CN115974699A - Preparation method of aromatic diamine - Google Patents
Preparation method of aromatic diamine Download PDFInfo
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- CN115974699A CN115974699A CN202211670376.4A CN202211670376A CN115974699A CN 115974699 A CN115974699 A CN 115974699A CN 202211670376 A CN202211670376 A CN 202211670376A CN 115974699 A CN115974699 A CN 115974699A
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- aldehyde
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- phenylenediamine
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Abstract
The invention provides a preparation method of aromatic diamine. The preparation method comprises the following steps: aromatic diamine is prepared with aromatic diamine and aldehyde or ketone as material and through adding acid ion exchange resin, and reductive amination in hydrogen atmosphere with metal catalyst. The preparation method has simple process flow and low production cost.
Description
Technical Field
The invention relates to a preparation method of aromatic diamine, belonging to the technical field of fine chemical engineering.
Background
The chain extender is very important for the synthesis of polyurethane, and directly influences the mechanical property and the process property of the product. Chain extenders are more in variety, and are divided into two general categories according to reactive groups: diamine chain extenders containing 2 amino groups (primary or secondary), and diol chain extenders containing 2 hydroxyl groups (primary or secondary). While the difunctional alcoholamines containing both 1 amino group and 1 hydroxyl group can also be used as chain extenders for polyurethanes, their use is relatively rare.
The secondary amine group is replaced by one hydrogen atom on the primary amino group, and the reactivity of the secondary amine group is lower than that of the primary amino group, so that the secondary amine chain extender has the characteristic of longer pot life and can be used for room-temperature curing formulations.
The synthesis method of the secondary amine mainly comprises the following two synthesis methods: (1) Direct alkylation of primary amines is the most common classical method for the most direct synthesis of secondary amines. Generally, halogenated hydrocarbons or their substitutes, sulfates, sulfonates, are reacted with excess primary amines. The disadvantage is the poor chemical selectivity and the inevitable occurrence of over-alkylation reactions. (2) Reductive amination is also one of the important processes for the preparation of secondary amines from primary amines. The method generally employed is that a primary amine and an aldehyde first form an imine or an imine ion intermediate, which is then reduced in situ to a secondary amine.
Chinese patent CN113912514A introduces a preparation method of an aromatic diamine chain extender, which takes acid and Lewis acid as composite catalysts, takes water as a reaction medium, and synthesizes aromatic diamine by Michael addition reaction of aromatic diamine primary amine and acrylonitrile. Chinese patent CN103261145 describes a method for synthesizing aliphatic polyamine with secondary amino group by reacting polyamine with aldehyde compound to obtain aldimine, and then performing hydrogenation reaction. The method adopts a two-step method, needs to distill imine and has a complex flow. Chinese patent CN114315607A describes a method for reacting alpha-hydroxycarboxylic acid with a catalyst by using primary diamine and ketone as raw materials. The method needs post-treatment of alpha-hydroxycarboxylic acid and has complex process.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a preparation method of aromatic diamine, which has simple process flow and reduces the production cost.
In order to achieve the purpose, the invention provides a preparation method of aromatic diamine, which takes aromatic diamine primary diamine and aldehyde (or ketone) as raw materials, adds acid ion exchange resin, and carries out reductive amination through a metal catalyst in a hydrogen atmosphere to obtain aromatic diamine secondary amine.
In one embodiment of the present invention, the aromatic primary diamine used is at least one selected from the group consisting of:
p-phenylenediamine or m-phenylenediamine and diamines in which the benzene ring of p-phenylenediamine or m-phenylenediamine is substituted with a C1-4 linear or branched alkyl group.
In one embodiment of the present invention, the aromatic primary diamine used is at least one selected from the group consisting of:
4,4 '-methylenedianiline and 4,4' -methylenedianiline are diamines in which the benzene ring is substituted with a linear or branched alkyl group having 1 to 4 carbon atoms.
In a further embodiment of the present invention, the aromatic primary diamine used is at least one member selected from the group consisting of those represented by the following structural formulae:
wherein R is H or straight-chain or branched-chain alkyl with 1-4 carbon atoms, and R can be the same or different.
In a further embodiment of the invention, the aromatic primary diamine used is at least one member selected from the group consisting of 3,5-diethyltoluenediamine, 4,4 '-methylenebis (2,6-diethyl) aniline, 4,4' -methylenebis aniline, 4,4 '-methylenebis (2-ethylaniline), p-phenylenediamine, m-phenylenediamine, 4,4' -methylenebis (2-methyl-6-ethylaniline).
In a specific embodiment of the invention, the aldehyde used is one or a combination of several of linear or branched alkyl aldehydes with 2-12 carbon atoms.
In a specific embodiment of the present invention, the ketone used is one or a combination of several kinds of linear or branched alkyl ketones with 2 to 12 carbon atoms.
In a further embodiment of the present invention, the aldehyde used is at least one selected from the group consisting of acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, isovaleraldehyde, caproaldehyde, cyclohexanal, heptaldehyde, caprylic aldehyde, nonanal, capric aldehyde, undecyl aldehyde, dodecanal, 2-ethylbutyraldehyde, benzaldehyde, phenylacetaldehyde.
In a further embodiment of the present invention, the ketone used is at least one selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, cyclohexanone, isophorone, methyl tert-butyl ketone, cyclobutanone, cyclopentanone, acetophenone.
In one embodiment of the invention, the molar ratio of aromatic primary diamine to aldehyde (or ketone) is 1:2-10. Preferably 1:4-6. Specifically, it may be 1:4, 1:5, 1:6.
In one embodiment of the present invention, the acidic ion exchange resin used is a large-pore strong-acid ion exchange resin, such as a large-pore sulfonic anion exchange resin. Furthermore, the addition amount of the acidic ion exchange resin is 1-20% of the mass of the aromatic diamine primary amine. Preferably 5-10%. Specifically, it may be 5%, 6%, 7%, 8%, 9%, 10%.
In one embodiment of the present invention, the metal catalyst used is selected from platinum, palladium, ruthenium, rhodium or nickel supported on activated carbon, alumina or silica; preferably palladium on activated carbon. Specifically, the addition amount of the metal catalyst is 0.1-10% of the mass of the aromatic diamine primary amine; preferably 4% -6%. Specifically, it may be 4%, 5%, 6%.
In one embodiment of the invention, the reductive amination is carried out at a temperature of 40 to 150 ℃ and at a pressure of 0.5 to 8MPa. The preferred temperature is 70-100 deg.C, and the preferred pressure is 2-5MPa.
According to the preparation method of the aromatic diamine, hydrogen protons are dissociated in a system through the acidic ion exchange resin, and the hydrogen protons can effectively catalyze imine synthesis and hydrogenation, so that the reaction conditions are reduced, the reaction is carried out under relatively mild conditions, and the reaction time is shortened. In addition, the acidic ion exchange resin is separated by filtration in the post-treatment process, no other operation is needed, and the operation is simple. The filtered acidic ion exchange resin can be recycled, thereby reducing the production cost.
The aromatic diamine obtained by the preparation method can be used as a curing agent or a chain extender of polyurethane, coating, adhesive, waterproof coating, polyurea and epoxy resin, has a long pot life, is used for adjusting the operation time, and endows the product with excellent physical properties and good tear strength.
Detailed Description
The following detailed description of preferred embodiments of the invention will be made.
Example 1
This example provides a method for preparing an aromatic secondary diamine, comprising the following steps:
216g of p-phenylenediamine, 1032g of n-valeraldehyde, 20g of strongly acidic ion exchange resin Amberlyst 15 and 12g of Pd/C catalyst are sequentially put into a 2L high-pressure reaction kettle at room temperature, and a feeding port is closed. The reaction solution was replaced with nitrogen gas 3 times at room temperature, and then replaced with hydrogen gas at about 1MPa 3 times. Heating to 60 ℃, and reacting for 6 hours under the condition of 2MPa of hydrogen. Cooling to room temperature, exhausting and replacing with nitrogen. Filtering the reaction solution, wherein the filter residue is a mixture of strong acid ion exchange resin and Pd/C, and can be recycled. The filtrate was subjected to distillation under reduced pressure using a rotary evaporator to distill off water produced by the reaction, excess aldehyde and by-produced alcohol. When the concentrated solution was analyzed by gas chromatography, it was found that the conversion of p-phenylenediamine was 100% and the content of N, N' -di-N-pentylp-phenylenediamine was 96.3%.
Example 2
This example provides a method for preparing an aromatic secondary diamine, comprising the following steps:
216g of m-phenylenediamine, 1060g of benzaldehyde, 30g of strongly acidic ion exchange resin and 20g of Pd/C catalyst are sequentially put into a 2L high-pressure reaction kettle at room temperature, and a feeding port is closed. The reaction solution was replaced with nitrogen gas 3 times at room temperature, and then replaced with hydrogen gas at about 1MPa 3 times. Heating to 100 ℃, and carrying out heat preservation reaction for 10 hours under the hydrogen of 4 MPa. Cooling to room temperature, exhausting and replacing with nitrogen. Filtering the reaction solution, wherein the filter residue is a mixture of strong acid ion exchange resin and Pd/C, and can be recycled. The filtrate was subjected to reduced pressure distillation using a rotary evaporator to distill off water produced by the reaction, excess aldehyde and by-produced alcohol. When the concentrated solution was analyzed by a gas chromatograph, it was found that the conversion of m-phenylenediamine was 100% and the content of N, N' -benzhydryl m-phenylenediamine was 97.6%.
Example 3
This example provides a method for preparing an aromatic secondary diamine, comprising the following steps:
297g of 4,4' -methylenedianiline, 696g of propionaldehyde, 30g of strongly acidic ion exchange resin and 20g of Pd/C catalyst are sequentially put into a 2L high-pressure reaction kettle at room temperature, and a feeding port is closed. The reaction solution was replaced with nitrogen gas 3 times at room temperature, and then replaced with hydrogen gas at about 1MPa 3 times. The temperature is increased to 80 ℃, and the reaction is carried out for 5 hours under the condition of 3MPa of hydrogen. Cooling to room temperature, exhausting and replacing with nitrogen. Filtering the reaction solution, wherein the filter residue is a mixture of strong acid ion exchange resin and Pd/C, and can be recycled. The filtrate was subjected to distillation under reduced pressure using a rotary evaporator to distill off water produced by the reaction, excess aldehyde and by-produced alcohol. When the concentrated solution was analyzed by gas chromatography, it was found that the conversion of 4,4 '-methylenedianiline was 100% and the content of 4,4' -methylenebis (N-propylaniline) was 94.1%.
Comparative example 1
This comparative example provides a process for the preparation of an aromatic secondary diamine, which is essentially the same as example 2 except that:
when the concentrated solution was analyzed by a gas chromatograph using basic ion exchange resin D392 as the ion exchange resin, it was found that the conversion of m-phenylenediamine was 40% and the content of N, N' -dibenzyl-m-phenylenediamine was 12%.
Comparative example 2
This comparative example provides a process for the preparation of an aromatic secondary diamine, which is essentially the same as example 2 except that:
the reductive amination temperature is 160 ℃ and the pressure is 10MPa. When the concentrated solution was analyzed by a gas chromatograph, it was found that the conversion of m-phenylenediamine was 80% and the content of N, N' -benzhydryl m-phenylenediamine was 70%.
The above embodiments are only for illustrating the technical idea and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention by this means. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A method for preparing aromatic diamine, wherein the method comprises the following steps:
taking aromatic diamine primary amine and aldehyde or ketone as raw materials, adding acidic ion exchange resin, and carrying out reductive amination through a metal catalyst in a hydrogen atmosphere to obtain aromatic diamine secondary amine; the aromatic binary primary amine is one or a combination of more of p-phenylenediamine, m-phenylenediamine and diamine of which benzene ring is substituted by straight chain or branched chain alkyl with the carbon atom number of 1-4, 4,4' -methylene dianiline and diamine of which benzene ring is substituted by straight chain or branched chain alkyl with the carbon atom number of 1-4;
the aldehyde is one or a combination of more of linear chain or branched chain alkyl aldehyde with 2-12 carbon atoms;
the ketone is one or a combination of more than one of straight chain or branched chain alkyl ketone with 2-12 carbon atoms.
2. The method according to claim 1, wherein the aromatic primary diamine has any one of the following general formulae:
wherein R is H or C1-4 linear chain or branched chain alkyl, and R can be same or different.
3. The production method according to claim 1 or 2, wherein the aromatic primary diamine is one or a combination of 3,5-diethyltoluenediamine, 4,4 '-methylenebis (2,6-diethyl) aniline, 4,4' -methylenedianiline, 4,4 '-methylenebis (2-ethylaniline), p-phenylenediamine, m-phenylenediamine, 4,4' -methylenebis (2-methyl-6-ethylaniline).
4. The production method according to claim 1, wherein the aldehyde is at least one selected from the group consisting of acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, isovaleraldehyde, caproaldehyde, cyclohexanal, heptaldehyde, caprylic aldehyde, pelargonic aldehyde, capric aldehyde, undecylic aldehyde, dodecanal, 2-ethylbutyraldehyde, benzaldehyde, and phenylacetaldehyde.
5. The production method according to claim 1, wherein the ketone is at least one selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, cyclohexanone, isophorone, methyl tert-butyl ketone, cyclobutanone, cyclopentanone, and acetophenone.
6. The method according to claim 1, wherein the molar ratio of the aromatic primary diamine to the aldehyde or ketone is 1:2-10.
7. The method according to claim 6, wherein the molar ratio of the aromatic primary diamine to the aldehyde or ketone is 1:4-6.
8. The production method according to claim 1, wherein the acidic ion exchange resin is a large-pore sulfonic acid-based ion exchange resin;
preferably, the addition amount of the acidic ion exchange resin is 1-20% of the mass of the aromatic diamine primary amine.
9. The production method according to claim 1, wherein the metal catalyst is platinum, palladium, ruthenium, rhodium or nickel supported on activated carbon, alumina, or silica;
the addition amount of the metal catalyst is 0.1-10% of the mass of the aromatic diamine primary amine.
10. The process of claim 1 wherein the reductive amination is carried out at a temperature of 40 ℃ to 150 ℃ and a pressure of 0.5MPa to 8MPa.
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