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
- ketone
- diamine
- aromatic
- phenylenediamine
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- 150000004984 aromatic diamines Chemical class 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 24
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 20
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 20
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 150000002576 ketones Chemical class 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 238000006268 reductive amination reaction Methods 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- -1 aromatic diamine primary amine Chemical class 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 230000002378 acidificating effect Effects 0.000 claims description 11
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 11
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 claims description 11
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 9
- 150000004985 diamines Chemical class 0.000 claims description 9
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 7
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 7
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 6
- 150000003141 primary amines Chemical class 0.000 claims description 5
- YGHRJJRRZDOVPD-UHFFFAOYSA-N 3-methylbutanal Chemical compound CC(C)CC=O YGHRJJRRZDOVPD-UHFFFAOYSA-N 0.000 claims description 4
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 claims description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 4
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims description 4
- HFJRKMMYBMWEAD-UHFFFAOYSA-N dodecanal Chemical compound CCCCCCCCCCCC=O HFJRKMMYBMWEAD-UHFFFAOYSA-N 0.000 claims description 4
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 claims description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims description 4
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- KMPQYAYAQWNLME-UHFFFAOYSA-N undecanal Chemical compound CCCCCCCCCCC=O KMPQYAYAQWNLME-UHFFFAOYSA-N 0.000 claims description 3
- RVCHQYCXJDVJQF-UHFFFAOYSA-N (3,5-diethylphenyl)methanediamine Chemical compound CCC1=CC(CC)=CC(C(N)N)=C1 RVCHQYCXJDVJQF-UHFFFAOYSA-N 0.000 claims description 2
- FOYHNROGBXVLLX-UHFFFAOYSA-N 2,6-diethylaniline Chemical compound CCC1=CC=CC(CC)=C1N FOYHNROGBXVLLX-UHFFFAOYSA-N 0.000 claims description 2
- UNNGUFMVYQJGTD-UHFFFAOYSA-N 2-Ethylbutanal Chemical compound CCC(CC)C=O UNNGUFMVYQJGTD-UHFFFAOYSA-N 0.000 claims description 2
- QJENIOQDYXRGLF-UHFFFAOYSA-N 4-[(4-amino-3-ethyl-5-methylphenyl)methyl]-2-ethyl-6-methylaniline Chemical compound CC1=C(N)C(CC)=CC(CC=2C=C(CC)C(N)=C(C)C=2)=C1 QJENIOQDYXRGLF-UHFFFAOYSA-N 0.000 claims description 2
- CBEVWPCAHIAUOD-UHFFFAOYSA-N 4-[(4-amino-3-ethylphenyl)methyl]-2-ethylaniline Chemical compound C1=C(N)C(CC)=CC(CC=2C=C(CC)C(N)=CC=2)=C1 CBEVWPCAHIAUOD-UHFFFAOYSA-N 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- SHQSVMDWKBRBGB-UHFFFAOYSA-N cyclobutanone Chemical compound O=C1CCC1 SHQSVMDWKBRBGB-UHFFFAOYSA-N 0.000 claims description 2
- KVFDZFBHBWTVID-UHFFFAOYSA-N cyclohexanecarbaldehyde Chemical compound O=CC1CCCCC1 KVFDZFBHBWTVID-UHFFFAOYSA-N 0.000 claims description 2
- KSMVZQYAVGTKIV-UHFFFAOYSA-N decanal Chemical compound CCCCCCCCCC=O KSMVZQYAVGTKIV-UHFFFAOYSA-N 0.000 claims description 2
- FXHGMKSSBGDXIY-UHFFFAOYSA-N heptanal Chemical compound CCCCCCC=O FXHGMKSSBGDXIY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229940100595 phenylacetaldehyde Drugs 0.000 claims description 2
- PJGSXYOJTGTZAV-UHFFFAOYSA-N pinacolone Chemical compound CC(=O)C(C)(C)C PJGSXYOJTGTZAV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000004970 Chain extender Substances 0.000 description 8
- 150000003335 secondary amines Chemical group 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 150000002466 imines Chemical class 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- RGSLUNYPVJQYPO-UHFFFAOYSA-N 1-n,3-n-dibenzylbenzene-1,3-diamine Chemical compound C=1C=CC=CC=1CNC(C=1)=CC=CC=1NCC1=CC=CC=C1 RGSLUNYPVJQYPO-UHFFFAOYSA-N 0.000 description 1
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000004705 aldimines Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 125000004427 diamine group Chemical group 0.000 description 1
- 150000002009 diols Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57123148A (en) * | 1981-01-26 | 1982-07-31 | Sumitomo Chem Co Ltd | Production of secondary amine by reductive alkylation |
| JP2000256277A (en) * | 1999-03-09 | 2000-09-19 | Mitsui Chemicals Inc | Production of n-alkyl-substituted aromatic amino compound |
| CN1660751A (en) * | 2003-11-17 | 2005-08-31 | 萨索尔德国有限公司 | Condensation and hydrogenation reaction for preparing carbonyl contained products |
| US20060217567A1 (en) * | 2005-03-28 | 2006-09-28 | Lee John Y | Diimines and secondary diamines |
| US20080315155A1 (en) * | 2005-12-30 | 2008-12-25 | Albemarle Corporation | Diamines Having Reduced Color |
| CN103261145A (en) * | 2010-12-17 | 2013-08-21 | Sika技术股份公司 | Amines having secondary aliphatic amino groups |
| CN103467305A (en) * | 2012-06-08 | 2013-12-25 | 中国石油化工股份有限公司 | Method for continuously preparing N, N'-bis(1,4-dimethylpentyl)-p-phenylenediamine |
| CN104402797A (en) * | 2014-10-08 | 2015-03-11 | 景县本源精化有限公司 | Preparation method of N,N'-alkylated diaminodiphenyl-methane curing agent |
| CN106431932A (en) * | 2015-08-04 | 2017-02-22 | 江苏圣奥化学科技有限公司 | Synthesis method of N-2-ethylhexyl-N'-phenyl p-phenylenediamine |
| CN109201046A (en) * | 2018-09-06 | 2019-01-15 | 青岛科技大学 | A kind of preparation method and applications of the residual tar base mesoporous carbon supported noble metal catalyst of kettle |
| CN109988080A (en) * | 2019-04-19 | 2019-07-09 | 武汉理工大学 | A method of using macropore strong acid cation exchanger resin as catalyst preparation imines |
| CN111909039A (en) * | 2020-09-07 | 2020-11-10 | 江苏湘园化工有限公司 | Preparation method of aliphatic series dibasic secondary amine with high steric hindrance effect |
-
2022
- 2022-12-25 CN CN202211670376.4A patent/CN115974699A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57123148A (en) * | 1981-01-26 | 1982-07-31 | Sumitomo Chem Co Ltd | Production of secondary amine by reductive alkylation |
| JP2000256277A (en) * | 1999-03-09 | 2000-09-19 | Mitsui Chemicals Inc | Production of n-alkyl-substituted aromatic amino compound |
| CN1660751A (en) * | 2003-11-17 | 2005-08-31 | 萨索尔德国有限公司 | Condensation and hydrogenation reaction for preparing carbonyl contained products |
| US20060217567A1 (en) * | 2005-03-28 | 2006-09-28 | Lee John Y | Diimines and secondary diamines |
| US20080315155A1 (en) * | 2005-12-30 | 2008-12-25 | Albemarle Corporation | Diamines Having Reduced Color |
| CN103261145A (en) * | 2010-12-17 | 2013-08-21 | Sika技术股份公司 | Amines having secondary aliphatic amino groups |
| CN103467305A (en) * | 2012-06-08 | 2013-12-25 | 中国石油化工股份有限公司 | Method for continuously preparing N, N'-bis(1,4-dimethylpentyl)-p-phenylenediamine |
| CN104402797A (en) * | 2014-10-08 | 2015-03-11 | 景县本源精化有限公司 | Preparation method of N,N'-alkylated diaminodiphenyl-methane curing agent |
| CN106431932A (en) * | 2015-08-04 | 2017-02-22 | 江苏圣奥化学科技有限公司 | Synthesis method of N-2-ethylhexyl-N'-phenyl p-phenylenediamine |
| CN109201046A (en) * | 2018-09-06 | 2019-01-15 | 青岛科技大学 | A kind of preparation method and applications of the residual tar base mesoporous carbon supported noble metal catalyst of kettle |
| CN109988080A (en) * | 2019-04-19 | 2019-07-09 | 武汉理工大学 | A method of using macropore strong acid cation exchanger resin as catalyst preparation imines |
| CN111909039A (en) * | 2020-09-07 | 2020-11-10 | 江苏湘园化工有限公司 | Preparation method of aliphatic series dibasic secondary amine with high steric hindrance effect |
Non-Patent Citations (2)
| Title |
|---|
| STEFAN MICHLIK等: "The Iridium-Catalyzed Synthesis of Symmetrically and Unsymmetrically Alkylated Diamines under Mild Reaction Conditions", ADV. SYNTH. CATAL., vol. 354, 6 March 2012 (2012-03-06), pages 847 - 862 * |
| 丁巧灵;张群峰;丰枫;卢春山;马磊;: "醛/酮与胺还原烷基化反应的研究进展", 化工生产与技术, vol. 19, no. 3, 25 June 2012 (2012-06-25), pages 24 - 27 * |
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