolysis reaction is carried out with half the energizing time and the energizing electricity.
  • a solid form of azodicarbonamide is formed.
  • the suspension was filtered, washed with water and dried under reduced pressure.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

　L'invention concerne un procédé de production d'azodicarbonamide économique, sûr et plus respectueux de l'environnement. Selon la présente invention, dans un système homogène ou un système miscible hétérogène d'eau ou de solvant organique ou de solution ionique, et d'un solvant organique et/ou d'une solution ionique et d'eau, de l'azodicarbonamide est produit en utilisant du peroxyde d'hydrogène dans de l'urée et en faisant réagir du chlore actif ou des ions de chlore actifs et un composé de brome actif tel que le brome actif ou des ions brome actif et/ou une forme active dérivée d'un peroxyde d'hydrogène, ou en oxydant électrolytiquement un intermédiaire de la manière souhaitée afin d'obtenir une cible, et en recyclant et en utilisant les sous-produits réactionnels.
PCT/JP2015/075926 2014-09-12 2015-09-11 Nouveau procédé de production d'azodicarbonamide Ceased WO2016039466A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201580049311.XA CN106795105B (zh) 2014-09-12 2015-09-11 偶氮二甲酰胺的新型制造方法
JP2016547809A JP6165349B2 (ja) 2014-09-12 2015-09-11 アゾジカルボンアミドの新規製造法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014074315 2014-09-12
JPPCT/JP2014/074315 2014-09-12

Publications (1)

Publication Number Publication Date
WO2016039466A1 true WO2016039466A1 (fr) 2016-03-17

Family

ID=55459209

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/075926 Ceased WO2016039466A1 (fr) 2014-09-12 2015-09-11 Nouveau procédé de production d'azodicarbonamide

Country Status (3)

Country Link
JP (1) JP6165349B2 (fr)
CN (1) CN106795105B (fr)
WO (1) WO2016039466A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102019111060A1 (de) * 2019-04-29 2020-10-29 Rheinisch-Westfälische Technische Hochschule (Rwth) Aachen Katalysatoren für die katalytische Synthese von Harnstoff
CN118530146A (zh) * 2024-05-31 2024-08-23 中国天辰工程有限公司 一种偶氮二甲酰胺的制备方法
CN119059940A (zh) * 2024-07-17 2024-12-03 中国天辰工程有限公司 一种偶氮二甲酰胺的制备方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4886822A (fr) * 1972-02-23 1973-11-15
JPS5217424A (en) * 1975-07-31 1977-02-09 Ugine Kuhlmann Process for manufacturing azodicarbonamides from hydrazines
JPS52133924A (en) * 1976-04-28 1977-11-09 Otsuka Chem Co Ltd Preparation of azodicarbonamides
JPS5398926A (en) * 1977-02-09 1978-08-29 Otsuka Chem Co Ltd Preparation of azodicarbonamides
JP2002080448A (ja) * 2000-08-31 2002-03-19 Eiwa Kasei Kogyo Kk ヒドラゾジカルボンアミドの精製方法
JP2002080449A (ja) * 2000-07-19 2002-03-19 Bayer Ag ケチミンを経由したヒドラゾジカーボンアミド（ｈｄｃ）の製造方法
WO2012147953A1 (fr) * 2011-04-28 2012-11-01 大塚化学株式会社 Nouveau procédé de production d'azodicarbonamide
JP2013540743A (ja) * 2010-09-21 2013-11-07 ブロミン・コンパウンズ・リミテツド ブロモ尿素の調製方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1008557B1 (fr) * 1997-08-11 2007-12-26 Ebara Corporation Procede et appareil d'electrolyse hydrothermale
JP2004043900A (ja) * 2002-07-12 2004-02-12 Permelec Electrode Ltd 過酢酸の電解合成方法
GB0918616D0 (en) * 2009-10-23 2009-12-09 3M Innovative Properties Co Method of preparing highly fluorinated carboxylic acids and their salts

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4886822A (fr) * 1972-02-23 1973-11-15
JPS5217424A (en) * 1975-07-31 1977-02-09 Ugine Kuhlmann Process for manufacturing azodicarbonamides from hydrazines
JPS52133924A (en) * 1976-04-28 1977-11-09 Otsuka Chem Co Ltd Preparation of azodicarbonamides
JPS5398926A (en) * 1977-02-09 1978-08-29 Otsuka Chem Co Ltd Preparation of azodicarbonamides
JP2002080449A (ja) * 2000-07-19 2002-03-19 Bayer Ag ケチミンを経由したヒドラゾジカーボンアミド（ｈｄｃ）の製造方法
JP2002080448A (ja) * 2000-08-31 2002-03-19 Eiwa Kasei Kogyo Kk ヒドラゾジカルボンアミドの精製方法
JP2013540743A (ja) * 2010-09-21 2013-11-07 ブロミン・コンパウンズ・リミテツド ブロモ尿素の調製方法
WO2012147953A1 (fr) * 2011-04-28 2012-11-01 大塚化学株式会社 Nouveau procédé de production d'azodicarbonamide

Also Published As

Publication number Publication date
JP6165349B2 (ja) 2017-07-19
CN106795105A (zh) 2017-05-31
JPWO2016039466A1 (ja) 2017-04-27
CN106795105B (zh) 2019-11-15

Similar Documents

Publication Publication Date Title
EP2054341B1 (fr) Procédés d'oxydation de bromures pour produire du brome et des catalyseurs utiles
KR20150056627A (ko) 이산화탄소로부터 카복실산을 생산하기 위한 통합 공정
CN111732520B (zh) 一种3-甲基-2-氨基苯甲酸的制备方法
WO2007125975A1 (fr) Procédé de production de 1,2,3,4-tétrachlorohexafluorobutane
JP6165349B2 (ja) アゾジカルボンアミドの新規製造法
JP2005515145A (ja) 無害な臭素化試薬の製造
US11339052B2 (en) Method for manufacturing sulfur tetrafluoride
CN103360316A (zh) 一种氟虫腈的制备方法
CN110753679A (zh) 形成氯丙醇和环氧丙烷的方法和系统
CN100398500C (zh) 一种生态友好的溴苯合成方法
CN106432069A (zh) 一种2‑氨基‑5‑氯‑吡啶的制备方法
JP5378205B2 (ja) ハロゲン化カルボニル基含有化合物の電気化学的調製方法
Raju et al. Electrochemical chlorination of toluene by two-phase electrolysis
JPH0238573B2 (fr)
JP3564979B2 (ja) パーフルオロアルキルカルボン酸の製造方法
JP2604826B2 (ja) １級アルコールからアルデヒドへの高選択的酸化方法
JP5637729B2 (ja) 一塩化ヨウ素水溶液の製造方法
JPWO2010104028A1 (ja) 電気分解を利用した芳香族ハロゲン化合物の製造方法
Sharma et al. NH4Br–Br2 Catalysed Oxidative Bromination of Aromatic Compounds
CN101443481B (zh) 制备含卤代羰基的化合物的电化学方法
IL217393A (en) A method of producing iodine added material
CN107827725B (zh) 一种制备α-单溴代芳香酮的方法
RU2601752C1 (ru) Способ бромирования ксилолов в кольцо
JP5572421B2 (ja) ３，５−ジ−ｔｅｒｔ−ブチルハロゲノベンゼンの製造方法
JP2005272324A (ja) ３−ホルミル−５−トリフルオロメチルベンゾニトリル誘導体とその製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15840196

Country of ref document: EP

Kind code of ref document: A1

DPE2 Request for preliminary examination filed before expiration of 19th month from priority date (pct application filed from 20040101)
ENP Entry into the national phase

Ref document number: 2016547809

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15840196

Country of ref document: EP

Kind code of ref document: A1