WO2016058207A1 - Procédé de préparation de 3-aminométhyl-3,5,5-triméthylcyclohexylamine - Google Patents

Procédé de préparation de 3-aminométhyl-3,5,5-triméthylcyclohexylamine Download PDF

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WO2016058207A1
WO2016058207A1 PCT/CN2014/089027 CN2014089027W WO2016058207A1 WO 2016058207 A1 WO2016058207 A1 WO 2016058207A1 CN 2014089027 W CN2014089027 W CN 2014089027W WO 2016058207 A1 WO2016058207 A1 WO 2016058207A1
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catalyst
cyano
trimethylcyclohexanone
ipn
oxide
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PCT/CN2014/089027
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Chinese (zh)
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王坤
陈长生
姜庆梅
黎源
崔娇英
邵仁龙
陈忠英
蒋万凯
李昂
丁可
胡江林
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万华化学集团股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
    • C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
    • C07C209/52—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of imines or imino-ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/33—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C07C211/34—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings of a saturated carbon skeleton
    • C07C211/36—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings of a saturated carbon skeleton containing at least two amino groups bound to the carbon skeleton

Definitions

  • the invention relates to a method for preparing an aliphatic diamine, in particular to a method for preparing 3-aminomethyl-3,5,5-trimethylcyclohexylamine.
  • 3-aminomethyl-3,5,5-trimethylcyclohexylamine (also known as isophoronediamine, abbreviated as IPDA) is a 3-isocyanate-methylene-3,5,5-trimethyl group.
  • a raw material such as cyclohexyl isocyanate (also known as isophorone diisocyanate, abbreviated as IPDI) or polyamide can also be used as a curing agent for an epoxy resin.
  • the mainstream preparation method of IPDA usually includes an imidization step and a hydrogenation step, first through 3-cyano-3,5,5-trimethylcyclohexanone (also known as isophorone nitrile, Acronym IPN) reacts with liquid ammonia to form 3-cyano-3,5,5-trimethylcyclohexylimine (also known as isophorone nitrile imine, IPNI for short), followed by the presence of IPNI and hydrogen in liquid ammonia.
  • the reductive amination reaction is carried out catalytically to obtain IPDA.
  • the imidization step and the hydrogenation step for the preparation of IPDA from IPN are usually carried out in two or three separate reactors, and are also reported in the literature to be completed in one reactor.
  • IPDA IP-amination hydrogenation
  • direct hydrogenation of IPN to form amino alcohol (IPAA) which is caused by insufficient imidization of IPN
  • formation of secondary amines which are derived from nitrogen atoms. It is determined by the electronegativity difference and molecular structure of carbon atoms; the formation of bis-IPDA precursors is also determined by the electronegativity difference of carbon and nitrogen atoms.
  • IPDA liquid ammonia
  • solvent solvent
  • catalyst and cocatalyst are produced in one reactor at 50-120 ° C and 5-15 MPa hydrogen pressure in a one-step process.
  • This method inevitably produces a large amount of decyanolated products (a), (b) and amino alcohols (c), thereby limiting the yield of IPDA.
  • German Patent Publication No. DE 10 142 635 A1 discloses a three-step process for the preparation of IPDA comprising an imidization step and two hydrogenation steps, wherein the imidization step is carried out by IPN with excess liquid ammonia at 20-150 ° C and 50-300
  • the reaction under the pressure of Ba produces 3-cyano-3,5,5-trimethylcyclohexanoneimine (IPNI), optionally on an acidic metal oxide catalyst.
  • IPNI 3-cyano-3,5,5-trimethylcyclohexanoneimine
  • the disadvantage of this method is that the amount of amino alcohol (c), secondary amine (d) and bis-IPDA (e) is large, which limits the yield of IPDA.
  • the following figure shows the side reaction history of IPDA prepared by IPN amination hydrogenation.
  • the research on the preparation of IPDA by IPN amination hydrogenation has focused on the hydrogenation step.
  • the imidization step is a reversible reaction, and the means for generally adjusting the imidization reaction rate is achieved by adjusting the reaction temperature and the use of the catalyst, but the effect is not significant.
  • the space velocity of the imidization step is usually only 0.5-20 g IPN/(ml catalyst ⁇ hour) due to the imidization reaction rate, and the space velocity is not high, resulting in a reaction site.
  • the amount of catalyst required is large, the equipment is bulky, and the cost is high.
  • the existing IPDA preparation process cannot overcome the defects of many by-products and low space velocity in the imidization step, so it is necessary to seek a new IPDA preparation process to overcome the above technical defects.
  • the object of the present invention is to provide a preparation method of 3-aminomethyl-3,5,5-trimethylcyclohexylamine (IPDA), which can effectively reduce secondary products such as secondary amines, amino alcohols and bis-IPDA.
  • IPDA 3-aminomethyl-3,5,5-trimethylcyclohexylamine
  • the production yields higher yields, and the method can also significantly increase the imidization rate of IPN, thereby greatly increasing the reaction space velocity and reducing the basic investment of equipment.
  • IPDA 3-aminomethyl-3,5,5-trimethylcyclohexylamine
  • step b) adding a basic acid value adjuster to the partially imidized reaction liquid obtained in the step a) in an amount of 0.2 to 5 Torr, preferably 0.5 to 3 Torr, in a hydrogen atmosphere. Or continue the imidization reaction without hydrogen atmosphere;
  • step b) Hydrogenating the product obtained in step b) in the presence of hydrogen, liquid ammonia and a catalyst to form IPDA.
  • IPN materials are usually acidic. It is well known to those skilled in the art that under alkaline conditions, IPN readily deacylates to form an undesired de-cyano product, and IPN acidity is advantageous for reducing the production of de-cyano products, and thus imidization is generally not considered in the art.
  • the acid value of the IPN material is adjusted in the step.
  • the imidization step will generate more bis-IPDA precursors, while the imidization reaction rate is not high and the space velocity is low; while the raw material IPN is alkaline, although it will decrease
  • the formation of the bis-IPDA precursor in the imidization step is reduced, but the IPN undergoes a large number of decyanolation reactions during the reaction, thereby reducing the reaction yield of the IPDA.
  • the inventors have found that when the raw material IPN has an appropriate acid value level, it helps to accelerate the imidization reaction rate of IPN and reduce the amount of IPAA produced in the hydrogenation process; and after the IPN imidization reaction proceeds to a certain extent, Adding a certain amount of basic acid value regulator can effectively inhibit the nucleophilic reaction rate of nitrogen atoms and carbon atoms, thereby inhibiting the formation of secondary amine groups and bis-IPDA precursors, thereby reducing amino alcohols and secondary amines in the hydrogenation step. And the content of double-IPDA. Literature research shows that the relationship between the imidization reaction rate and the acid value of the system has not been reported.
  • the process of the present invention divides the reaction into three steps, namely two imidization steps a) and b) and one hydrogenation step c), first controlling the acid value of the raw material IPN within a certain range, but still being acidic, After the imidization reaction is carried out to a certain extent, a certain amount of basic acid value is added to the reaction solution.
  • the agent makes the IPN extremely weakly acidic or slightly alkaline. This not only ensures that no excessive de-cyano product is produced, but also the content of the bis-IPDA precursor in the imidization step is well controlled, and the reaction rate of the imidization reaction is greatly improved. Intermediate secondary amines, amino alcohols, and bis-IPDA production were all significantly inhibited.
  • step a) the IPN is reacted with liquid ammonia to an IPN conversion of 50 to 80%, preferably 60 to 70%, to obtain the partially imidized reaction liquid.
  • a basic acid number modifier is more advantageous for reducing the formation of the denitrile product, the amino alcohol and the bis-IPDA precursor.
  • the acid value of the raw material IPN of the step a) can be adjusted according to the quality of the raw material, by adding an acidic compound or a basic compound.
  • the acidic compound is selected from an organic acid or a mineral acid which does not have strong oxidizing property and strong corrosivity, and preferably one or more of phosphoric acid, acetic acid, boric acid, oxalic acid, benzoic acid and carbonic acid, more preferably It is phosphoric acid and/or acetic acid.
  • the basic compound is selected from the group consisting of oxides, hydroxides or carbonates of alkali metals, oxides, hydroxides or carbonates of alkaline earth metals, or oxides, hydroxides or carbons of rare earth metals
  • the acid salts preferably one or more of an oxide, hydroxide or carbonate of an alkali metal, or an oxide, hydroxide or carbonate of an alkaline earth metal, more preferably Li 2 O, Na 2 O, K 2 O, Rb 2 O, Cs 2 O, LiOH, NaOH, KOH, RbOH, CsOH, Li 2 CO 3 , Na 2 CO 3 , K 2 CO 3 , Rb 2 CO 3
  • Particularly preferred are LiOH and/or NaOH
  • step a) is carried out at a temperature of from 30 to 100 ° C and a pressure of from 0.5 to 30 MPa, more preferably at a temperature of from 40 to 60 ° C and a pressure of from 15 to 20 MPa.
  • the alkaline acid number adjusting agent involved in step b) is selected from the group consisting of oxides, hydroxides or carbonates of alkali metals, oxides, hydroxides or carbonates of alkaline earth metals. a salt, or one or more of an oxide, hydroxide or carbonate of a rare earth metal, more preferably an oxide, hydroxide or carbonate of an alkali metal, or an oxide or hydroxide of an alkaline earth metal.
  • One or more of the substances or carbonates more preferably Li 2 O, Na 2 O, K 2 O, Rb 2 O, Cs 2 O, LiOH, NaOH, KOH, RbOH, CsOH, Li 2 CO 3 , Na 2 CO 3 , K 2 CO 3 , Rb 2 CO 3 , MgO, CaO, SrO, BaO, Mg(OH) 2 , Ca(OH) 2 , Sr(OH) 2 , Ba(OH) 2 , MgCO 3
  • CaCO 3 , SrCO 3 or BaCO 3 is particularly preferably LiOH and/or NaOH.
  • step b) is at a temperature of 20 to 80 ° C and a pressure of 0.5 to 30 MPa. It is more preferably carried out at a temperature of 20 to 40 ° C and a pressure of 15 to 20 MPa.
  • the IPN in steps a) and b) is imidized with liquid ammonia, and the reaction may be carried out using a catalyst or not using a catalyst, preferably a catalyst.
  • the catalyst may be any useful imidization catalyst, such as an acidic metal oxide, an acidic ion exchange resin, a heteropolyacid, a sulfonic acid group-containing organopolysiloxane or activated carbon.
  • step a) uses an acidic metal oxide, more preferably gamma-alumina is used as a catalyst.
  • step b) uses activated carbon as the catalyst.
  • a higher imidization reaction rate can be obtained by controlling the acid value of the raw material IPN and adding a basic acid value regulator during the imidization reaction.
  • the IPN conversion rate described in step a) can be controlled by adjusting the airspeed.
  • the space velocity can be controlled by adjusting the catalyst volume and the IPN feed rate. At a certain temperature and time, when the feed amount of IPN is constant, the volume of the filled catalyst determines the conversion rate of IPN.
  • the space velocity control of step a) and step b) is from 30 to 200 grams of IPN / (ml catalyst ⁇ hour), preferably from 50 to 150 grams of IPN / (ml of catalyst ⁇ hour), more preferably from 70 to 100 grams of IPN / (ml catalyst ⁇ hour).
  • the "airspeed” is the mass of the raw material IPN treated per unit time of the catalyst per unit time, and the unit is gram IPN / (ml catalyst ⁇ hour). It should be noted that when no catalyst is used in the steps a) and b), the volume of the "catalyst" in the unit of the space velocity "g IPN / (ml catalyst ⁇ hour)" should be correspondingly replaced for the filling reaction. The volume of inert material added is well understood by those skilled in the art.
  • the molar ratio of liquid ammonia to IPN is from 5 to 200:1, preferably from 10 to 100:1, more preferably from 20 to 50:1.
  • the imidization of IPN in step a) and step b) can be carried out without the addition of a solvent or in the presence of a solvent, such as an alcohol or an ether, such as methanol, ethanol, butanol Or tetrahydrofuran.
  • a solvent such as an alcohol or an ether, such as methanol, ethanol, butanol Or tetrahydrofuran.
  • the reaction is carried out without adding a solvent.
  • the total conversion of IPN to imine in the product obtained in step b) reaches 90 to 99%, and the selectivity is higher than 99%, which is significantly higher than the current level in the industry.
  • step c) is carried out at a temperature of from 50 to 130 ° C and a pressure of from 10 to 30 MPa, preferably at a temperature of from 80 to 120 ° C and a pressure of from 15 to 20 MPa.
  • the reaction liquid in step c) has a temperature rise of 20 to 30 ° C, that is, the outlet temperature of the hydrogenation reactor in which step c) is carried out is 20 to 30 ° C higher than the inlet temperature.
  • Such temperature rise control can It is guaranteed that the cis isomer ratio of the product IPDA is in the range of 75-80%, which is more favorable for downstream industrial applications.
  • the molar ratio of hydrogen to IPN is from 3 to 1000:1, preferably from 10 to 500:1, particularly preferably from 20 to 100:1.
  • Hydrogen may be mixed with the imidized material after the imidization reaction, or may be mixed with IPN or liquid ammonia prior to imidization.
  • step c) is a hydrogenation step which can be carried out by various existing hydrogenation methods without particular limitation.
  • the catalyst of step c) may be supported or Raney type, for example: supported copper, supported nickel, supported cobalt, Raney copper, Raney nickel or Raney cobalt, wherein the supported catalyst
  • the carrier can be a common catalyst carrier.
  • the catalyst described in the step c) preferably employs a supported cobalt catalyst, more preferably a cobalt-alumina-supported cobalt catalyst, and particularly preferably a cobalt-alumina composite nanotube array membrane catalyst.
  • the cobalt and alumina composite nanotube array membrane catalyst is preferably prepared by the method disclosed in the patent document CN103464162A, and the preparation method comprises the following steps:
  • Co is added in an amount of 20 to 30% by weight
  • Al is added in an amount of 70% to 80% by weight based on the sum of the weights of both Co and Al.
  • the space velocity on the catalyst used in step c) is controlled to be from 0.5 to 20 grams of IPN per (ml of catalyst per hour), more preferably from 5 to 15 grams of IPN per milliliter of catalyst per hour. ).
  • the three steps of the process of the invention may be carried out separately in three separate reactors or in the same reactor. It is preferably carried out in three separate reactors separately to facilitate continuous production.
  • steps a) and b) are each carried out continuously using a tubular reactor.
  • steps a) and b) IPN and liquid ammonia are fed from below the tubular reactor and discharged above, in such a way that the reaction is more complete.
  • the reaction of step c) is carried out in a tubular reactor, more preferably in a trickle bed tubular reactor.
  • the inventors started from the imidization reaction rule and found that when the initial acid value of IPN is in the range of 0.02-0.50 mgKOH/g, especially 0.05-0.30 mgKOH/g, and when the imidization reaction proceeds to After a certain degree, the imidization reaction is continued by adding an alkaline acid value regulator of 0.2 to 5 Torr, preferably 0.5 to 3 Torr of the initial IPN molar amount, and the finally obtained IPDA reaction solution ensures the content of the de-cyano product. In the lower case, the secondary amine, amino alcohol and bis-IPDA content are also lower than those reported in the literature, and the IPDA reaction yield is close to 99%.
  • the reaction rate of the IPN imidization reaction step is greatly increased, and the space velocity on the imidization catalyst can reach 70 to 100 g IPN / (ml catalyst ⁇ hour), so that it can be achieved with less catalyst
  • the size of the two-stage imidization reactor is only about 1/5 of the traditional process, which reduces the basic investment of the device construction; at the same time, the reaction rate is greatly improved, the reaction time is saved, and the reaction time is only About 1/5 of the prior art.
  • Pressure refers to gauge pressure
  • Figure 1 shows a flow chart of an embodiment of the invention.
  • FIG. 1 A flow of a specific embodiment of the method of the present invention is shown in FIG.
  • the original The IPN and the liquid ammonia enter the primary imidization reactor 1 for imidization, and the obtained partially imidized reaction solution and the basic acid value regulator enter the secondary imidization reactor 2, and continue.
  • the imidization reaction, the obtained product and hydrogen enter the hydrogenation reactor 3, and finally IPDA is obtained.
  • hydrogen may also be added prior to the imidization reaction step, that is, hydrogen and the raw material IPN together with the liquid ammonia are introduced into the primary imidization reactor 1.
  • the reactor used in the following examples is: the primary imidization reactor 1 and the secondary imidization reactor 2 have a diameter of 20 mm and a height of 100 mm, and the primary imidization reactor 1 is filled with 10 mL. ⁇ -alumina pellet having a diameter of 0.5 mm; the secondary imidization reactor 2 is filled with 10 mL of rod-shaped activated carbon having a diameter of 0.5 mm and a length of 2 mm; the hydrogenation reactor 3 has a diameter of 40 mm and a height of 200 mm, and is filled.
  • Cobalt and alumina composite nanotube array membrane catalyst prepared by the method of Example 2 in the patent document CN103464162A.
  • the acid value of IPN is controlled at 0.30 mgKOH/g, and is added to the primary imidization reactor 1 together with liquid ammonia.
  • the IPN feed rate is 700 g/h
  • the feed rate of liquid ammonia is 2850 g/h
  • the hydrogen flow rate 9500 standard L / h, temperature control at 40 ° C, reaction pressure 20MPa, to obtain a partially imidized reaction solution;
  • step c) The product obtained in step b) is fed to the hydrogenation reactor 3, the inlet temperature of the hydrogenation reactor 3 is controlled at 80 ° C, the outlet temperature is controlled at 100 ° C, and the reaction pressure is 20 MPa.
  • the space velocity of the catalyst in each reactor is shown in Table 1:
  • the acid value of IPN is controlled at 0.15mgKOH/g, and is added to the primary imidization reactor 1 together with liquid ammonia.
  • the IPN feed rate is 800g/h
  • the feed rate of liquid ammonia is 1645g/h
  • the temperature is controlled.
  • the reaction pressure is 15 MPa to obtain a partially imidized reaction solution;
  • step c) The product obtained in step b) is fed to the hydrogenation reactor 3, and hydrogen is introduced at a flow rate of 2170 standard L/h.
  • the inlet temperature of the hydrogenation reactor 3 is controlled at 80 ° C, the outlet temperature is controlled at 100 ° C, and the reaction pressure is 15 MPa.
  • the space velocity of the catalyst in each reactor is shown in Table 3:
  • the acid value of IPN is controlled at 0.05 mg KOH/g, and is added to the primary imidization reactor 1 together with liquid ammonia.
  • the IPN feed rate is 1000 g/h
  • the feed rate of liquid ammonia is 5150 g/h
  • the hydrogen flow rate is 10000 standard L / h
  • the temperature is controlled at 60 ° C
  • the reaction pressure is 20 MPa, to obtain a partially imidized reaction liquid;
  • step c) The product obtained in step b) is fed to a hydrogenation reactor 3, the inlet temperature of the hydrogenation reactor 3 is controlled at 90 ° C, the outlet temperature is controlled at 120 ° C, and the reaction pressure is 20 MPa.
  • the space velocity of the catalyst in each reactor is shown in Table 5:
  • Reactor 1 outlet Reactor 2 outlet Reactor 3 outlet IPN conversion rate 60.50% 85.14% - Double-IPDA precursor content 0.10% 0.93% - IPDA content - —— 86.76% Secondary amine content - —— 6.74% Amino alcohol content - —— 2.50% Double-IPDA content - —— 2.37% De-cyano product content - —— 0.25%
  • the IPN conversion rate at the outlet of the reactor 2 is significantly lower than that in the first embodiment, and the secondary amine, amino alcohol and bis-IPDA content in the product are higher, and the IPDA yield is higher. low.
  • the acid value of the reaction liquid was adjusted in the hydrogenation step c), and the content of secondary products such as secondary amine, amino alcohol and bis-IPDA in the product was higher than that in Example 1, and the yield of IPDA was low.
  • step a) did not adjust the acid value of IPN, the acid value of the IPN raw material was higher, the imidization reaction rate was significantly lower than that of Example 1, the imidization reaction was incomplete, and the by-products in the final product increased, IPDA The yield is low.

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Abstract

L'invention concerne un procédé de préparation de 3-aminométhyl-3,5,5-triméthylcyclohexylamine. Le procédé comprend les étapes consistant à : a) réguler l'indice d'acide de 3-cyano-3,5,5-triméthylcyclohexanone à 0,02-0,50 mg de KOH/g, faire réagir avec de l'ammoniac liquide pour obtenir un liquide de réaction partiellement imidisé ; b) ajouter un régulateur alcalin de l'indice d'acide au liquide de réaction partiellement imidisé obtenu dans l'étape a) en une quantité d'addition de 0,2-5‰ du poids molaire de la 3-cyano-3,5,5-triméthylcyclohexanone pour poursuivre une réaction d'imidisation ; et c) hydrogéner le produit obtenu dans l'étape b) en présence d'hydrogène, d'ammoniac liquide et d'un catalyseur pour produire la 3-aminométhyl-3,5,5-triméthylcyclohexylamine. Le procédé de préparation présente un rendement en 3-aminométhyl-3,5,5-triméthylcyclohexylamine proche de 99 % et présente une plus vitesse spatiale augmentée, une efficacité de réaction augmentée, ce qui permet d'économiser les coûts en catalyseur et en équipement.
PCT/CN2014/089027 2014-10-14 2014-10-21 Procédé de préparation de 3-aminométhyl-3,5,5-triméthylcyclohexylamine WO2016058207A1 (fr)

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ES2696529T3 (es) * 2016-06-10 2019-01-16 Evonik Degussa Gmbh Composición de resina epoxi que contiene 2-(3-(aminometil)-3,5,5-trimetilciclohexil)propan-1,3-diamina (AM-CPDA) como endurecedor
CN107857704B (zh) * 2017-11-21 2020-04-10 万华化学集团股份有限公司 一种制备3-氨甲基-3,5,5-三甲基环己胺的方法及用于该方法的催化剂
CN108017547B (zh) 2017-12-22 2019-07-02 浙江新和成股份有限公司 一种异佛尔酮腈亚胺加氢还原制备异佛尔酮二胺的方法
CN109608639A (zh) * 2018-11-30 2019-04-12 万华化学集团股份有限公司 一种有机聚硅氧烷催化剂及其制备方法和应用

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US6022999A (en) * 1997-12-18 2000-02-08 Basf Aktiengesellschaft Preparation of 3-aminomethyl-3,5,5-trimethylcyclohexylamine having a cis/trans isomer ratio of at least 70:30
CN101568516A (zh) * 2006-12-22 2009-10-28 巴斯夫欧洲公司 氢化3-氰基-3,5,5-三甲基环己基亚胺的连续方法
CN102531917A (zh) * 2010-12-08 2012-07-04 赢创德固赛有限责任公司 用于制备3-氨甲基-3,5,5-三甲基环己胺的方法
CN102924291A (zh) * 2011-08-08 2013-02-13 烟台万华聚氨酯股份有限公司 3-氨甲基-3,5,5-三甲基环己胺的制备方法

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Publication number Priority date Publication date Assignee Title
US5491264A (en) * 1993-07-27 1996-02-13 E. I. Du Pont De Nemours And Company Preparation of isophorone diamine
US6022999A (en) * 1997-12-18 2000-02-08 Basf Aktiengesellschaft Preparation of 3-aminomethyl-3,5,5-trimethylcyclohexylamine having a cis/trans isomer ratio of at least 70:30
CN101568516A (zh) * 2006-12-22 2009-10-28 巴斯夫欧洲公司 氢化3-氰基-3,5,5-三甲基环己基亚胺的连续方法
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CN102924291A (zh) * 2011-08-08 2013-02-13 烟台万华聚氨酯股份有限公司 3-氨甲基-3,5,5-三甲基环己胺的制备方法

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