CN115073319A - Modification separation method of alicyclic amine isomer - Google Patents
Modification separation method of alicyclic amine isomer Download PDFInfo
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- CN115073319A CN115073319A CN202210746130.4A CN202210746130A CN115073319A CN 115073319 A CN115073319 A CN 115073319A CN 202210746130 A CN202210746130 A CN 202210746130A CN 115073319 A CN115073319 A CN 115073319A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/32—Separation; Purification; Stabilisation; Use of additives
- C07C253/34—Separation; Purification
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- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- 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
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- 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
Abstract
The invention provides a method for modifying and separating alicyclic amine isomers. The method comprises the following steps: modifying the PACM heterogeneous mixture by acrylonitrile to obtain a mixture of mononitrile ethyl-cis PACM, cis-trans PACM and trans-trans PACM, and rectifying to extract cis-trans PACM and trans-trans PACM; the mixture of cis-trans PACM and trans-trans PACM extracted by acrylonitrile modification rectification is used for obtaining the mixture of mononitrile ethyl-cis-trans/trans-cis PACM and trans-trans PACM, and the trans-trans PACM is extracted by rectification; the inverse PACM extracted by acrylonitrile modification and rectification is used to obtain the mononitrile ethyl-inverse PACM. By adopting the method, the pure products of different acrylonitrile modified PACM isomers can be accurately obtained.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a modification separation method of alicyclic amine isomers.
Background
Epoxy resin is essentially a thermosetting material, and the application field thereof has penetrated from daily necessities to various fields such as high and new technology field. At present, the application market of common epoxy resin is nearly saturated, and the demand of epoxy resin in high-end fields like the electronic industry, the automobile industry, the marine industry, the container industry and the like is increasing day by day, and a lot depends on import. Therefore, the development prospect in the field of epoxy resin is very broad, and higher requirements are also put forward on the quality of the curing agent, so that the development of a high-end curing agent with obvious differentiation and more excellent performance is required.
Diaminodicyclohexylmethane (PACM) is a very important alicyclic diamine, three stereoisomers with different thermodynamic properties of trans-trans, cis-trans and cis-cis exist, the composition ratio of the three isomers directly determines the properties and the applications of PACM products and derivative products, and the PACM with single or specific isomers is difficult to obtain by adopting a separation means; for example, common trans-PACMs are PACM 20, PACM 50 and PACM 70, the application fields of which are completely different, only PACM 20 can be applied in the field of epoxy curing agents, and the production technology difficulty is very high, which seriously influences the application expansion of PACM and derivatives thereof in the field of high-end epoxy, so that an isomer separation means of PACM or derivatives thereof needs to be developed.
CN109535007A discloses a method for separating diaminodicyclohexylmethane isomers, wherein a ketone compound and PACM are condensed to generate an imine compound, and then the imine compound is decomposed under the action of a catalyst to obtain the PACM and the ketone compound of a specific isomer again; the process of the invention is too complex, and the PACM separation can be realized only by multi-step catalysis, the technical difficulty is higher, and the product purity is lower.
CN 102040524B discloses a separation processing method of 4, 4' -diaminodicyclohexyl methane isomer, the invention adopts a mode of repeatedly extracting by solvent and then carrying out physical crystallization for separation, but the effect is general, only PACM 50 can be separated to obtain two products of PACM 20 and PACM 70, single or specific isomer can not be obtained, and the invention has limited application range.
CN 107406365B discloses an isomerization method of diamino dicyclohexyl methane, the invention adopts imine compounds and alkaline earth metal to carry out isomerization reaction with PACM, and finally the PACM 70 compound is generated by the conversion of PACM 50; the invention also has no means for separating PACM isomers, and has little meaning.
In summary, the methods for separating isomers of PACM and derivatives thereof have been reported to a very small extent so far, which makes the PACM 20 production technology difficult and the productivity unable to meet the market demand of high-end epoxy resin, so that it is necessary to develop a separation means for isomers of PACM derivatives with more excellent performance.
Disclosure of Invention
The invention aims to provide a method for separating isomers of modified alicyclic amine, aiming at the defects of the prior PACM and derivative isomer separation method technology thereof. The method realizes the separation of three isomers of trans-trans, cis-trans and cis-cis of the mononitrile ethyl PACM and the preparation of products by a one-step method through accurately controlling the reaction temperature and the material ratio, and has very obvious value for improving the application performance of the PACM and deriving the differential PACM products.
In order to achieve the purpose, the invention provides the following technical scheme:
a process for the modified separation of diaminodicyclohexylmethane (PACM) isomers, the process comprising the steps of:
s1: modifying the PACM heterogeneous mixture by acrylonitrile to obtain a mixture of mononitrile ethyl-cis PACM, cis-trans PACM and trans-trans PACM, and rectifying to extract cis-trans PACM and trans-trans PACM;
s2: the mixture of cis-trans PACM and trans-trans PACM extracted by acrylonitrile modification S1 rectification is used for obtaining the mixture of mononitrile ethyl-cis-trans/trans-cis PACM and trans-PACM, and the trans-trans PACM is extracted by rectification;
s3: the inverse PACM extracted by the rectification of acrylonitrile modified S2 is used to obtain mononitrile ethyl-inverse PACM.
The PACM of the present invention is a typical symmetric methane bridge saturated alicyclic structure having three structures: cis, trans and trans, the structural formulas of which are respectively as follows:
and for the product mononitrile ethyl PACM, it has four structures: cis-cis, cis-trans, trans-cis and trans, the structural formulas of which are respectively as follows:
the normal solid melting points of the three isomers of the PACM are respectively about 36 ℃, 61 ℃ and 65 ℃, the stability and the melting points of the product have certain differences due to different compositions of the contained stereoisomers of the PACM at normal temperature, for example, the PACM 50 is liquid at normal temperature, and the PACM 20 is liquid at normal temperature; therefore, the structural stability of the three parts still has certain difference at different temperatures, and the three parts are separated based on the invention. Wherein, the mononitrile ethyl-cis-trans/trans-cis PACM refers to mononitrile ethyl-cis-trans PACM and mononitrile ethyl-trans-cis PACM.
In the invention, the PACM isomeric mixture of S1 contains 4, 4' -diaminodicyclohexyl methane, and the composition of the PACM isomeric mixture is that the content of trans-trans PACM is 10-70 wt%, the content of cis-trans PACM is 15-70 wt%, and the content of cis-cis PACM is 10-40 wt%; preferably, the content of trans-trans PACM is 15-65 wt%, the content of cis-trans PACM is 20-65 wt%, and the content of cis-trans PACM is 15-35 wt%.
In the present invention, the molar weight ratio of acrylonitrile to PACM isomeric mixture added in S1 is (0.1-0.4): 1, preferably (0.15-0.35): 1.
In the invention, a diluent is added or not added to the S1, and ethanol is preferably added as the diluent; preferably, the diluent is added in an amount of 1 to 20 wt%, preferably 5 to 10 wt% of the PACM isomeric mixture.
In the invention, the reaction temperature of S1 is 5-15 ℃, preferably 8-12 ℃.
In the invention, the reaction time of S1 is 0.5-5 h, preferably 1-2 h; preferably, the rectification temperature of S1 is 150-250 ℃, and preferably 180-230 ℃; the pressure is 1-5 KPa absolute pressure, 2-3 KPa absolute pressure is preferred, and the treatment time is 1-6 h, 2-4 h is preferred.
In the present invention, the molar weight ratio of S2 acrylonitrile to the PACM isomeric mixture is (0.2-0.7): 1, preferably (0.20-0.65): 1.
In the invention, the reaction temperature of S2 is 18-30 ℃, preferably 20-25 ℃.
In the invention, the reaction time of the S2 is 0.5-5 h, preferably 1-2 h; preferably, the rectification temperature of S2 is 150-250 ℃, and preferably 190-240 ℃; the pressure is 1-5 KPa absolute pressure, 2-3 KPa absolute pressure is preferred, and the treatment time is 1-6 h, 2-4 h is preferred.
In the present invention, the molar weight ratio of S3 acrylonitrile to PACM is (0.1-0.7): 1, preferably (0.15-0.65): 1.
In the invention, the reaction temperature of S3 is 35-50 ℃, preferably 40-45 ℃.
In the invention, the reaction time of the S3 is 0.5-5 h, preferably 1-2 h.
It is another object of the present invention to provide a PACM isomer product containing mononitrile ethyl groups.
The product is prepared by the modification and separation method, and is one or more of monoethyl mononitrile-cis PACM, monoethyl mononitrile-cis/trans-cis-PACM and ethyl mononitrile-trans-PACM; preferably, the purity of the PACM isomer product containing mononitrile ethyl is more than or equal to 99 wt%.
It is a further object of the present invention to provide the use of a process for the modified separation of diaminodicyclohexylmethane (PACM) isomers.
The application of the method for modifying and separating the diaminodicyclohexylmethane (PACM) isomer is to separate the diaminodicyclohexylmethane (PACM) isomer and respectively prepare the PACM isomer containing mononitrile ethyl.
In the present invention, the pressures are all absolute pressures unless otherwise specified.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
1) the separation of three isomers of trans-trans, cis-trans and cis-cis of the mononitrile ethyl PACM and the preparation of the product are realized by controlling the reaction temperature and the material ratio.
2) The purities of different isomers of the nitrile ethyl PACM can reach more than 99 wt%.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the examples.
Sources of reaction raw materials:
PACM 20: 15 wt% of trans-trans, 50 wt% of cis-trans, 35 wt% of cis-cis, and Wanhua chemical;
the PACM 50: 45 wt% of trans-trans, 30 wt% of cis-trans, 25 wt% of cis-cis, and Wanhua chemical;
the PACM 70: trans-trans 65 wt%, cis-trans 20 wt%, cis-cis 15 wt%, Wanhua chemical;
acrylonitrile: purity is more than or equal to 99.5 percent, Beijing Yinuoki company;
2-pentanone: the purity is more than or equal to 99.0 percent, and the alatin is used;
Pd/C catalyst: metal content 4 wt%, zhuangyi wangfeng corporation;
ZSM-5 catalyst: jicang nanometer corporation;
ethanol: purity is more than or equal to 99.5 percent, Beijing Yinuoki company;
the test method comprises the following steps:
gas chromatography: agilent 7890 and DB-5(30 mm. times.0.25 mmID. times.0.25 μm) were used, with a sample injector temperature of 280 ℃ and a detector temperature of 300 ℃. The temperature-raising program is as follows: the initial column temperature was 50 ℃ and held for 2 min; heating to 80 deg.C at 5 deg.C/min, and maintaining for 0 min; the temperature is raised to 300 ℃ at a speed of 15 ℃/min and kept for 15 min. The component content was determined by normalization.
A rectifying tower: diameter of tower
The tower is 1400mm high and made of glass tower structure, and the tower is filled with
Stainless steel theta-net ring type packing. The tower bottom is a three-neck flask with the volume of 1000ml and is arranged outside the towerThe wall is plated with a metal heat-insulating film, and the power is 300W for heating and heat insulation.
Example 1
S1: adding 210g of PACM 20(1mol) and 10.5g of ethanol into a three-neck flask, dropwise adding 18.55g of acrylonitrile (0.35mol) when heating to 8 ℃, stirring at a constant temperature for reacting for 2 hours to obtain reaction mother liquor A; distilling the mother liquor A at the normal pressure of 80 ℃ for 1h, then carrying out rectification purification for 2h at the temperature of 180 ℃ and the absolute pressure of 2KPa, collecting cis-trans PACM and trans-trans PACM at the tower top, and collecting mononitrile ethyl-cis PACM at the tower bottom, wherein the purity is 99.2 wt%.
S2: continuously adding ethanol extracted from distillation of S1 and cis-trans PACM and trans-trans PACM extracted from the top of the tower into a three-neck flask for bottom paving, dropwise adding 26.5g of acrylonitrile (0.5mol) when the mixture is heated to 20 ℃, and stirring and reacting for 2 hours at constant temperature to obtain reaction mother liquor B; and distilling the mother liquor B at the normal pressure and the temperature of 80 ℃ for 1h, then carrying out rectification and purification for 2h under the conditions of 190 ℃ and absolute pressure of 2KPa, collecting trans-trans PACM at the tower top, and collecting mono-nitrile ethyl-cis-trans/trans-cis PACM at the tower bottom, wherein the purity is 99.3 wt%.
S3: continuously adding ethanol extracted from distillation of S2 and reverse reaction PACM extracted from the top of the tower into a three-neck flask for bottom paving, dropwise adding 7.95g of acrylonitrile (0.15mol) when heating to 40 ℃, stirring at a constant temperature for reacting for 2 hours to obtain reaction mother liquor C; after the mother liquor C is distilled for 1h at the normal pressure and the temperature of 80 ℃, the purity of the mononitrile ethyl-trans-PACM extracted from the tower bottom is 99.1 wt%.
Example 2
S1: adding 210g of PACM 50(1mol) and 21g of ethanol into a three-neck flask, dropwise adding 13.25g of acrylonitrile (0.25mol) when heating to 12 ℃, and stirring at a constant temperature for reaction for 1 hour to obtain reaction mother liquor A; distilling the mother liquor A at the normal pressure of 80 ℃ for 1h, then carrying out rectification and purification for 4h at the temperature of 200 ℃ and the absolute pressure of 3KPa, collecting cis-trans PACM and trans-trans PACM at the tower top, and collecting mononitrile ethyl-cis PACM at the tower bottom, wherein the purity is 99.3 wt%.
S2: continuously adding ethanol extracted from distillation of S1 and cis-trans PACM and trans-trans PACM extracted from the top of the tower into a three-neck flask for bottom paving, dropwise adding 15.9g of acrylonitrile (0.3mol) when the mixture is heated to 25 ℃, and stirring and reacting for 1 hour at constant temperature to obtain reaction mother liquor B; and distilling the mother liquor B at the normal pressure of 80 ℃ for 1h, then carrying out rectification and purification for 4h at the temperature of 220 ℃ and the absolute pressure of 3KPa, collecting trans-trans PACM at the tower top, and collecting mono-nitrile ethyl-cis-trans/trans-cis PACM at the tower bottom, wherein the purity is 99.6 wt%.
S3: continuously adding ethanol extracted from distillation of S2 and reverse reaction PACM extracted from the top of the tower into a three-neck flask for bottom paving, dropwise adding 23.85g of acrylonitrile (0.45mol) when the temperature is heated to 45 ℃, stirring and reacting for 1h at constant temperature to obtain reaction mother liquor C; after the mother liquor C is distilled for 1h at the normal pressure and the temperature of 80 ℃, the purity of the mononitrile ethyl-trans-PACM extracted from the tower bottom is 99.2 wt%.
Example 3
S1: adding 210g of PACM 70(1mol) and 12.6g of ethanol into a three-neck flask, dropwise adding 7.95g of acrylonitrile (0.15mol) when heating to 10 ℃, stirring at a constant temperature for reacting for 2 hours to obtain reaction mother liquor A; distilling the mother liquor A at the normal pressure of 80 ℃ for 1h, then carrying out rectification and purification for 3h at the temperature of 230 ℃ and the absolute pressure of 2KPa, collecting cis-trans PACM and trans-trans PACM at the tower top, and collecting mononitrile ethyl-cis PACM at the tower bottom, wherein the purity is 99.2 wt%.
S2: continuously adding ethanol extracted from distillation of S1 and cis-trans PACM and trans-trans PACM extracted from the top of the tower into a three-neck flask for bottom paving, dropwise adding 13.3g of acrylonitrile (0.25mol) when the mixture is heated to 22 ℃, and stirring and reacting for 2 hours at constant temperature to obtain reaction mother liquor B; and distilling the mother liquor B at the normal pressure of 80 ℃ for 1h, then carrying out rectification and purification for 2h at the temperature of 240 ℃ and the absolute pressure of 2KPa, collecting trans-trans PACM at the tower top, and collecting mono-nitrile ethyl-cis-trans/trans-cis PACM at the tower bottom, wherein the purity is 99.4 wt%.
S3: adding ethanol extracted from distillation of S2 and reverse reaction PACM extracted from the top of the tower into a three-neck flask continuously for bottom paving, adding 34.45g of acrylonitrile (0.65mol) dropwise when the mixture is heated to 42 ℃, stirring and reacting for 2 hours at constant temperature to obtain reaction mother liquor C; after the mother liquor C is distilled for 1h at the normal pressure and the temperature of 80 ℃, the purity of the mononitrile ethyl-trans-PACM extracted from the tower bottom is 99.3 wt%.
Example 4
S1: adding 210g of PACM 20(1mol) and 16.8g of ethanol into a three-neck flask, dropwise adding 18.6g of acrylonitrile (0.35mol) when heating to 10 ℃, stirring at a constant temperature for reacting for 1h to obtain reaction mother liquor A; distilling the mother liquor A at the normal pressure of 80 ℃ for 1h, then carrying out rectification and purification for 2h at the temperature of 190 ℃ and the absolute pressure of 3KPa, collecting cis-trans PACM and trans-trans PACM at the tower top, and collecting mononitrile ethyl-cis PACM at the tower bottom, wherein the purity is 99.1 wt%.
S2: continuously adding ethanol extracted from distillation of S1 and cis-trans PACM and trans-trans PACM extracted from the top of the tower into a three-neck flask for bottom paving, dropwise adding 29.2g of acrylonitrile (0.55mol) when the mixture is heated to 25 ℃, and stirring and reacting for 1 hour at constant temperature to obtain reaction mother liquor B; and distilling the mother liquor B at the normal pressure of 80 ℃ for 1h, then carrying out rectification and purification for 3h under the conditions of 200 ℃ and absolute pressure of 3KPa, collecting trans-trans PACM at the tower top, and collecting mono-nitrile ethyl-cis-trans/trans-cis PACM at the tower bottom, wherein the purity is 99.4 wt%.
S3: continuously adding ethanol extracted from distillation of S2 and reverse reaction PACM extracted from the top of the tower into a three-neck flask for bottom paving, dropwise adding 9.5g of acrylonitrile (0.18mol) when the temperature is heated to 40 ℃, stirring and reacting for 1h at constant temperature to obtain reaction mother liquor C; after the mother liquor C is distilled for 1h at the normal pressure and the temperature of 80 ℃, the purity of the mononitrile ethyl-trans-PACM extracted from the tower bottom is 99 wt%.
Comparative example 1
In the case of the embodiment of comparative example 1, the amount of acrylonitrile was varied.
S1: adding 210g of PACM 20(1mol) and 10.5g of ethanol into a three-neck flask, dropwise adding 29.15g of acrylonitrile (0.55mol) when heating to 8 ℃, stirring at a constant temperature for reacting for 2 hours to obtain reaction mother liquor A; distilling the mother liquor A at the normal pressure of 80 ℃ for 1h, then carrying out rectification purification for 2h at the temperature of 180 ℃ and the absolute pressure of 2KPa, collecting cis-trans PACM and trans-trans PACM at the tower top, and collecting mononitrile ethyl-cis-trans PACM at the tower bottom, wherein the purity is 95.8 wt%.
S2: continuously adding ethanol extracted from distillation of S1 and cis-trans PACM and trans-trans PACM extracted from the top of the tower into a three-neck flask for bottom paving, dropwise adding 34.5g of acrylonitrile (0.65mol) when the mixture is heated to 20 ℃, and stirring and reacting for 2 hours at constant temperature to obtain reaction mother liquor B; and distilling the mother liquor B at the normal pressure of 80 ℃ for 1h, then carrying out rectification and purification for 2h at the temperature of 190 ℃ and the absolute pressure of 2KPa, collecting trans-trans PACM at the tower top, and collecting mono-nitrile ethyl-cis-trans/trans-cis PACM at the tower bottom, wherein the purity is 93.6 wt%.
S3: continuously adding ethanol extracted from distillation of S2 and reverse reaction PACM extracted from the top of the tower into a three-neck flask for bottom paving, dropwise adding 13.25g of acrylonitrile (0.25mol) when heating to 40 ℃, stirring at a constant temperature for reacting for 2 hours to obtain reaction mother liquor C; after the mother liquor C is distilled for 1h at the normal pressure and the temperature of 80 ℃, the purity of the mononitrile ethyl-trans-PACM extracted from the tower bottom is 99.1 wt%.
Comparative example 2
The reaction temperature was varied in comparison with the protocol in example 2.
S1: adding 210g of PACM 50(1mol) and 21g of ethanol into a three-neck flask, dropwise adding 13.25g of acrylonitrile (0.25mol) when heating to 50 ℃, and stirring at a constant temperature for reaction for 1 hour to obtain reaction mother liquor A; distilling the mother liquor A at the normal pressure of 80 ℃ for 1h, then carrying out rectification and purification for 4h at the temperature of 200 ℃ and the absolute pressure of 3KPa, collecting cis-trans PACM and trans-trans PACM at the tower top, and collecting mononitrile ethyl-cis PACM at the tower bottom, wherein the purity is 94.3 wt%.
S2: continuously adding ethanol extracted from distillation of S1 and cis-trans PACM and trans-trans PACM extracted from the top of the tower into a three-neck flask for bottom paving, dropwise adding 15.9g of acrylonitrile (0.3mol) when the temperature is heated to 50 ℃, and stirring and reacting for 1 hour at constant temperature to obtain reaction mother liquor B; distilling the mother liquor B at the normal pressure of 80 ℃ for 1h, then carrying out rectification purification for 4h at the temperature of 220 ℃ under the absolute pressure of 3KPa, and collecting reverse reaction PACM at the tower top with the purity of 99.2 wt%; mononitrile ethyl-cis-trans-cis-PACM is extracted from the bottom of the tower, and the purity is 91.6 wt%.
S3: continuously adding ethanol extracted from distillation of S2 and reverse reaction PACM extracted from the top of the tower into a three-neck flask for bottom paving, dropwise adding 23.85g of acrylonitrile (0.45mol) when heating to 50 ℃, stirring at constant temperature for reacting for 1h to obtain reaction mother liquor C; after the mother liquor C is distilled for 1h at the normal pressure and the temperature of 80 ℃, the purity of the mononitrile ethyl-trans-PACM extracted from the tower bottom is 99.2 wt%.
Comparative example 3
The separation of the nitrile ethyl PACM isomers was carried out using the method provided in the patent publication No. CN 109535007A.
S1: adding 210g of PACM 20(1mol), 189g of 2-pentanone (3.3mol) and 6.3g of Pd/C catalyst into a three-neck flask, and stirring and reacting at a constant temperature for 2 hours when the temperature is heated to 80 ℃ to obtain reaction mother liquor A; the conversion rate of PACM can reach 99.5% by gas phase analysis.
S2: filtering the reaction mother liquor A by using filter paper, adding the filtered reaction mother liquor A into another three-neck flask, adding 16.8g of ZSM-5 catalyst, heating the mixture to 80 ℃, stirring the mixture at a constant temperature for reaction for 2 hours to obtain reaction mother liquor A, rectifying and purifying the reaction mother liquor A for 2 hours at 190 ℃ under the absolute pressure of 50Pa, and collecting tower top fraction A1, wherein the total amount is 73.5 g. The purity of the PACM is 99.5 percent through gas phase analysis, wherein the content of cis-PACM is 96.5 percent; the mixture was further mixed with 18.6g of acrylonitrile and stirred at 30 ℃ for 0.5h to obtain reaction mother liquor A2, and after the mother liquor A2 was distilled at 80 ℃ under normal pressure for 1h, the purity of the corresponding product was 96.5% by chromatography to obtain the mono-nitrile-ethyl cis-PACM.
S3: adding the S2 rectification overhead fraction A1 into a three-neck flask, adding 16.8g of ZSM-5 catalyst, stirring and reacting for 2 hours at constant temperature when heating to 50 ℃ to obtain reaction mother liquor B, rectifying and purifying the mother liquor B for 2 hours at 190 ℃ under the absolute pressure of 50Pa, and collecting overhead fraction B1, wherein the total amount is 105 g. The purity of the PACM is 99.5 percent through gas phase analysis, wherein the content of cis-trans PACM is 95.5 percent; the reaction mother liquor B2 was obtained by further mixing it with 26.5g of acrylonitrile and stirring at 40 ℃ for 0.5h, and the purity of the mononitrile cis-trans PACM was 95.0% by chromatographic analysis of the corresponding product after distillation of the mother liquor B2 at 80 ℃ under normal pressure for 1 h.
S4: adding the S3 rectification overhead fraction B1 into a three-neck flask, adding 16.8g of ZSM-5 catalyst, stirring and reacting for 2 hours at constant temperature when heating to 30 ℃ to obtain reaction mother liquor C, placing the mother liquor C under the conditions of 190 ℃ and absolute pressure of 50Pa for rectification and purification for 2 hours, and collecting overhead fraction D1, wherein the total amount is 31.5 g. The purity of the PACM is 99.5 percent through gas phase analysis, wherein the content of the trans-PACM is 95.2 percent; the reaction mother liquor D2 was obtained by further mixing with 8.0g of acrylonitrile and stirring at 50 ℃ for 0.5h, and the purity of the corresponding product was 94.9% by chromatography after the mother liquor D2 was distilled at 80 ℃ under normal pressure for 1 h.
The application of the present invention is not limited to the above embodiments, and any modifications or changes made by those skilled in the art within the spirit of the present invention are included in the scope of the present invention.
Claims (7)
1. A process for the modified separation of diaminodicyclohexylmethane (PACM) isomers, characterized in that it comprises the following steps:
s1: modifying the PACM heterogeneous mixture by acrylonitrile to obtain a mixture of mononitrile ethyl-cis PACM, cis-trans PACM and trans-trans PACM, and rectifying to extract cis-trans PACM and trans-trans PACM;
s2: the mixture of cis-trans PACM and trans-trans PACM extracted by acrylonitrile modification S1 rectification is used for obtaining the mixture of mononitrile ethyl-cis-trans/trans-cis PACM and trans-PACM, and the trans-trans PACM is extracted by rectification;
s3: the inverse PACM extracted by the rectification of acrylonitrile modified S2 is used to obtain mononitrile ethyl-inverse PACM.
2. The process of claim 1, wherein the PACM isomeric mixture of S1 comprises 4, 4' -diaminodicyclohexylmethane having a composition comprising 10 to 70 wt% trans-trans PACM, 15 to 70 wt% cis-trans PACM, and 10 to 40 wt% cis-cis PACM; preferably, the content of trans-trans PACM is 15-65 wt%, the content of cis-trans PACM is 20-65 wt%, and the content of cis-trans PACM is 15-35 wt%.
3. The process according to claim 1 or 2, characterized in that the molar weight ratio of acrylonitrile added in S1 to PACM isomeric mixture is (0.1-0.4): 1, preferably (0.15-0.35): 1;
and/or, the S1 is added or not added with a diluent, preferably ethanol is added as the diluent;
preferably, the addition amount of the diluent is 1-20 wt% of the PACM isomeric mixture, preferably 5-10 wt%;
and/or the reaction temperature of S1 is 5-15 ℃, preferably 8-12 ℃;
and/or the reaction time of the S1 is 0.5-5 h, preferably 1-2 h;
preferably, the rectification temperature of S1 is 150-250 ℃, and preferably 180-230 ℃; the pressure is 1-5 KPa absolute pressure, 2-3 KPa absolute pressure is preferred, and the treatment time is 1-6 h, 2-4 h is preferred.
4. The process of any of claims 1-3, wherein the molar weight ratio of S2 acrylonitrile to PACM isomeric mixture is (0.2-0.7): 1, preferably (0.20-0.65): 1;
and/or the reaction temperature of S2 is 18-30 ℃, preferably 20-25 ℃;
and/or the reaction time of the S2 is 0.5-5 h, preferably 1-2 h;
preferably, the rectification temperature of S2 is 150-250 ℃, and preferably 190-240 ℃; the pressure is 1-5 KPa absolute pressure, 2-3 KPa absolute pressure is preferred, and the treatment time is 1-6 h, 2-4 h is preferred.
5. The process of any one of claims 1 to 4, wherein the molar weight ratio of S3 acrylonitrile to PACM is (0.1-0.7): 1, preferably (0.15-0.65): 1;
and/or the reaction temperature of S3 is 35-50 ℃, preferably 40-45 ℃;
and/or the reaction time of the S3 is 0.5-5 h, preferably 1-2 h.
6. A mono-cyanoethyl-containing PACM isomer product, prepared by the modified separation process of any one of claims 1 to 5, wherein said product is one or more of mono-cyanoethyl-cis-PACM, mono-cyanoethyl-cis-trans/cis-PACM, mono-cyanoethyl-trans-PACM;
preferably, the purity of the PACM isomer product containing mononitrile ethyl is greater than or equal to 99 wt%.
7. Use of a modified separation process for diaminodicyclohexylmethane (PACM) isomers, which is the modified separation process of any one of claims 1 to 5, for separating diaminodicyclohexylmethane (PACM) isomers while separately producing PACM isomers containing mononitrile ethyl groups.
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| US20060051524A1 (en) * | 2002-05-31 | 2006-03-09 | Gibbons Wayne M | Hybrid polymer materials for liquid crystal alignment layers |
| CN102040524A (en) * | 2010-11-25 | 2011-05-04 | 浙江台州清泉医药化工有限公司 | Separation processing method for isomer mixture of 4,4'-methylenebis(cyclohexylamine) |
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| US20060051524A1 (en) * | 2002-05-31 | 2006-03-09 | Gibbons Wayne M | Hybrid polymer materials for liquid crystal alignment layers |
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