WO2012176631A1 - Procédé de production d'un composé isocyanate contenant un groupe éthyléniquement insaturé - Google Patents

Procédé de production d'un composé isocyanate contenant un groupe éthyléniquement insaturé Download PDF

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WO2012176631A1
WO2012176631A1 PCT/JP2012/064785 JP2012064785W WO2012176631A1 WO 2012176631 A1 WO2012176631 A1 WO 2012176631A1 JP 2012064785 W JP2012064785 W JP 2012064785W WO 2012176631 A1 WO2012176631 A1 WO 2012176631A1
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group
ethylenically unsaturated
isocyanate compound
unsaturated group
producing
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PCT/JP2012/064785
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English (en)
Japanese (ja)
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智光 加藤
大野　勝俊
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昭和電工株式会社
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Priority to JP2012546656A priority Critical patent/JP5165815B2/ja
Publication of WO2012176631A1 publication Critical patent/WO2012176631A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C263/00—Preparation of derivatives of isocyanic acid
    • C07C263/04—Preparation of derivatives of isocyanic acid from or via carbamates or carbamoyl halides

Definitions

  • the present invention relates to a method for producing an ethylenically unsaturated group-containing isocyanate compound. More specifically, the present invention relates to a method for producing an ethylenically unsaturated group-containing isocyanate compound by thermal decomposition of a trisubstituted urea compound, at least one of which is a substituent having an ethylenically unsaturated bond.
  • Such monomer compounds having an unsaturated group and an isocyanate group in the molecule are coating materials, ultraviolet curable coatings, thermosetting coatings, molding materials, adhesives, inks, resists, optical materials, stereolithography materials, and printing plate materials. It is useful as a raw material monomer for resins used in fields such as dental materials and polymer battery materials.
  • Japanese Patent Application Laid-Open No. 2006-232797 (Pamphlet of International Publication No. 2005/092842; Patent Document 1) and Japanese Patent Application Laid-Open No. 2007-55993 (Pamphlet of International Publication No. 2006/049264; Patent Document) 2) discloses a method for producing a compound having an ethylenically unsaturated group and an isocyanate group in the molecule by synthesizing carbamic acid chloride using an amine derivative and phosgene as a reaction raw material and further thermally decomposing them. .
  • Patent Document 1 and Patent Document 2 are widely used industrially.
  • toxic phosgene is used as a raw material, it is necessary to be careful in management, and the generated hydrogen chloride is Since by-products added to the ethylenically unsaturated double bond are formed, it is necessary to distill through zinc chloride, activated carbon, silicic acid catalyst, etc., or a complicated step of dehydrochlorination using an equivalent amount of base is required. Therefore, development of an alternative manufacturing method is desired.
  • JP-A-6-263712 discloses a method for producing an isocyanate group-containing ester compound that is thermally decomposed at a temperature of 100 to 160 ° C. using an organotin catalyst. There is a problem that is low.
  • Japanese Patent Laid-Open No. 10-182484 discloses silylation of the nitrogen position of ethylenically unsaturated urethane using a silylation aid and the obtained ethylenic unsaturated compound.
  • a method for decomposing saturated N-silyl-urethane at a temperature of 70 to 120 ° C. is disclosed, trimethylchlorosilane used as a silylating agent is highly sensitive to moisture and reacts violently with water. It has to be handled in an inert gas such as argon and has a drawback that it is difficult to use as an industrial raw material.
  • JP-A-55-33480 U.S. Pat. No. 4,223,145; Patent Document 5
  • JP-A-03-48651 European Patent No. 0408277; Patent Document 6
  • JP-A-55-33480 U.S. Pat. No. 4,223,145; Patent Document 5
  • JP-A-03-48651 European Patent No. 0408277; Patent Document 6
  • JP-A-55-33480 U.S. Pat. No. 4,223,145; Patent Document 5
  • JP-A-03-48651 European Patent No. 0408277
  • Patent Document 6 disclose trisubstituted ureas.
  • JP 2006-232797 A (Pamphlet of International Publication No. 2005/092842) JP 2007-55993 A (Pamphlet of International Publication No. 2006/049264) JP-A-6-263712 Japanese Patent Laid-Open No. 10-182484 (US Pat. No. 5,990,345) JP 55-33480 A (US Pat. No. 4,223,145) JP-A-3-48651 (European Patent No. 0408277)
  • An object of the present invention is to provide a method for producing an ethylenically unsaturated group-containing isocyanate compound without using phosgene as a raw material in view of the problems of the prior art, wherein hydrogen chloride is an ethylenically unsaturated double bond. It is an object of the present invention to provide a production method capable of obtaining an ethylenically unsaturated group-containing isocyanate compound in a high yield, in which the formation of by-products added to the polymer and the polymerization reaction of double bonds are suppressed.
  • the inventors of the present invention have used hydrogen chloride in which a trisubstituted urea compound, at least one of which has an ethylenically unsaturated bond, is used in the presence of hydrogen chloride gas.
  • hydrogen chloride gas By pyrolysis under specific conditions in which the gas precipitates as amine hydrochloride, ethylene by which hydrogen chloride is added to the ethylenically unsaturated double bond can be greatly reduced and no dehydrochlorination step is required.
  • the present inventors have found a method capable of stably obtaining a polymerizable unsaturated group-containing isocyanate compound in a high yield, and have completed the present invention.
  • the present invention includes the following matters.
  • [1] (i) The following general formula (1) at a temperature of 50 to 200 ° C. (Wherein R 0 represents an ethylenically unsaturated group, R 2 and R 3 each independently represents an optionally branched alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 8 carbon atoms)
  • (Iii) A method for producing an ethylenically unsaturated group-containing isocyanate compound, characterized by further comprising a step (aging step B) of maintaining the temperature after completion of the aging step A.
  • the trisubstituted urea compound represented by the general formula (1) is represented by the general formula (2) (In the formula, m is 1 or 2, X represents an alkylene group which may be substituted with a single bond or an alkyl group having 1 to 4 carbon atoms when m is 1, and when m is 2, Represents a methine group which may be substituted with an alkyl group having 1 to 4 carbon atoms, R 1 represents a hydrogen atom or a methyl group, R 2 and R 3 represent the same meaning as in the above item [1], and Z represents (1) an alkyl group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 1 to 5 carbon atoms, or an alkylene group having 1 to 4 carbon atoms which may be substituted with a phenyl group, and (2) an ether bond.
  • a good alkylene group having 1 to 12 carbon atoms, (3) an arylene group having 6 to 15 carbon atoms, or (4) —C 6 H 4 —CH 2 — or —C 6 H 4 —C 2 H 4 — n is 0 or 1.
  • the method for producing an ethylenically unsaturated group-containing isocyanate compound according to any one of items [1] to [3], wherein the isocyanate compound represented by the formula: [5] The process for producing an ethylenically unsaturated group-containing isocyanate compound as described in any one of [1] to [4] above, wherein a solvent to which a polymerization inhibitor is added is used.
  • the polymerization inhibitor is selected from the group consisting of 2,6-di-t-butyl-4-hydroxytoluene, phenothiazine, and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl
  • m represents 1, X represents a methine group substituted with a single bond or a methyl group, and Z represents a methylene group optionally substituted with a phenyl group An ethylene group optionally substituted with a phenyl group, a propylene group optionally substituted with two methyl groups or two ethoxycarbonyl groups, a butylene group optionally containing an ether bond, a phenylene group, or a methylenephenyl group.
  • R 2 and R 3 in formula (2) each independently represents a methyl group or an ethyl group.
  • a highly polymerizable ethylenically unsaturated group-containing isocyanate compound can be produced in a high yield by a thermal decomposition reaction of a trisubstituted urea compound having an ethylenically unsaturated bond. Since the production method of the present invention does not use toxic phosgene as a raw material and can significantly reduce the by-product of adding hydrogen chloride to an ethylenically unsaturated double bond, a complicated processing step is unnecessary, and environmental and safety. Easy management.
  • the ethylenically unsaturated group-containing isocyanate compound obtained by the production method of the present invention has an ethylenically unsaturated double bond and an isocyanate group in the same molecule, other unsaturated compounds such as methyl methacrylate and methyl acrylate
  • a functional polymer material having an isocyanate group can be produced by copolymerization with (meth) acrylates such as styrene or the like.
  • an electronic material in which a monomer, oligomer or polymer having an active hydrogen such as hydroxyl group, amino group or carboxyl group is reacted with an isocyanate group to introduce an unsaturated bond and cured by ultraviolet rays, electron beams, heat, etc.
  • Materials resist, pressure-sensitive adhesive, film, etc.
  • the target compound is obtained by thermal decomposition.
  • the compounds represented by all general formulas in this specification include all stereoisomers such as cis and trans.
  • R 0 represents an ethylenically unsaturated group, preferably an acryloyloxyethyl group, a methacryloyloxyethyl group, an acryloyloxyethyloxyethyl group, a methacryloyloxyethyloxyethyl group or a bisacryloyloxymethyl group
  • R 2 and Each R 3 independently represents an optionally branched alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 8 carbon atoms, preferably a methyl group or an ethyl group.
  • R 2 and R 3 may be the same or different.
  • the trisubstituted urea compound is preferably a compound represented by the general formula (2).
  • m is 1 or 2
  • X represents an alkylene group which may be substituted with a single bond or an alkyl group having 1 to 4 carbon atoms when m is 1, and when m is 2, carbon This represents a methine group optionally substituted with an alkyl group of 1 to 4, and a methine group substituted with a single bond or a methyl group is preferred.
  • R 1 represents a hydrogen atom or a methyl group.
  • R 2 and R 3 represent the same meaning as described above.
  • Z represents (1) an alkyl group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 1 to 5 carbon atoms, or an alkylene group having 1 to 4 carbon atoms which may be substituted with a phenyl group, and (2) an ether bond.
  • n is 0 or 1.
  • the compound represented by the general formula (2) can be produced by a conventionally known method, but a commercially available product may be used.
  • known production methods for example, JP-A-60-87254 and JP-A-2009-229499 disclose N-methyl-N ′-(1-methyl-1-phenyl-3-butenyl-N— ( A method for obtaining 1-phenylethyl) urea and 2- (N, N-diethylureido) ethyl methacrylate is disclosed, and a commercially available product is, for example, sold by MP Biomedical. And N-allyl-N′-ethylurea.
  • Ethylenically unsaturated group-containing isocyanate compound having an isocyanate group and at least one ethylenically unsaturated bond in the molecule obtained by the production method of the present invention is obtained from a trisubstituted urea compound represented by the general formula (1).
  • R 0 —NCO obtained, preferably represented by the following general formula (3).
  • the symbols in the formula have the same meaning as described above.
  • the compound represented by the general formula (3) is not particularly limited, but preferred specific examples include 2-propylene isocyanate (compound 1), 1-phenyl-2-propylene isocyanate (compound 2), 4 , 4-dimethylpentene-5-isocyanate (compound 3), 2,4,4-trimethylpentene-5-isocyanate (compound 4), 3,3-dimethylpentene-5-isocyanate (compound 5), 2-allyl- 2-isocyanatomethyl-malonic acid diethyl ester (compound 6), 1-phenyl-3-methyl-3-butene isocyanate (compound 7), 4-vinylbenzene isocyanate (compound 8), 2-methacryloyloxyethyl isocyanate (compound 9) ), 1-isocyanatomethyl-4-vinyl-benzene (compound 10), 2-acryloyloxyethyl isocyanate (compound 11), 2- (2-methacryloyloxyethyloxy) e
  • Table 1 shows the relationship between the preferable compounds 1 to 14 and the general formula (3).
  • the compound represented by the general formula (4) is one of the intermediates of the production method of the present invention (hereinafter, the compound represented by the general formula (4) may be abbreviated as a production intermediate). .)
  • the production intermediate obtained by the production method according to the present invention is not particularly limited, but as a preferred specific example, a compound represented by the following formula (5) (production intermediate of 2-acryloyloxyethyl isocyanate)
  • an intermediate (by-product) of the production method according to the present invention there is a biuret obtained by reacting the trisubstituted urea and isocyanate in addition to the compound represented by the general formula (4), and also includes an ester bond.
  • an ester decomposition product generated by ester decomposition in the presence of an acidic substance (hydrogen chloride) is also mentioned as a by-product.
  • the method for producing an ethylenically unsaturated group-containing isocyanate compound of the present invention comprises: (I) a step (thermal decomposition step) of subjecting the trisubstituted urea compound represented by the general formula (1) to a thermal decomposition reaction in a solution containing hydrogen chloride at a predetermined temperature; (Ii) after completion of the thermal decomposition step, a step of blowing hydrogen chloride gas into the reaction solution maintained at the temperature (aging step A); (Iii) After completion of the aging step A, a step of holding at the temperature (aging step B) is further included.
  • Thermal decomposition process It is preferable to perform a thermal decomposition process by dripping the solution of a trisubstituted urea compound, blowing hydrogen chloride gas in the solvent hold
  • the amount of hydrogen chloride gas used in the pyrolysis step is usually 0.2 to 4.0 molar equivalents, preferably 0, of hydrogen chloride gas per mole of trisubstituted urea compound by the end of the reaction.
  • the amount is from 5 to 2.0 molar equivalents, more preferably from 1.0 to 2.0 molar equivalents.
  • the solvent used in the pyrolysis step the solvent in which hydrogen chloride gas is blown and the raw material trisubstituted urea compound solution is added dropwise, and the raw material trisubstituted urea compound solution solvent
  • the hydrogen chloride blown in is not limited. What precipitates the salt (amine hydrochloride) of gas and the decomposition product (amine compound) of a trisubstituted urea compound is preferable.
  • xylene, toluene, ethylbenzene, dichlorobenzene, chlorobenzene, decane, and undecane are preferable because they are easily available.
  • the amount of solvent used is usually 0.2 to 10.0 L, preferably 0.5 to 8.0 L, more preferably 1.0 to 5.0 L with respect to 1 mole of the trisubstituted urea compound. .
  • the side reaction rate such as ester decomposition becomes faster due to the increase in concentration, so that the yield decreases.
  • stirring is hindered by the generated salt, which may cause a reduction in reaction efficiency.
  • the amount of the solvent used is large, the reaction rate may be remarkably reduced due to a decrease in concentration.
  • a polymerization inhibitor may be used to avoid polymerization reaction.
  • the polymerization inhibitor is not particularly limited, but phenol, hydroquinone, p-methoxyphenol, hydroquinone monomethyl ether, t-butylcatechol, 2,6-di-t-butylhydroxytoluene (BHT), cresol, Catechol, 2,5-di-t-butylhydroquinone, 2,6-di-t-butylphenol, 6-t-butyl-m-cresol, 2,6-di-t-butyl-p-cresol, 4-t -Phenols such as butylcatechol, 2,4-dimethyl-6-t-butylphenol, 2-t-butylhydroquinone, 2-t-butyl-4-methoxyphenol, benzoquinone, 1,2-naphthoquinone, phenothiazine, methylene blue, 4-Hydroxy-2,2,6,6
  • the amount of the polymerization inhibitor used is 500 to 10000 mass ppm, preferably 1000 to 8000 mass ppm, more preferably 2000 to 6000 mass ppm, and particularly preferably 3000 to 5000 ppm by mass with respect to the reaction solvent.
  • the amount of the polymerization inhibitor used is small, the yield is remarkably lowered due to the polymerization of the product or the trisubstituted urea compound.
  • an isocyanate group and a polymerization inhibitor will react, and a yield will fall.
  • the concentration of the raw material trisubstituted urea compound solution to be dropped is 2.0 mol / L to 20.0 mol / L, preferably 3.0 mol / L to 15.0 mol / L, more preferably 5.0 mol / L. L to 10.0 mol / L.
  • concentration of the raw material trisubstituted urea compound is low, the supply takes time, the reaction time becomes long, and the yield due to an increase in heat history decreases.
  • the concentration of the raw material trisubstituted urea compound is high, the viscosity is high and it is difficult to supply.
  • the concentration of the trisubstituted urea compound in the reaction solution after being dropped into the solvent maintained at a predetermined temperature is 0.1 to 5.0 mol / L, preferably 0.1 to 2.0 mol with respect to the reaction solution. / L, more preferably 0.1 to 1.0 mol / L or more.
  • concentration of the tri-substituted urea compound is small, the reaction rate decreases.
  • concentration of the trisubstituted urea compound is large, the yield decreases due to an increase in the side reaction progress rate such as ester decomposition.
  • the dropping rate of the trisubstituted urea compound solution represented by the general formula (1) is 0.1 to 10.0 g / min, preferably 0.5 to 8.0 g / min in terms of mass of the trisubstituted urea compound.
  • the amount is preferably 0.9 to 4.0 g / min.
  • the amount of hydrogen chloride gas blown is 0.5 to 6.0 molar equivalents, preferably 0.8 to 4.0 molar equivalents, more preferably 1 to 2.0 molar equivalents per mole of the trisubstituted urea compound. It is.
  • the blowing amount is small, the unreacted trisubstituted urea compound increases, and the yield decreases due to insufficient decomposition of a specific byproduct.
  • the amount of blowing is large, the hydrogen chloride Michael adduct to the double bond increases and the yield decreases.
  • the blowing time of hydrogen chloride gas is usually 0.2 to 10.0 hours, preferably 0.5 to 8.0 hours, more preferably 1.0 to 5.0 hours. If the blowing time is short, the loss of hydrogen chloride due to excessive blowing of hydrogen chloride increases. On the other hand, if the blowing time is long, by-products such as ester decomposition increase due to an increase in thermal history, and the yield decreases.
  • the hydrogen chloride gas is preferably blown into the liquid phase part in the reaction system.
  • hydrogen chloride gas is blown into the gas phase portion in the reaction system, blow-through hydrogen chloride increases and the reaction rate decreases. It is preferable to stir the reaction system.
  • the stirring conditions are usually 50 to 1000 rpm, preferably 100 to 800 rpm, more preferably 200 to 600 rpm. When the stirring speed is low, the reaction speed decreases due to a decrease in stirring efficiency.
  • the system temperature in the pyrolysis step is usually 50 to 200 ° C, preferably 80 to 180 ° C, more preferably 120 to 140 ° C. A lower temperature results in a slower reaction rate. On the other hand, higher temperatures increase the possibility of polymerization.
  • the aging step is performed in the same reaction system following the thermal reaction step.
  • the hydrogen chloride gas blowing location in the aging step A and the system temperature in the aging steps A and B are the same as those in the thermal decomposition step.
  • the system temperature may be changed within ⁇ 10 ° C. of the temperature of the pyrolysis step.
  • the blowing rate of hydrogen chloride gas in the aging step A is preferably the same as or lower than the blowing rate in the thermal decomposition step. If it is faster than the blowing speed in the thermal decomposition process, the loss due to blow-through of hydrogen chloride increases.
  • the amount of hydrogen chloride gas blown in the aging step A is usually 0 to 5.0 molar equivalents, preferably 0 to 2.0 molar equivalents, more preferably 0 to 1.0 molar equivalents per 1 mole of the trisubstituted urea compound. It is. If the amount blown is small, the yield decreases due to insufficient decomposition of a specific by-product (production intermediate). On the other hand, when the blowing amount is large, hydrogen chloride loss due to blowing through increases.
  • the aging time is 0.1 to 6.0 hours, preferably 0.3 to 4.0 hours, more preferably 0.5 to 2.0 hours in the aging step A in which hydrogen chloride gas is blown.
  • the aging step B after the completion of the hydrogen chloride gas blowing, it is 0.1 to 4.0 hours, preferably 0.3 to 2.0 hours, more preferably 0.5 to 1.0 hours. If the aging time is short, the yield decreases due to insufficient decomposition of a specific by-product (production intermediate). On the other hand, if the aging time is long, by-products increase due to an increase in heat history, and the yield decreases.
  • the amine hydrochloride generated by the reaction of the blown hydrogen chloride gas and the decomposition product (amine compound) of the trisubstituted urea compound and precipitated in the reaction system may be removed. Filtration is common as a removal method. Moreover, when it reacts in the solvent with low solubility with respect to water, you may extract the produced
  • the remaining solvent is distilled off.
  • the operation and apparatus for the distillation are not particularly limited, but those having a rectification and reflux apparatus are preferred.
  • a thin film distillation apparatus can also be used.
  • Example 1 Preparation of Compound 9 A 1 L four-necked flask equipped with a stirrer, a condenser and a thermometer was charged with 570 g of solvent xylene and 0.5 g of polymerization inhibitor BHT and heated to 130 ° C. in an oil bath. While blowing dry hydrogen chloride gas into the solvent at 90 mL / min, in a separate 250 mL container, 121 g of 2- (N, N-diethylureido) ethyl methacrylate and 100 g of xylene were mixed and added dropwise over 2 hours. (Pyrolysis process).
  • Comparative Example 1 The thermal decomposition process part in Example 1 is referred to as Comparative Example 1.
  • the yield of 2-methacryloyloxyethyl isocyanate (compound 9) sampled, analyzed and calculated at the end of the thermal decomposition step of Example 1 was 69.5% (see Table 2).
  • Example 2 Preparation of compound 11 In the same manner as in Example 1, except that 116 g of 2- (N, N-diethylureido) ethyl acrylate was used instead of 121 g of 2- (N, N-diethylureido) ethyl methacrylate.
  • the desired 2-acryloyloxyethyl isocyanate (Compound 11) was obtained (yield 78%).
  • the yield of the by-product (production intermediate represented by the formula (5)) was 9.4%.
  • Example 3 Preparation of Compound 13 The procedure was carried out except that 156 g of 2,2-[(N, N-diethylureido) -methyl] ethyl bisacrylate was used instead of 121 g of 2- (N, N-diethylureido) ethyl methacrylate.
  • the desired 1,1- (bisacryloyloxymethyl) ethyl isocyanate (Compound 13) was obtained (yield 76%).
  • the yield of the by-product (production intermediate represented by the formula (8)) was 4.2%.
  • Example 4 Preparation of Compound 12 Example 1 except that 136 g of 2- [2- (N, N-diethylureido) ethyloxy] ethyl methacrylate was used instead of 121 g of 2- (N, N-diethylureido) ethyl methacrylate.
  • the desired 2- (2-methacryloyloxyethyloxy) ethyl isocyanate was obtained (yield 85%).
  • the yield of the by-product (production intermediate represented by the formula (7)) was 5.2%.
  • Comparative Example 2 In a 200 mL four-necked flask equipped with a stirrer and a thermometer, 110 g of xylene as a solvent, 0.2 g of BHT as a polymerization inhibitor and 20 g of 2- (N, N-diethylureido) ethyl methacrylate were added, and the system temperature was cooled with ice. Then, 3.3 g of hydrogen chloride was blown in at 10 ° C. or lower. The liquid into which hydrogen chloride was blown was placed in an autoclave container, sealed, and reacted at 130 ° C. for 2 hours.
  • Comparative Example 3 In a 100 mL three-necked flask equipped with a stirrer, a condenser, and a thermometer, 60 g of solvent xylene, 0.1 g of polymerization inhibitor BHT, 10 g of 2- (N, N-diethylureido) ethyl methacrylate and pyridine hydrochloride11. 1 g was added and stirred at 130 ° C. for 2 hours. The reaction solution was cooled, the salt was removed by filtration, and the solvent was distilled off to obtain the desired 2-methacryloyloxyethyl isocyanate (yield 10%).

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Cette invention concerne un procédé de production d'un composé isocyanate contenant un groupe éthyléniquement insaturé, ledit procédé consistant à : (i) soumettre un composé urée à trois substitutions de formule générale (1) (les symboles étant définis dans la description) à une étape de décomposition thermique dans une solution contenant du chlorure d'hydrogène à une température de 50 à 200 °C (étape de décomposition thermique) ; (ii) après l'étape de décomposition, effectuer une étape consistant à introduire du chlorure d'hydrogène dans une solution réactionnelle maintenue à la température susmentionnée (étape de maturation A) ; et (iii) après l'étape de maturation A, effectuer une étape consistant à maintenir la solution réactionnelle à la température susmentionnée (étape de maturation B). Selon l'invention, le composé isocyanate contenant un groupe éthyléniquement insaturé peut être produit avec un rendement élevé et régulier tout en réduisant considérablement la production de sous-produits sans nécessiter d'utiliser du phosgène comme matière première et sans nécessiter d'étape d'élimination de l'acide chlorhydrique.
PCT/JP2012/064785 2011-06-24 2012-06-08 Procédé de production d'un composé isocyanate contenant un groupe éthyléniquement insaturé WO2012176631A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014210735A (ja) * 2013-04-19 2014-11-13 株式会社リコー （メタ）アクリル酸エステル化合物、活性エネルギー線硬化型組成物、インクジェット記録用インク

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5533480A (en) * 1978-08-26 1980-03-08 Akzo Nv Manufacture of organic monoisocyanate or polyisocyanate
JPS61277659A (ja) * 1985-05-28 1986-12-08 ザ・グツドイヤ−・タイヤ・アンド・ラバ−・カンパニ− （１―イソシアナト―１―メチルエチル）―３又は４―（１―メチルエテニル）ベンゼンからの官能基が付与された単量体単位を含む重合体
US4873364A (en) * 1988-12-09 1989-10-10 Arco Chemical Technology, Inc. Process for the preparation of methylene diphenylene diisocyanates and polymethylene polyphenylene poly (diisocyanates)
JPH0348651A (ja) * 1989-07-12 1991-03-01 Arco Chem Technol Inc 脂肪族イソシアネートの製造方法
JPH06157449A (ja) * 1992-08-13 1994-06-03 Chem Linz Ag Ｎ，ｎ，ｎ’− トリ置換された尿素の分解によってイソシアナートを製造する方法
JP2003040927A (ja) * 2001-07-30 2003-02-13 Yamaguchi Technology Licensing Organization Ltd 光学活性ポリメタクリレート誘導体及び分離剤並びに分離方法
JP2004035841A (ja) * 2002-07-08 2004-02-05 Hitachi Chem Co Ltd 接着シート並びに半導体装置及びその製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5533480A (en) * 1978-08-26 1980-03-08 Akzo Nv Manufacture of organic monoisocyanate or polyisocyanate
JPS61277659A (ja) * 1985-05-28 1986-12-08 ザ・グツドイヤ−・タイヤ・アンド・ラバ−・カンパニ− （１―イソシアナト―１―メチルエチル）―３又は４―（１―メチルエテニル）ベンゼンからの官能基が付与された単量体単位を含む重合体
US4873364A (en) * 1988-12-09 1989-10-10 Arco Chemical Technology, Inc. Process for the preparation of methylene diphenylene diisocyanates and polymethylene polyphenylene poly (diisocyanates)
JPH0348651A (ja) * 1989-07-12 1991-03-01 Arco Chem Technol Inc 脂肪族イソシアネートの製造方法
JPH06157449A (ja) * 1992-08-13 1994-06-03 Chem Linz Ag Ｎ，ｎ，ｎ’− トリ置換された尿素の分解によってイソシアナートを製造する方法
JP2003040927A (ja) * 2001-07-30 2003-02-13 Yamaguchi Technology Licensing Organization Ltd 光学活性ポリメタクリレート誘導体及び分離剤並びに分離方法
JP2004035841A (ja) * 2002-07-08 2004-02-05 Hitachi Chem Co Ltd 接着シート並びに半導体装置及びその製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014210735A (ja) * 2013-04-19 2014-11-13 株式会社リコー （メタ）アクリル酸エステル化合物、活性エネルギー線硬化型組成物、インクジェット記録用インク

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