WO2018124453A1 - Procédé de production de maléimide n-substitué à l'aide d'un catalyseur acide solide - Google Patents

Procédé de production de maléimide n-substitué à l'aide d'un catalyseur acide solide Download PDF

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WO2018124453A1
WO2018124453A1 PCT/KR2017/012499 KR2017012499W WO2018124453A1 WO 2018124453 A1 WO2018124453 A1 WO 2018124453A1 KR 2017012499 W KR2017012499 W KR 2017012499W WO 2018124453 A1 WO2018124453 A1 WO 2018124453A1
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Prior art keywords
maleimide
catalyst
substituted
amine
substituted maleimide
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PCT/KR2017/012499
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English (en)
Korean (ko)
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천주영
최준선
김지연
조왕래
김경수
염응섭
이원균
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주식회사 엘지화학
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Priority claimed from KR1020170133529A external-priority patent/KR102175831B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US16/091,475 priority Critical patent/US10487052B2/en
Priority to JP2019503184A priority patent/JP6697124B2/ja
Priority to EP17887093.7A priority patent/EP3421451B1/fr
Priority to CN201780024748.7A priority patent/CN109071432B/zh
Publication of WO2018124453A1 publication Critical patent/WO2018124453A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
    • C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
    • C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
    • C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
    • C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
    • C07D207/452—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide with hydrocarbon radicals, substituted by hetero atoms, directly attached to the ring nitrogen atom
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to a method for synthesizing N-substituted maleimide using zirconium (IV) hydrogenphosphate as a solid acid catalyst.
  • the maleimide compound is a compound useful as a raw material for water support fees, pharmaceutical pesticides, and the like, and in particular, styrene resins such as ABS resins, AS resins, AB resins, ACS resins, AES resins, AAS resins, polyvinyl chloride resins, In order to improve heat resistance of polymethyl methacrylate resins and phenol resins, they are frequently used as one of copolymerization components. Among them, N-phenyl maleimide (hereinafter also referred to as PMI) is excellent in terms of reactivity and heat resistance, and is particularly widely used.
  • PMI N-phenyl maleimide
  • maleimide compound About the manufacturing method of a maleimide compound, 1) the method obtained by dehydrating maleic anhydride (henceforth MAH) and primary amines in one step, 2) maleamine from maleic anhydride and primary amines Many methods conventionally, such as the method of producing
  • N-phenyl maleimide is aniline (henceforth ANL)
  • maleamic acid is N-phenyl maleamic acid (henceforth PMA).
  • the inventors of the present invention have solved the above problems when using zirconium hydrogenphosphate as a solid acid catalyst in the method for preparing N-phenylmaleimide of 2). It has been found that the present invention has been completed.
  • Patent Document 1 Republic of Korea Patent Publication No. 10-1051543 (Registered July 18, 2011)
  • the problem to be solved of the present invention is to use a zirconium hydrogen phosphate (Zirconium (IV) hydrogenphosphate) solid acid catalyst as a catalyst for the N-substituted maleimide synthesis reaction, thereby minimizing the loss of the catalyst to supplement the catalyst during the synthesis reaction It is to provide a method for producing unnecessary N-substituted maleimide.
  • Zirconium (IV) hydrogenphosphate zirconium (IV) hydrogenphosphate
  • the solid acid catalyst can be separated and recovered through simple filtration, so that the separation and recovery process is simplified, and the activity of the separated and recovered catalyst is reduced, washed or calcined.
  • the complete regeneration of the catalyst there is provided a method for producing N-substituted maleimide without limitation of the solvent that can be used in the catalyst washing process.
  • Another object of the present invention is to provide a method for producing N-substituted maleimide having high yield of N-substituted maleimide.
  • the present invention is to solve the above problems
  • the catalyst provides a method for producing N-substituted maleimide, characterized in that the zirconium hydrogen phosphate (Zirconium (IV) hydrogenphosphate) solid acid catalyst.
  • N-substituted maleimide production method of the present invention by using a zirconium hydrogen phosphate solid acid catalyst during the synthesis reaction of N-substituted maleimide, there is an effect that unnecessary replacement of the catalyst during the synthesis reaction to minimize the loss of the catalyst.
  • the solid acid catalyst is capable of separating and recovering the catalyst through simple filtration, and thus, the separation and recovery process of the catalyst is simple, and the catalyst can be completely regenerated by washing or firing. There is an effect that the solvent can be used without any kind.
  • the zirconium hydrogen phosphate solid acid catalyst has an effect of high N-substituted maleimide synthesis yield.
  • 1 is a flowchart showing the procedure of the N-substituted maleimide production method of the present invention.
  • FIG. 2 is a flowchart showing the procedure of a conventional method for producing N-substituted maleimide.
  • the present invention is a.
  • the catalyst provides a method for producing N-substituted maleimide, characterized in that the zirconium hydrogen phosphate (Zirconium (IV) hydrogenphosphate) solid acid catalyst.
  • Step 1) is a step for synthesizing N-substituted maleimide, by introducing maleic anhydride and primary amine in the presence of an organic solvent and a catalyst to form N-substituted maleimide It is characterized by synthesizing.
  • maleimide compound About the manufacturing method of a maleimide compound, 1) the method obtained by dehydrating maleic anhydride and a primary amine in one step, 2) maleic anhydride is produced
  • N-substituted maleimide production method of the present invention maleic anhydride and primary amine are heated to acylate in one step to obtain N-substituted maleamic acid as an intermediate, and the N is substituted on the surface of the catalyst in two steps.
  • N-substituted maleimide can be synthesize
  • maleic anhydride or aniline may be used as it is, but is preferably used in the form of a solution dissolved in an organic solvent.
  • the following dehydration ring closure imidation reaction of N-phenyl maleamic acid can be performed in a solution (organic solvent) as it is.
  • the organic solvent used in the present invention is insoluble or immiscible in water, inert to the reaction, and capable of releasing water generated by the dehydration ring closure reaction of N-substituted maleamic acid through the azeotropic distillation. Do not participate.
  • the boiling point is at least 50 ° C. or higher for the smooth progress of the reaction, and the boiling point is lower than 170 ° C. for the stability of the resulting N-substituted maleimide.
  • suitable organic solvents for this reaction include benzene, toluene, xylene, o-xylene, ethylbenzene, isopropylbenzene, cumene, mesitylene, tert-butylbenzene, pseudocumene, trimethylhexane, octane, tetra Chloroethane, nonane, chlorobenzene, ethylcyclohexane, m-dichlorobenzene, sec-butylbenzene, p-dichlorobenzene, decane, p-cymene, o-dichlorobenzene, butylbenzene, decahydronaphthalene, te
  • the amount of the organic solvent to be used is not particularly limited. However, the amount of the organic solvent is about 1 to 20 times (by weight) more preferably about 1 to 20 times the amount of the primary amine to be used as a raw material, in order to satisfy the economic conditions while smoothly carrying out the reaction. The range of 2 to 10 times (by weight) is appropriate.
  • the amount of the organic solvent is less than 2 times, there is a problem in that the yield is not easy to effectively remove the water produced through the dehydration ring-closure reaction of the N-substituted maleamic acid from the reaction system, if the amount exceeds 10 times synthesized In the process of separating the organic solvent from the N-substituted maleimide solution, excessive energy is consumed, which is not preferable from an economic point of view.
  • the organic solvent should be determined in consideration of environmental factors and solubility, price and ease of handling of N-substituted maleimide, and moreover, a solvent suitable for easy removal and reuse after completion of the reaction should be selected.
  • maleic anhydride and primary amine may be dissolved in the same organic solvent or in another organic solvent, but are preferably dissolved in the same organic solvent.
  • the concentration of maleic anhydride or primary amine in the case of using maleic anhydride or primary amine in the form of a solution dissolved in an organic solvent is not particularly limited as long as it can dissolve maleic anhydride or primary amine. Do not. Specifically, it is preferable that 0-500 g of organic solvents, more preferably 10-200 g are added and melt
  • the primary amine is a saturated or unsaturated alkylamine having 1 to 20 carbon atoms, cycloalkylamine having 5 to 20 carbon atoms, cycloalkylamine having 6 to 20 carbon atoms or 6 to 20 carbon atoms
  • One kind of primary amine selected from among aromatic alkylamines may be used, specifically, methyl amine, ethyl amine, n-propyl amine, isopropyl amine, n-butyl amine, sec-butyl amine, iso-butyl amine , at least one selected from the group consisting of tert-butylamine, n-hexyl amine, n-octyl amine, n-decyl amine, n-dodecyl amine, cyclohexyl amine and aniline can be used.
  • Aniline can be used as the primary amine to synthesize phenyl maleimide.
  • the amount of maleic anhydride is preferably used in an amount of 1.0 to 1.3 molar ratio relative to the primary amine used in the synthesis of N-substituted maleimides.
  • maleic anhydride is used at less than 1.0 molar ratio, problems of yield reduction and by-products increase.
  • the maleic anhydride is used at 1.3 molar ratio or higher, unreacted maleic anhydride remains excessive after N-substituted maleimide synthesis. It is not preferable in terms of.
  • the N-substituted maleimide production method of the present invention synthesizes N-substituted maleimides using a heterogeneous solid acid catalyst rather than a homogeneous liquid catalyst or a supported catalyst. It is characterized by being able to solve the problem.
  • the homogeneous system means that the reactants of the N-substituted maleimide synthesis reaction and the catalyst have the same phase
  • the heterogeneous system means that the reactants and the catalyst have different states.
  • the heterogeneous solid acid catalyst used in the present invention is characterized in that the zirconium hydrogen phosphate (Zirconium (IV) hydrogenphosphate).
  • Zirconium hydrogenphosphate (Zirconium (IV) hydrogenphosphate, Zr (HPO 4 ) 2 ) is an acidic, inorganic cation exchange material with a layered structure, with high thermal and chemical stability, solid ion conductivity, resistance to ionizing radiation, and To introduce different types of molecules of different sizes into their layers.
  • the zirconium hydrogen phosphate may exist in a variety of states having a variety of interlayer space and crystal structure, the most widely known zirconium hydrogen phosphate is alpha type of Zr (HPO 4 ) 2 ⁇ H 2 O and Zr (PO 4 ) (H 2 PO 4 ) ⁇ 2H 2 O.
  • the zirconium hydrogen phosphate may be utilized in various fields such as drug delivery, catalysis, nanocomposites, nuclear waste management or clinical dialysis machine.
  • the zirconium hydrogen phosphate used as the solid acid catalyst is an amorphous zirconium hydrogen phosphate rather than the crystalline structures of the alpha type and the gamma type, and the degree of hydration may vary depending on the reaction conditions. Can be displayed.
  • the method for preparing N-substituted maleimide compounds of the present invention can minimize the possibility of loss of the catalyst by using a heterogeneous solid acid catalyst having a different state from the reactant of the N-substituted maleimide synthesis reaction.
  • the yield of N-substituted maleimides is high by using zirconium hydrogen phosphate.
  • the catalyst of the present invention is a solid in a state different from the reactants, and the loss of the active component by water, which is a by-product generated during the synthesis of N-substituted maleimide, and the loss of the catalyst in the phase separation process after completion of the synthesis reaction.
  • the zirconium hydrogen phosphate used in the present invention is structurally very stable, and since the reactivity with water is low, it is not necessary to replenish and regenerate the catalyst during the reaction, thereby preparing N-substituted maleimides. The process also has the effect of being simplified.
  • the zirconium hydrogen phosphate of the present invention has a higher yield of N-substituted maleimide synthesis than other solid acid catalysts, and specifically, when zirconium hydrogen phosphate is added in an amount of 0.06 weight or more relative to the input reaction solvent, N-substituted male
  • the yield of mids synthesis can be made 70% or more.
  • the heterogeneous solid acid catalyst of the present invention should be added in an appropriate amount from the viewpoint of process operation and cost, specifically, it is added in a weight ratio of 0.01 to 1.0 weight ratio, more specifically 0.05 to 0.5 with respect to the input reaction solvent. desirable.
  • the total reaction time is low because the ratio of N-substituted maleamic acid converted per unit time is low, and if it exceeds 1.0 weight ratio, the reaction medium is generated according to the production of N-substituted maleamic acid as an intermediate product. Agitation due to increased solids may not be smooth.
  • the metal-containing compound and the stabilizer may be coexisted in the reaction system and reacted.
  • the metal-containing compound used at this time is not particularly limited, but at least one metal oxide, acetate, maleate, succinate salt selected from the group consisting of zinc, chromium, palladium, cobalt, nickel, iron and aluminum. of succinic acid, nitrates, phosphates, chlorides and sulfates. Of these, zinc acetate is particularly effective.
  • the amount of these used is 0.005 to 0.5 mol%, preferably 0.01 to 0.1 mol%, as a metal, based on maleic anhydride and / or primary amine as a raw material.
  • methoxybenzoquinone, p-methoxyphenol, phenothiazine, hydroquinone, alkylated diphenyl amines, methylene blue, tert-butyl catechol, tert-butylhydroquinone, dimethyldithiocarba Mate zinc, dimethyldithiocarbamate, copper dibutyldithiocarbamic acid, copper salicylate, thiodipropionic acid esters, mercaptobenzimidazole, triphenyl phosphite, alkyl phenols, alkyl bisphenols, and the like are used as a stabilizer.
  • the effect of these stabilizers plays a role of making the N-substituted maleimide produced by the dehydration ring closure imidization reaction stably exist without deterioration even at a high temperature of the imidization reaction.
  • the addition amount is not specifically limited, 0.001 to 0.5 mol% can be used with respect to maleic anhydride and / or primary amine which are raw materials.
  • the said stabilizing effect can fully be exhibited and the problem mixed in a product can also be avoided.
  • the reaction temperature of the N-substituted maleimide of step 1) is generally 50 to 200 ° C, more preferably 100 to 140 ° C.
  • the synthesis reaction temperature is less than 50 °C, a problem that the yield is lowered, when the temperature is 200 °C or more, the polymerization of N-substituted maleimide synthesized by side reaction is inhibited, the purity and yield of the synthesized N-substituted maleimide This deterioration problem occurs.
  • reaction pressure in the present invention, and it can be selected in a wide range from reduced pressure, atmospheric pressure and pressure.
  • the reaction may vary depending on conditions such as the type of solvent, the amount of raw materials, the amount of catalyst and the reaction temperature, but is generally about 1 to 16 hours, more preferably within 1 to 10 hours.
  • Step 2) is a separation and recovery step for reusing the catalyst, characterized in that the catalyst is separated and recovered from a solution containing N-substituted maleimide.
  • a solution layer in which N-substituted maleimide is dissolved is first separated from the catalyst layer to separate layers, and secondly, a catalyst remaining in the product through a washing solvent.
  • the catalyst was separated and recovered by removing and removing impurities.
  • the separation of the homogeneous catalyst is not easy, and the supported catalyst also loses the active ingredient in the carrier, and a large amount of wastewater is generated, making the separation and recovery process difficult and complicated.
  • the catalyst used in the N-substituted maleimide production method of the present invention uses a zirconium hydrogen phosphate, which is a structural acid and a chemically stable solid acid as a solid acid catalyst, so that cooling and reheating processes are unnecessary, thereby adding energy. No input is required and the catalyst is filtered by simple filtration even at a temperature from the lowest temperature at which the product does not precipitate as a solid on the solution containing the product to the break point of the solution containing the product, more specifically at a high temperature of 70 to 160 ° C. Since separation and recovery of the catalyst are possible, there is an effect of simplifying the separation and recovery of the catalyst.
  • the washing solvent that can be used to wash the impurities in the washing or calcining process for regenerating the activity of the catalyst has a limitation, and the catalyst can not be regenerated through the simple calcining process. There was a limit to give.
  • a heterogeneous solid acid catalyst is used as a catalyst, and when the activity of the separated and recovered catalyst is partially reduced, the catalyst is maintained while the stability of the catalyst is maintained by washing with a washing solvent without any kind. It is possible to regenerate, and when the catalyst is completely inactive because the activity is completely reduced, there is a characteristic that the catalyst can be easily regenerated through a calcination process.
  • the washing solvent that can be used in the washing process can be used without limitation, a polar solvent, specifically, at least one polar solvent selected from the group consisting of water, acetone, sulfoxide series and cyclic polar organic solvent containing oxygen Can be used.
  • the reactant is stored by mixing the catalyst which has been separated, recovered and regenerated with N-substituted maleimide compounds mixed with an organic solvent of the same type as used in the synthesis reaction to ensure fluidity. It can be transferred to a tank or synthesis reactor for reuse.
  • the method for preparing N-substituted maleimide compounds of the present invention uses a heterogeneous zirconium hydrogenphosphate solid acid catalyst as a catalyst, thereby minimizing the loss of the catalyst.
  • Separation and recovery of catalysts including the limitation of solvents that can be used to separate catalysts generated in the production process, the generation of large amounts of waste water in the removal of residual catalysts and impurities, and the need for energy input for cooling and reheating, and The regeneration process can solve complex problems.
  • the supported catalyst was separated by filtration to recover an N-phenyl maleimide o-xylene solution.
  • the recovered N-phenyl maleimide o-xylene solution was heated to 80 ° C. under 10 mmHg reduced pressure, and o-xylene was removed by distillation under reduced pressure to prepare N-phenyl maleimide.
  • N-phenyl maleimide was prepared in the same manner as in Example 1, except that 0.8 g of the zirconium (IV) hydrogenphosphate solid acid catalyst was added in Example 1.
  • N-phenyl maleimide was prepared in the same manner as in Example 1 except that 0.6 g of a Zirconium (IV) hydrogenphosphate solid acid catalyst was added in Example 1.
  • N-phenyl maleimide was prepared in the same manner as in Example 1, except that the solid acid catalyst described in Table 1 was used instead of the zirconium hydrogen phosphate solid acid catalyst in Example 1.
  • Comparative Examples 1 to 10 are the same as Examples 1 to 3 solid acid catalyst or a catalyst of the Phosphate series Even if using the N-phenyl maleimide (PMI) yield or ANL (aniline) based selectivity is not confirmed that high.
  • PMI N-phenyl maleimide
  • ANL aniline
  • Examples 1 to 3 using the zirconium hydrogen phosphate solid acid catalyst showed that the N-phenyl maleimide (PMI) yield and the ANL (aniline) standard Selectivity were excellent.
  • PMI N-phenyl maleimide
  • ANL aniline

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

La présente invention concerne un procédé de production d'un maléimide N-substitué à l'aide d'un catalyseur acide solide hétérogène. Particulièrement, l'objectif de la présente invention est de fournir un procédé de production d'un maléimide N-substitué, dans lequel, à l'aide d'un catalyseur solide acide de l'hydrogénophosphate de zirconium (IV) en tant que catalyseur d'une réaction de synthèse de maléimide N-substitué, la perte du catalyseur est minimisée, les processus de séparation et de récupération du catalyseur sont simplifiés, le catalyseur peut être complètement régénéré par lavage ou cuisson lorsque l'activité du catalyseur séparé et récupéré est réduite, il n'y a pas de restriction sur le choix du solvant de lavage, et le rendement de synthèse de maléimide N-substitué est élevé.
PCT/KR2017/012499 2016-12-28 2017-11-06 Procédé de production de maléimide n-substitué à l'aide d'un catalyseur acide solide WO2018124453A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US16/091,475 US10487052B2 (en) 2016-12-28 2017-11-06 Synthesis method of N-substituted maleimide using solid acid catalysts
JP2019503184A JP6697124B2 (ja) 2016-12-28 2017-11-06 固体酸触媒を用いたｎ‐置換マレイミドの製造方法
EP17887093.7A EP3421451B1 (fr) 2016-12-28 2017-11-06 Procédé de production de maléimide n-substitué à l'aide d'un catalyseur acide solide
CN201780024748.7A CN109071432B (zh) 2016-12-28 2017-11-06 使用固体酸催化剂的n-取代马来酰亚胺的合成方法

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KR20160181021 2016-12-28
KR10-2016-0181021 2016-12-28
KR1020170133529A KR102175831B1 (ko) 2016-12-28 2017-10-13 고체산 촉매를 이용한 n-치환 말레이미드 제조방법
KR10-2017-0133529 2017-10-13

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
EP3578544A4 (fr) * 2017-12-21 2019-12-11 Lg Chem, Ltd. Procédé de purification de maléimide n-substitué

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EP0213933A2 (fr) * 1985-08-28 1987-03-11 Nippon Shokubai Co., Ltd. Préparation de maléimide
US4786738A (en) * 1984-06-18 1988-11-22 Nippon Shokubai Kagaku Kogyo Co., Ltd. Method for production of maleimides
KR20090054494A (ko) * 2007-11-27 2009-06-01 주식회사 엘지화학 Ｎ-치환 말레이미드류의 제조방법
KR20090069016A (ko) * 2007-12-24 2009-06-29 금호석유화학 주식회사 Ｎ－치환 말레이미드류의 제조방법

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US4786738A (en) * 1984-06-18 1988-11-22 Nippon Shokubai Kagaku Kogyo Co., Ltd. Method for production of maleimides
EP0213933A2 (fr) * 1985-08-28 1987-03-11 Nippon Shokubai Co., Ltd. Préparation de maléimide
KR20090054494A (ko) * 2007-11-27 2009-06-01 주식회사 엘지화학 Ｎ-치환 말레이미드류의 제조방법
KR20090069016A (ko) * 2007-12-24 2009-06-29 금호석유화학 주식회사 Ｎ－치환 말레이미드류의 제조방법

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KAMIYA, Y. ET AL.: "Zirconium Phosphate with a High Surface Area as a Water-tolerant Solid Acid", CATALYSIS LETTERS, vol. 94, no. 1- 2, April 2004 (2004-04-01), pages 45 - 47, XP002456899 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3578544A4 (fr) * 2017-12-21 2019-12-11 Lg Chem, Ltd. Procédé de purification de maléimide n-substitué
US10899708B2 (en) 2017-12-21 2021-01-26 Lg Chem, Ltd. Method for purifying n-substituted maleimide

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