WO2018038415A1 - N-치환 말레이미드 제조용 탈수 반응 촉매, 이의 제조 방법, 및 n-치환 말레이미드의 제조 방법 - Google Patents
N-치환 말레이미드 제조용 탈수 반응 촉매, 이의 제조 방법, 및 n-치환 말레이미드의 제조 방법 Download PDFInfo
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- WO2018038415A1 WO2018038415A1 PCT/KR2017/008296 KR2017008296W WO2018038415A1 WO 2018038415 A1 WO2018038415 A1 WO 2018038415A1 KR 2017008296 W KR2017008296 W KR 2017008296W WO 2018038415 A1 WO2018038415 A1 WO 2018038415A1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
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- 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
Definitions
- Dehydration reaction catalyst for producing N-substituted maleimide preparation method thereof, and preparation method for N-substituted maleimide
- the present invention minimizes the formation of by-products and does not decrease in activity even after several reuses, and thus can be reused, and a dehydration reaction catalyst for preparing N-substituted maleimide which can be maintained for a long time reaction reaction, a method for preparing the same, and N-substituted maleimide It relates to a method for producing.
- N-substituted maleimides have been used in various fields as raw materials or intermediates for pharmaceuticals, pesticides, dyes and high molecular materials.
- N-substituted maleimides are usefully used as monomers or intermediates for high molecular compounds or composites, and are widely used as monomers for improving heat resistance of styrene resins.
- maleic acid monoamide maleamic acid
- amines such as butylamine octylamine, decylamine and dodecylamine and maleic anhydride
- a known process in the laboratory is to react maleic anhydride and aniline in the presence of a sodium acetate catalyst using a dehydrating agent such as acetic anhydride (Org. Synth. Col l., 1973 Vol. 5, page 944).
- a dehydrating agent such as acetic anhydride
- this method is a costly drawback because it requires stoichiometric use of additional costly auxiliary compounds such as acetic anhydride. There is this.
- a method of dehydrating and cyclizing maleic acid monoamide under milder conditions as an effective dehydrating catalyst is more commercially effective.
- N-substituted maleimide minimizes the formation of by-products and does not reduce the activity even after several reuses.
- the present invention is to provide a dehydration reaction catalyst for the production of N- substituted maleimide that can minimize the by-product generation and can be reused because the activity is not reduced even after several times reuse can be maintained.
- the present invention is to provide a method for producing the dehydration reaction catalyst for producing the N-substituted maleimide.
- the present invention also provides a method for preparing N-substituted maleimide in the presence of the catalyst.
- a dehydration reaction catalyst for the production of N-substituted maleimide represented by the following formula (1).
- X is 0.5 to 1.5
- a and b are each independently 0 to 8
- c is 1 to 4.
- the catalyst of Chemical Formula 1 may have c / x of 1.5 to 2.67.
- a method for producing a dehydration reaction catalyst for producing N-substituted maleimide comprising the step of mixing the zirconium precursor and phosphate compound to precipitate the catalyst represented by the formula (1).
- Precipitating the catalyst may include stirring the mixture comprising the zirconium precursor and the phosphate compound at a temperature of about 30 to 95 ° C. In addition, the mixture may be stirred for about 30 minutes to 12 hours.
- the preparation method may further comprise the step of washing the precipitated catalyst with alcohol after the step of precipitating the catalyst. Also, with alcohol After washing, the method may further include calcining at a temperature of about 300 to 600 ° C. for about 4 to 12 hours.
- N comprising the step of dehydrating cyclic reaction of maleic anhydride (malei c anhydride) and aromatic or aliphatic primary amine
- a method for producing substituted maleimide is provided.
- an N- substituted maleimide comprising the step of dehydrating the aromatic or aliphatic monoamide of maleic acid.
- the aromatic or aliphatic monoamide of maleic acid is a product obtained by reacting maleic anhydride with an aromatic or aliphatic primary amine, and the monoamide can be reacted without being separated from the reaction mixture.
- the aromatic primary amine may be aniline, naphthylamine, urludine, dimethylaniline, chloroaniline, dichloroaniline, hydroxyaniline, nitroaniline or phenylenediamine.
- the aliphatic primary amine may be methylamine, ethylamine, propylamine, butylamine, benzylamine, cyclonuxylamine or ethylenediamine.
- the catalyst according to an embodiment of the present invention can secure high catalyst activity and purity by minimizing by-product formation in the production of N-substituted maleimide, and can be reused because the activity does not decrease even after several reuses. This has an excellent effect of being maintained. [Specific contents to carry out invention]
- a dehydration reaction catalyst for producing N-substituted maleimide represented by the following formula (1).
- X is 0.5 to 1.5
- a and b are each independently 0 to 8
- c is 1 to 4.
- the catalyst of Chemical Formula 1 may have c / x of 1.5 to 2.67.
- the dehydration reaction catalyst for preparing the N-substituted maleimide may be represented by the following formula (2).
- N-substituted maleimides are generally obtained by reacting maleic anhydride with an amine under an acid catalyst, followed by dehydration cyclization through an intermediate maleic acid monoamide (maleami c acid). .
- maleami c acid maleic acid monoamide
- APSI 2- Anilino-N-phenyl-succinimide
- APSI 2-ani l-o-N-phenyl succinimide
- PPMA 2- Anilino-N-phenyl-succinimide
- MA malei c acid
- FA fumaric acid
- the catalyst represented by Chemical Formula 1, which is designed to solve this problem, has been found to be effective in terms of increasing N-substituted maleimide purity and catalytic activity and maintaining the activity for a long time even after several reuses.
- the main by-products of APSI and PPMA that is, the other by-products exhibited an excellent effect of producing less.
- the dehydration reaction catalyst for preparing N-substituted maleimide of the present invention is characterized by an amorphous catalyst having a structure represented by Chemical Formula 1.
- the catalyst of Formula 1 is X in the aspect of significantly improving the purity and catalytic activity of the N-substituted maleimide obtained as a final reactant than conventional zirconium phosphate, etc., X is 0.5 to 1, a and b are each independently 0 to 4 It may be preferable that c is 1 to 2. In particular, X and c of Formula 1 may be made in the range that c / x is 1.5 to 2.5, preferably 1.65 to 2.45, 1.8 to 2.3.
- the zirconium phosphate catalyst represented by Chemical Formula 1 is referred to as a ZrP catalyst.
- the dehydration reaction catalyst for the production of N-substituted maleimide of the present invention can analyze the acid strength and the amount of acid point through N3 ⁇ 4-TPD measured by a method of heating and desorbing ammonia gas.
- the catalyst of the present invention may exhibit two peaks at about 125 to 145 ° C. and about 285 to 297 ° C., respectively.
- the peak produced at about 125 to 145 ° C may have a desorption amount of 3.7 to 4.2 yang, about 285 to The peak produced at 297 ° C. may show a desorption amount between 1.65 and 1.95 kPa.
- N- substituted maleimide preparative dehydration catalyst of the invention is about 300 ° Desorption peaks are observed below C, so it can be determined that the catalytic acid strength has a moderate acid strength.
- the dehydration reaction catalyst for preparing N-substituted maleimide of Chemical Formula 1 may have a surface area of 450 m 2 / g or less or 1 to 450 m 2 / g, preferably 400 m 2 / g or less or 3 to 3, measured using a BET apparatus. 400 m 2 / g, more preferably 300 m 2 / g or less or 5 to 300 m 2 / g.
- the dehydration reaction catalyst for preparing N—substituted maleimide of Formula 1 has a pore si ze of about 5 to 30 nm, preferably 6 to 25 nm, and more preferably about 8 To 15 nm. When the pore size of the catalyst is less than about 5 nm or more than about 30 nm, the amount of side reaction occurs in the catalyst reaction and dehydration reaction efficiency for producing N-substituted maleimide may decrease. .
- N- substituted maleimide according to the invention for preparing dehydrated banung catalyst is amorphous or be crystalline mye have, for example, amorphous or rhombic structure of the climb sseumbik (orthorhombi c), such as phosphate (pyrophosphate) Pyro of ZrP 2 0 7 Can be.
- a crystalline form having a layered structure such as the conventional alpha-zirconium phosphate
- the method for preparing a catalyst represented by Formula 1 includes the step of precipitating the catalyst of Formula 1 by mixing a zirconium precursor and a phosphate compound. Since the catalyst of Formula 1 may be obtained as a precipitate when the zirconium precursor and the phosphate compound are mixed, the method of mixing the zirconium precursor and the phosphate compound is not particularly limited. Non-limiting For example, the precursors may be mixed one by one sequentially added to the reaction period, or black may be mixed at one time.
- the solvent is added and the precursors are added while stirring the solvent, or some precursor is added to the reactor and the other precursor is added while stirring the precursor,
- the mixture may be stirred to increase the amount of catalyst produced.
- a solvent such as water may be added, and the precursor may be sequentially or simultaneously added while stirring the solvent such as water.
- some of the precursors may be first introduced into the reaction vessel, and the remaining precursors may be sequentially or simultaneously added while stirring the precursors.
- precursors may be sequentially or simultaneously introduced into the reactor to form a mixture and to stir the mixture.
- the mixture of precursors can be continuously stirred even after all the precursors have been added to the reactor.
- the agitation of the mixture may proceed under a temperature of about 30 to 98 t :, preferably about 35 to 95 ° C. to facilitate the bonding between the metals.
- the agitation may be performed for a time period in which all the precursors added are well mixed to generate a large amount of precipitation.
- the agitation may be performed for about 30 minutes to 18 hours, preferably about 45 minutes to 12 hours.
- Such stirring temperature and stirring time can be produced reproducibly by performing at least about 30 minutes and / or at least about 30 ° C. in terms of making the precipitate well formed.
- it can be carried out by adjusting the upper limit of the stirring temperature and the stirring time in terms of increasing the overall process cost and efficiency.
- the precursor used in the manufacturing method may utilize all of the various precursors known in the art.
- zirconium precursors include zirconyl chloride, zirconyl bromide, zirconyl iodide and zirconyl nitrate trate) and the like.
- phosphate compound phosphoric acid and phosphate in which one or more protons of phosphoric acid are substituted with a cation of Group 1, 2 or 13 can be used. remind
- the precursors may be anhydrous or hydrate.
- the precursors may be used in an appropriate amount depending on the ratio of atoms and atom groups of the formula (1).
- Suitable solvents may be used for uniform mixing of the precursors.
- the solvent is not particularly limited, and water and the like are non-limiting examples.
- the manufacturing method may include the precipitated catalyst obtained in the step of precipitation of the catalyst the further step of washing with water or alcohol or, his common compound.
- the precipitate is usually washed with water, but in one embodiment of the present invention, the precipitate may be washed with alcohol or the like to prepare a catalyst having a larger surface area and an optimized pore size. Catalysts having such a large surface area and optimized pore s ize may exhibit better catalytic activity and higher selectivity of N-substituted maleimide in dehydration reaction when preparing N-substituted maleimide.
- the catalyst obtained after performing the washing process may further include calcining for about 4 to 12 hours at a temperature of about 100 to 500 ° C in terms of securing high activity and mechanical properties.
- the firing temperature may preferably be about 100 to 450 ° C., or about 100 to 400 1, and the firing time may be performed to about 5 to 10 hours or about 6 to 8 hours. That is, the firing temperature may be performed at a temperature of about 100 degrees or more in terms of precursor removal, and at a temperature of about 500 degrees or less or about 450 degrees C or less, or about 400 degrees C or less in terms of preventing a layered structure from being produced. Can be done.
- the firing time may be controlled in terms of generating a catalyst-like structure, performed in about 4 hours or more or about 5 hours or about 6 hours or more in terms of precursor removal, and about 12 hours or less in terms of generating an amorphous structure, or Up to about 10 hours or up to about 8 hours.
- the manufacturing method may further include a step generally employed in the art.
- X is 0.5 to 1.5
- a and b are each independently 0 to 8
- c is 1 to 4.
- another method of the production of N-substituted maleimide according to the present invention includes the reaction of maleic anhydride with an aromatic or aliphatic primary amine in the presence of a catalyst represented by the following formula (1) to form maleic acid monoamide; And a method for producing N-substituted maleimide by effectively dehydrating cyclization reaction without separating or separating maleic acid monoamide in the reaction product.
- X is 0.5 to 1.5, and a and b are each independently
- maleic anhydride malei c anhydr i de
- malei c anhydr i de malei c anhydr i de
- an aromatic or aliphatic primary amine and the like passed through an intermediate maleic acid monoamide (mal eami c ac id) to dehydrate the ring.
- the reaction can be provided to give N-substituted maleimide.
- maleic anhydride which is a starting material of the present invention, may be any and may be appropriately selected from commercially available maleic anhydride.
- Maleic anhydride is usually prepared by oxidation of benzene, n-butene or n-butane.
- aromatic primary amines which are another starting material of the present invention include aniline, naphthylamine, urluidine, dimethylaniline, chloroaniline, dichloroaniline, hydroxyaniline, nitroaniline and phenylenediamine. Preferred among them are aniline, urluidine, chloroaniline, dichloroaniline, hydroxyaniline and nitroaniline.
- aliphatic primary amines are methylamine, ethylamine, propylamine, butylamine, benzylamine, cyclocoilsilamine and ethylenediamine, of which methylamine, butylamine and cyclonuxylamine are preferred.
- aliphatic or aromatic primary amine it is preferable to use 0.8 mol to 1.2 mol per mol of maleic anhydride.
- the dehydration cyclization of the present invention may be carried out in an organic solvent in the presence of a catalyst represented by the formula (1) having the characteristics as described above.
- the first method of the present invention is to react the above-mentioned aromatic or aliphatic or aliphatic primary amine and maleic anhydride in the presence of a catalyst represented by Chemical Formula 1 in an organic solvent.
- reaction can be performed in any of a variety of ways, given the reaction and other factors, the most preferred method is to put a predetermined amount of maleic anhydride, primary amine / organic solvent and catalyst of formula 1 into the reactor, It is a method of effectively reacting by heating to a temperature, or putting a predetermined amount of maleic anhydride, an organic solvent, and a catalyst into a reaction vessel and heating it to a constant temperature, and slowly adding a primary amine thereto.
- the organic solvent used in the present invention may be any solvent capable of dissolving maleic anhydride, aromatic or aliphatic primary amine, and maleic acid monoamide, but is not a solvent that reacts with the catalyst of the above formula.
- Preferred solvents are aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, styrene and cumene Solvent.
- Particularly preferred solvents are benzene, toluene and xylene.
- the amount of the organic solvent used is not limited, but considering the reaction and economical efficiency, it is advantageous to use the product concentration to be about 10% to 50%, preferably about 15% to 35%.
- the reaction can be further improved.
- non-protic polar solvents are formamide, N-methylformamide, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane and nuxamethylphosphotriamide. Preferred of these are dimethylformamide, dimethylacetamide and dimethyl sulfoxide.
- the aprotic polar solvent can be used in a desired amount, it is preferable to use 50% or less, preferably about 2% to 30% with respect to the total amount of the solvent.
- the reaction width may be 50 to 160 ° C., preferably 70 to 140 ° C., considering the catalytic activity and thermal stability.
- the reaction pressure There is no particular limitation on the reaction pressure.
- the pressure ranges are normal pressure, pressure, and pressure.
- the reaction time may vary depending on the concentration of starting material, the amount of catalyst and solvent and the reaction temperature, and the reaction time may be about 4 to 6 hours, preferably about 3 to 8 hours.
- the N-substituted maleimide thus formed can be easily separated and collected by catalytic filtration from the reaction mixture and by evaporating the solvent of the mother liquor.
- It can be further purified by performing distillation, recrystallization, etc. according to a conventional method.
- the catalyst of formula 1 useful in the process of the invention can be reused repeatedly and treated to maintain the activity and regeneration of the catalyst.
- Such treatment may include washing with an organic solvent or the like usable for reaction.
- Two "second method of the invention is the dehydration ring crystallized in the presence of a catalyst after banung maleic anhydride and an aromatic or aliphatic primary amine in the absence, maleic acid monoamide of the formula (1) formed of the catalyst.
- the dehydration cyclization step is carried out in the same manner as the first method described above.
- the maleic acid monoamide formed can be directly dehydrated without separation from the reaction product.
- banung a "maleic anhydride with an amine as described above may be used by the maleic monoamide formed from a starting material.
- the synthesis of maleic acid monoamide is preferably carried out in an organic solvent.
- the organic solvent can be used in combination with an aromatic hydrocarbon solvent or the aprotic polar solvent described above.
- the reaction can be easily carried out at about 150 ° C. or less without using a catalyst in particular, and preferably at room temperature to 100 ° C.
- the reaction time depends on the reaction temperature and the solvent.
- the manufacturing method may further include a step generally employed in the art.
- the reaction product may have a conversion rate of primary amine of about 100% and the N-substituted maleimide produced
- the selectivity of may be about 80% or more, preferably about 83% or more, and more preferably about 85% or more.
- the reaction product may have a conversion rate of primary amine of about 100%, and the resulting N-
- the selectivity of the substituted maleimide may be at least about h, preferably at least about 78%, more preferably at least about 80%.
- the reaction product has an N-substituted maleimide having a conversion rate of about 99% or more.
- the selectivity of can be at least about 60%, preferably at least about 65%, more preferably at least about 70%. As such, even after repeated reuse two or three times in the catalyst The amount of residual phosphate-based component is approximately based on the content before use in reaction.
- the dehydration reaction catalyst for producing N-substituted maleimide of the present invention is about 20 weights more than before the first addition of the phosphate-based component included in the catalyst to the dehydration reaction, even after performing dehydration reaction at least two or three times in succession. % Or less, preferably about 15% by weight or less, more preferably about 5% by weight or less, so that only good loss of catalyst activity can be maintained.
- preferred embodiments of the present invention are provided to aid in understanding the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited thereto.
- Example 1 Example 1
- An aqueous solution was prepared by adding 12.208 g of ZrOCl 2 as a zirconium precursor to 300 mL of distilled water. 8.714 g of NH 4 H 2 P0 4 was added to the aqueous solution as a phosphate precursor, and the aqueous solution was stirred overnight at a temperature of about 95 ° C.
- ZrP zirconium phosphate catalyst
- the acid strength of the ZrP catalyst thus obtained was measured by ammonia elevated temperature desorption (NH3-TPD). As a result, a peak produced at about 130 ° C. (desorption amount of 4.04 ⁇ ol) and a peak at 292 ° C. (desorption amount of 1.835 ⁇ ol) was measured.
- the surface area is about 250 m 2 / g, it was confirmed that has a meso pore (meso pore) in the pore size (pore si ze) of 14.8 nm.
- the used catalyst was washed with 0-xylene (0-xylen), dried and reused twice (Example 1-2) and 3 Reactions (Examples 1-3) were performed and GC and LC analysis was performed on the product of each reaction by the same method as that of the reaction (Example 1-1).
- An aqueous solution was prepared by adding 14.601 g of zi rconium oxyni trate hydrate (N0 3 ) 2 ⁇ X3 ⁇ 40) to 300 mL of distilled water as a zirconium precursor. To the aqueous solution was added 10.564 g of NH 4 H 2 P0 4 as a phosphate precursor, and the aqueous solution was stirred at a temperature of about 95 ° C. overnight. Thereafter, the precipitate precipitated from the aqueous solution was washed with ethanol or water and calcined at 100 ° C.
- ZrP zirconium phosphate catalyst represented by Formula 2 as a dehydration reaction catalyst for preparing N-substituted maleimide.
- the acid strength of the ZrP catalyst thus obtained was measured by ammonia elevated temperature desorption (NH3-TPD). As a result, a peak produced at about 130 ° C (desorbed amount of 4.04 ⁇ ol) and a peak produced at 292 t (desorbed amount of 1.835 mmol ) was measured.
- the catalyst used was washed with 0-xylene (0-xylen), dried and reused twice (Example 2-2) and 3 Reactions (Example 2-3) were performed, and GC and IX analysis was performed on the product of each reaction by the same method as once reaction (Example 2-1).
- sol id was dried overnight in Aubon, and then calcined at 150 ° C. for 8 hours to produce N-substituted maleimide dehydration catalyst 20 wt% 3 ⁇ 4PO 4 / Si0 2 was obtained.
- Dehydration reaction catalyst 20 for preparing N-substituted maleimide obtained as described above Except for using wt% H 3 P0 4 / Si3 ⁇ 4, the same dehydration cyclization as in Example 1 was carried out once (Comparative Example 1-1), twice (Comparative Example 1-2), and 3 times (Comparative Example 1-2). Comparative Example 1-3) was carried out, and the product was subjected to GC and LC analysis.
- N-substituted maleimide dehydration semicoagulant 1.5 wt3 ⁇ 4 1 ⁇ / ⁇ (Preparation of 1 ⁇ 2)
- An aqueous solution was prepared by adding 20 g of a Si3 ⁇ 4 carrier (product name: SP952X) to 150 mL of distilled water. H 3 P0 4 was used as the phosphate compound. Was added, and the aqueous solution was stirred at a temperature of about 50 to 80 ° C. for 1 hour.
- sol id was obtained by removing ethanol under high temperature and reduced pressure using a rotary evaporator. The sol id was dried in an oven overnight and then calcined at 700 ° C. for 8 hours to prepare N-substituted maleimide dehydration reaction catalyst 1.5 wt P / Si0 2 was obtained.
- Example 1 Except for using the dehydration reaction catalyst 1.5 wt% P / Si0 2 for preparing N-substituted maleimide obtained as described above, the same dehydration cyclization reaction as in Example 1 was performed once (Comparative Example 2-1), Performed twice (Comparative Example 2-2) and GC and IX analysis was performed on the product.
- Table 1 The results of the product analysis for the preparation of N-substituted maleimide according to Examples 1 and 2 and Comparative Examples 1 and 2 are shown in Table 1 below.
- the catalysts prepared according to Example 1 and Comparative Example 1, as described above, before the reaction of the production of N-substituted maleimide and after the reaction of the production of N-substituted maleimide three times included
- the content of phosphoric acid component was performed by ICP analysis.
- the results of inductively coupled plasma (ICP) analysis of the phosphoric acid component content in the catalysts of Example 1 and Comparative Example 1 before and after the reaction were shown in Table 2 below.
- Examples 1 and 2 which are the dehydration reaction catalyst for preparing N-substituted maleimide according to the present invention, were found to produce less main by-products, APSI, PPMA and other by-products (others). .
- the activity of the zirconium phosphate-based catalysts of Examples 1 and 2 according to the present invention does not cause p loss even if water is generated, and the activity of the catalyst is maintained even after reuse. It can be seen that.
- the selectivity of N-substituted maleimide (PMI) was very excellent, 71.5% and 81.52%, respectively.
- the catalyst of Example 1 and Comparative Example 1 was confirmed by the ICP component analysis before and after the reaction whether the loss of the phosphate-based component (P).
- P phosphate-based component
- the ZrP catalyst of Example 1 according to the present invention that is, Zr (HP0 4 ) 2 catalyst P loss before and after the reaction was confirmed that almost less than about 5%.
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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US16/091,091 US10464050B2 (en) | 2016-08-24 | 2017-08-01 | Dehydration catalyst for preparing N-substituted maleimide, preparation method thereof, and method of preparing N-substituted maleimide |
CN201780026293.2A CN109070065A (zh) | 2016-08-24 | 2017-08-01 | 用于制备n-取代马来酰亚胺的脱水催化剂、其制备方法和n-取代马来酰亚胺的制备方法 |
JP2018550414A JP6646761B2 (ja) | 2016-08-24 | 2017-08-01 | N−置換マレイミド製造用の脱水反応触媒、その製造方法、及びn−置換マレイミドの製造方法 |
EP17843835.4A EP3417938A4 (en) | 2016-08-24 | 2017-08-01 | DEHYDRATION REACTION CATALYST FOR THE PREPARATION OF N-SUBSTITUTED MALEIMID, METHOD FOR THE PREPARATION THEREOF, AND METHOD FOR THE PRODUCTION OF N-SUBSTITUTED MALEIMID |
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KR10-2016-0107851 | 2016-08-24 | ||
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KR1020170097281A KR102146094B1 (ko) | 2016-08-24 | 2017-07-31 | N-치환 말레이미드 제조용 탈수 반응 촉매, 이의 제조 방법, 및 n-치환 말레이미드의 제조 방법 |
KR10-2017-0097281 | 2017-07-31 |
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PCT/KR2017/008296 WO2018038415A1 (ko) | 2016-08-24 | 2017-08-01 | N-치환 말레이미드 제조용 탈수 반응 촉매, 이의 제조 방법, 및 n-치환 말레이미드의 제조 방법 |
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Cited By (1)
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EP3421451A4 (en) * | 2016-12-28 | 2019-03-20 | LG Chem, Ltd. | PROCESS FOR PREPARING N-SUBSTITUTED MALEIMID USING A SOLID ACID CATALYST |
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EP3421451A4 (en) * | 2016-12-28 | 2019-03-20 | LG Chem, Ltd. | PROCESS FOR PREPARING N-SUBSTITUTED MALEIMID USING A SOLID ACID CATALYST |
US10487052B2 (en) | 2016-12-28 | 2019-11-26 | Lg Chem, Ltd. | Synthesis method of N-substituted maleimide using solid acid catalysts |
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