CN102976956B - Method for preparing 3-aminomethyl-3,5,5-trimethyl cyclohexylamine - Google Patents
Method for preparing 3-aminomethyl-3,5,5-trimethyl cyclohexylamine Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 84
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 150000003141 primary amines Chemical class 0.000 claims abstract description 55
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 150000002466 imines Chemical class 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 23
- OITMBHSFQBJCFN-UHFFFAOYSA-N 2,5,5-trimethylcyclohexan-1-one Chemical compound CC1CCC(C)(C)CC1=O OITMBHSFQBJCFN-UHFFFAOYSA-N 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- -1 Cycloalkyl amine Chemical class 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000005915 ammonolysis reaction Methods 0.000 claims description 5
- 150000004982 aromatic amines Chemical class 0.000 claims description 5
- 150000003973 alkyl amines Chemical class 0.000 claims description 4
- 150000003974 aralkylamines Chemical group 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229960001866 silicon dioxide Drugs 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 23
- 239000006227 byproduct Substances 0.000 abstract description 13
- JJDFVIDVSCYKDS-UHFFFAOYSA-N 1,3,3-trimethyl-5-oxocyclohexane-1-carbonitrile Chemical compound CC1(C)CC(=O)CC(C)(C#N)C1 JJDFVIDVSCYKDS-UHFFFAOYSA-N 0.000 abstract description 2
- 238000007098 aminolysis reaction Methods 0.000 abstract 2
- NNGAQKAUYDTUQR-UHFFFAOYSA-N cyclohexanimine Chemical compound N=C1CCCCC1 NNGAQKAUYDTUQR-UHFFFAOYSA-N 0.000 abstract 2
- BRRVXFOKWJKTGG-UHFFFAOYSA-N 3,3,5-trimethylcyclohexanol Chemical compound CC1CC(O)CC(C)(C)C1 BRRVXFOKWJKTGG-UHFFFAOYSA-N 0.000 abstract 1
- YFEAYNIMJBHJCM-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-ol Chemical compound CC1(C)CC(O)CC(C)(CN)C1 YFEAYNIMJBHJCM-UHFFFAOYSA-N 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910000564 Raney nickel Inorganic materials 0.000 description 6
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000007255 decyanation reaction Methods 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 0 CC(C)(CC(C)([*+])C1)CC1=N* Chemical compound CC(C)(CC(C)([*+])C1)CC1=N* 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N Isophorone Natural products CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000006268 reductive amination reaction Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 description 1
- 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 description 1
- 206010067484 Adverse reaction Diseases 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- HTJDQJBWANPRPF-UHFFFAOYSA-N Cyclopropylamine Chemical compound NC1CC1 HTJDQJBWANPRPF-UHFFFAOYSA-N 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 1
- 150000008431 aliphatic amides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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Abstract
The invention provides a method for preparing 3-aminomethyl-3,5,5-trimethyl cyclohexylamine. The method includes: a) reacting 3-cyano-3,5,5-trimethyl cyclohexanone with excess primary amine, while removing water of the reaction, so that IPN is substantially completely converted to an imine compound; b) in the presence of an aminolysis catalyst, mixing the resulting product from step a) with liquid ammonia so as to carry out the aminolysis reaction on the imine compound to form 3-cyano-3,5,5-trimethyl cyclohexylimine and the primary amine; and c) performing the hydrogenation reaction to 3-cyano-3,5,5-trimethyl cyclohexylimine obtained in step b) to get 3-carbamoylyl-3,5,5-trimethyl cyclohexylamine in the presence of hydrogen and a hydrogenation catalyst. The method of the present invention prevents the generation of major byproducts of 3,5,5-trimethyl cyclohexanol, and 3-aminomethyl-3,5,5-trimethyl cyclohexanol in the prior art, thereby improving the yield of 3-aminomethyl-3,5,5-trimethyl cyclohexylamine.
Description
Technical field
The present invention relates to a kind of preparation method of fatty amine, be specifically related to by 3-cyano group-3,5, the 5-trimethylcyclohexanone prepares the method for 3-aminomethyl-3,5,5-trimethyl cyclohexylamine.
Background technology
3-aminomethyl-3,5, the 5-trimethyl cyclohexylamine (claims again isophorone diamine, be called for short IPDA) be preparation 3-isocyanic ester methylene-3,5, the raw material of 5-3-methyl cyclohexanol based isocyanate (claim again isophorone diisocyanate, be called for short IPDI), polymeric amide etc., can also be as the solidifying agent of epoxy resin.
On technical scale, IPDA is by 3-cyano group-3,5, the 5-trimethylcyclohexanone (claims again cyan-3,5,5-trimethyl cyclohexanone, be called for short IPN) form 3-cyano group-3,5 with ammonia react, 5-trimethylcyclohexyl imines (claims again the cyan-3,5,5-trimethyl cyclohexanone imines, be called for short IPNI), IPNI carries out that reductive amination process makes subsequently under the existence of ammonia with catalytic way with hydrogen.Its reaction process is as follows:
US3,352,913 disclose a kind of IPN reacts the method for preparing IPDA with ammonia, hydrogen under the metal load type catalyst effect of the 8th family.The mol ratio of ammonia and IPN in the method (hereinafter referred to as the cyanamide ratio) is 10 to 30, and temperature of reaction is 70 to 130 ℃, and hydrogen pressure is 150atm.Because it is reversible reaction that IPN and ammonia react generate IPNI, IPN can't all be converted into IPNI, thereby the unreacted IPN of part also is hydrogenated to generate and is difficult to the 3-aminomethyl-3,5 separated with IPDA, 5-cyclonol (being called for short IPAA).The yield of the method gained IPDA only has 80%.
CN101568516A discloses the manufacture method of a kind of IPDA, wherein after the IPN imidization, make the incoming flow that contains IPNI react under the existence of hydrogenation catalyst with hydrogen and ammonia, the method is characterized in that after a part of IPNI has reacted, during reaction by making reaction mixture and not being the basic cpd of ammonia and/or the alkalescence that contacts to improve reaction mixture with basic catalyst.The method is by being adjusted to alkalescence by the IPNI incoming flow in reaction process, controlled the generation of unreacted IPN direct hydrogenation reaction, but alkali further add coming off of cyano group in membership aggravation IPN, generate CN-and 3,5,5-trimethylammonium-2-cyclonene.CN-can affect the activity of hydrogenation catalyst, make its lost of life, and 3,5,5-trimethylammonium-2-cyclonene hydrogenation generates by product 3,3, the 5-cyclonol, and the yield of IPDA is also undesirable.
All there is following defect in the method for the current industrialized IPDA of preparation:
1) reacting the reaction that generates IPNI with excess of ammonia due to IPN is reversible reaction, and IPN can't be converted into IPNI fully, causes part IPN to enter the hydrogenation reaction system and is generated IPAA by direct hydrogenation.
2) cyano group in IPN is extremely unstable under alkaline condition, and easily take off and form 3,5,5-trimethylammonium-2-cyclonene, and the product 3,3 of 3,5,5-trimethylammonium-2-cyclonene hydrogenation, the 5-cyclonol is not desirable product.Owing in the process of decyanation reaction, can producing free CN-, this will cause the reduction of activity of hydrocatalyst in addition.
In traditional preparation method, IPN reacts with excess of ammonia and generates IPNI and water, and the water generated combines with remaining ammonia and makes reaction system be alkalescence, therefore, and the generation that can't avoid the IPN decyanation to react.
Although in CN101568516A, disclosed method, by improving the alkalescence of IPNI reaction solution, makes the generation ratio of IPAA reduce, due to adding of extra alkali, make the decyanation reaction aggravation of IPN.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of new 3-aminomethyl-3,5,5-trimethyl cyclohexylamine (IPDA).Described method, can effectively avoid above-mentioned two by products 3,5, the generation of 5-cyclonol and IPAA, and then the yield of raising IPDA.
The preparation method of 3-aminomethyl-3,5,5-trimethyl cyclohexylamine of the present invention comprises the steps:
A) make IPN and excessive primary amine reaction, the water simultaneously generated except dereaction, make IPN basically all be converted into group with imine moiety; B) under ammonia solution catalyzer exists, by step a) in products therefrom mix with liquefied ammonia and make described group with imine moiety carry out ammonolysis reaction generation IPNI and described primary amine; And c) under the existence of hydrogen and hydrogenation catalyst to step b) IPNI that obtains carries out hydrogenation reaction and obtains IPDA.
Reaction scheme of the present invention is as follows:
According to one embodiment of the present invention, the primary amine of step in a) can be the primary amine of any type, as can be both that aliphatic amide can be also aromatic amine.According to a kind of embodiment, so long as can separate with IPDA, and with any alkyl primary amine of reactant or product generation side reaction, all not can be used for the present invention.Such as being selected from alkylamine, Cycloalkyl amine, arylamines, aralkylamine etc.Described primary amine can be mono amino amine, can be also polyamino amine, as diamines.Particularly, primary amine can be selected from C1-30 alkylamine, C3-30 Cycloalkyl amine, C6-30 arylamines and C7-30 aralkylamine; Be preferably selected from C1-10 alkylamine, C3-10 cycloalkyl base amine and C6-10 arylamines and C7-10 aralkylamine.More specifically, primary amine can be methylamine, ethamine, propylamine, butylamine, quadrol, propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, cyclopropane amine, pentamethylene amine, hexamethylene alkanamine, aniline or benzylamine, but is not limited to this.Most preferably those and the segregative lower boiling primary amine of IPDA, as methylamine, ethamine, propylamine, butylamine, quadrol, propylene diamine, butanediamine, hexanediamine, aniline etc., but be not limited to this.A kind of preferred embodiment according to the present invention, preferably select boiling point at those primary amine of 110 ℃-235 ℃.Another embodiment of the present invention, be also most preferred embodiment, adopts and do not need the IPDA separated, and purpose product itself is as primary amine.
According to one embodiment of the present invention, step a) in the imidization of IPN and described primary amine at 20-150 ℃, preferred 40-120 ℃, more preferably carry out under 50-80 ℃.
According to one embodiment of the present invention, step a) in the imidization of IPN and described primary amine can, under normal pressure, also can under reduced pressure carry out, preferably under reduced pressure carry out, reaction pressure can be for below 100Kpa, preferably below 50Kpa, more preferably below 20Kpa.
According to one embodiment of the present invention, step a) described in primary amine be excessive so that IPN complete reaction as much as possible.Specifically, total amino (NH2) of described primary amine and the mol ratio of IPN are in the scope of 1-20, preferably in the scope of 1-10, more preferably in the scope of 2-8.The excessive of primary amine is favourable to reaction, but too high primary amine ratio will increase the cost that primary amine reclaims.
According to one embodiment of the present invention, step adopts in a), and to make the method that water separates with reaction mixture can be any known suitable method, such as absorption, extraction, distillation etc.Preferably adopt distillation, particularly the method for underpressure distillation is dewatered.Those skilled in the art should know, when adopting the method for distillation dehydration, should select boiling point those primary amine higher than the boiling point (standard atmosphere is depressed 100 ℃) of water, preferably select boiling point at those primary amine more than 110 ℃.According to preferred embodiment, the boiling point of primary amine is below 235 ℃, with IPDA, separates being convenient to.
According to the preferred embodiment of the present invention, a) water-content in products therefrom should be low as much as possible for step, thereby impel the balance of imidization constantly to move to the group with imine moiety direction.But consider reaction efficiency and cost, the water-content in products therefrom should be below 300ppm, preferably at 200ppm, more preferably below 100ppm.
According to the preferred embodiment of the present invention, reaction and tripping device that step adopts in a) can be any existing suitable devices, can be selected according to actual needs and assemble.Such as but not limited to the reactor with water-retaining agent, fixed bed, can be also reactor, the fixed bed with distillation/rectifier unit.Be preferably the conversion unit with distillation/rectifier unit.These devices are known to those skilled in the art, do not repeat them here.
According to one embodiment of the present invention, step b) the ammonia solution catalyzer adopted can be acidic metal oxide, such as gama-alumina, titanium dioxide, zirconium dioxide, silicon-dioxide, zeolite etc., but be not limited to this.Preferred gama-alumina.
Step b) in, the consumption of liquefied ammonia is more much more favourable.According to one embodiment of the present invention, described liquefied ammonia and step are 5-200 as the mol ratio of the IPN of raw material in a), are preferably 10-100, more preferably 15-30.
According to one embodiment of the present invention, step b) under the pressure of the temperature of 20-200 ℃ and 10-30MPa, carry out, preferably under the pressure of the temperature of 50-150 ℃ and 10-20Mpa, carry out, more preferably carry out under the pressure of the temperature of 80-120 ℃ and 10-15Mpa.
According to the method for the invention, step b) can in tank reactor, carry out, also can in fixed-bed reactor, carry out, preferably in fixed-bed reactor, carry out.These reactors are known to those skilled in the art, do not repeat them here.
According to one embodiment of the present invention, step c) the described hydrogenation catalyst in can be common hydrogenation catalyst, can be for example the catalyzer of loading type, as Co/Al2O3, can be also Raney metal type catalyzer, thunderous Buddhist nun's cobalt or Raney's nickel.Preferred Raney's nickel or thunder Buddhist nun cobalt, more preferably Raney's nickel.
According to one embodiment of the present invention, step c) reaction conditions can be the normal condition of carrying out described reductive amination process.Particularly, can under the pressure of the temperature of 100-200 ℃ and 10-30Mpa, carry out, preferably carry out under the pressure of the temperature of 100-150 ℃ and 10-20MPa, more preferably carry out under the pressure of the temperature of 120-150 ℃ and 10-15Mpa.
According to one embodiment of the present invention, step c) can in the reactor of any routine, carry out, for example tank reactor, fixed-bed reactor, fluidized-bed reactor.Preferably in tank reactor and fixed-bed reactor, carry out, more preferably carry out in fixed-bed reactor.Do not repeat them here.
According to the preferred embodiment of the present invention, step c) in, when adopting fixed bed as reactor, the mol ratio of hydrogen and IPNI is 10-100, is preferably 20-80, more preferably 30-50.
When step a) in primary amine used while being IPDA, the IPDA of the final gained of at least a portion is turned back to step and carries out imidization as primary amine and IPN in a).
When step a) in primary amine used while being not IPDA, method of the present invention also further comprises steps d): make step c by rectifying) IPDA in the product that obtains separates with described primary amine, the primary amine that wherein separated returns to step and recycles in a).
In the present invention, take during IPN prepares the method for IPDA as raw material, the imidization that the primary amine of take carries out as raw material, thus can by dehydration, impel the balance of imidization constantly to move to the product direction simply, make IPN be converted into group with imine moiety substantially fully.Method of the present invention has been avoided on the one hand unreacted IPN decyanation under alkaline condition to generate 3,5,5-trimethylammonium-2-cyclonene and then be hydrogenated and has been generated 3,3, the 5-cyclonol, and unreacted IPN generated IPAA by direct hydrogenation, thus greatly improved productive rate; The trouble of also having avoided on the other hand by-product alcohols to be separated with IPDA.And primary amine can easily separate with IPDA after reaction finishes, and reclaim substantially fully, carry out recycle.Special in usining the most preferred embodiment of IPDA as primary amine, operate simpler.
The accompanying drawing explanation
Fig. 1 is the schematic diagram according to a kind of embodiment the inventive method reactive system used.
Embodiment
Now by reference to the accompanying drawings, and by embodiment, the present invention is done to further description, but the present invention is not limited to this.
The invention provides a kind of new method that is prepared IPDA by IPN.With the method that generates IPNI with ammonia and IPN reaction in existing method, compare, method of the present invention adopts primary amine to react the corresponding group with imine moiety of generation with IPN.Owing to adopting primary amine, therefore can easily from reaction mixture, remove the water that reaction generates, thereby impel reaction constantly to move to the product direction, finally make the basic complete reaction of raw material IPN generate group with imine moiety.And then with liquefied ammonia, the group with imine moiety of gained is converted into to IPNI, then carries out reduction amination and obtain IPDA.
Below with reference to Fig. 1, method of the present invention is described in further detail.
Fig. 1 is the schematic diagram according to the inventive method of one embodiment of the present invention conversion unit system used.At first, in step (a), IPN and excessive primary amine (1) enter in reaction fractionating tower (2) and are reacted, and water is realized in rectifying tower with reaction mixture separating.Water (4) is discharged from tower top, and dewatered product (3) is drawn at the bottom of tower.
Dewatered product (3) mainly contains the moisture of described group with imine moiety, unreacted primary amine and trace.For making the IPN complete reaction, in dewatered product (3), the amount of moisture need be as far as possible low, is for example 300ppm or lower, preferably 200ppm or lower, more preferably 100ppm or lower.
Then, in step (b), dewatered product (3) enters into the ammonolysis reaction device (6) of ammonia solution catalyzer with preparation IPNI together with liquefied ammonia (5).Reactor can be tank reactor, but preferred fixed-bed reactor.Through reaction obtain containing IPNI and in step (a) as the mixture (7) of the primary amine of raw material.
Finally, in step (c), the mixture (7) that step (b) obtains is introduced in hydrogenator (9) and is carried out hydrogenation reaction together with hydrogen (8), generates IPDA mother liquor (10).This step can adopt the reaction conditions identical with conventional IPNI hydrogenation reaction.The preferred Raney's nickel of hydrogenation catalyst or thunder Buddhist nun cobalt, more preferably Raney's nickel.Preferably adopt fixed bed as reactor, now, the mol ratio of hydrogen and IPNI is 10-100, is preferably 20-80, more preferably 30-50.
Gained IPDA mother liquor (10) can be processed and obtain IPDA by any conventional separation/purification.While for primary amine used, being other primary amine except IPDA, can IPDA be separated with primary amine by (not shown)s such as rectifier units.
Further illustrate the present invention below by specific embodiment, those skilled in the art should know, but the present invention is not limited to this.
The quantitative analysis of IPNI in following examples (7) and IPDA mother liquor (10) is carried out on Agilent-7980 type gas-chromatography, and analytical conditions for gas chromatography is as follows:
Chromatographic column: Agilent HP-5 (specification is 30m * 0.32mm * 0.25mm)
Injector temperature: 280 ℃
Splitting ratio: 30: 1
Post flow: 1.5ml/min
Column temperature: initial: 100 ℃
Temperature rise rate: 15 ℃/min is elevated to 260 ℃, keeps 8min after 260 ℃
Detector temperature: 280 ℃,
H2 flow: 35ml/min
Air flow quantity: 350ml/min
Embodiment 1:
Adopt reaction unit as shown in Figure 1 to carry out the present embodiment.
Reaction fractionating tower (2) is internal diameter 40mm, and long 1000mm inside is equipped with the θ ring filler of 2mm specification, and opening for feed is positioned at the middle part of reaction fractionating tower.Reactor (6) is long 200mm, and internal diameter 25mm is equipped with the gama-alumina bead of 1mm diameter in reactor.Reactor (9) is long 400mm, and internal diameter 25mm inside is equipped with the German G62RS of the Southern Co. hydrogenation catalyst of 1mm diameter.
The first step, IPN is with 165g/h, and IPDA enters in reaction fractionating tower from the middle part of reaction fractionating tower (2) with 510g/h, and the reactive distillation pressure tower is controlled at 50Kpa by vacuum pump, approximately 200 ℃ of tower reactor temperature, approximately 81 ℃ of tower top temperatures.
Second step, rectifying tower bottom product and liquefied ammonia enter in reactor (6) and carry out ammonolysis reaction by high-pressure pump, and the feeding rate of liquefied ammonia is 425g/h, and temperature of reaction is controlled at 100 ℃, and pressure-controlling is at 15Mpa.
The 3rd step, enter into again in hydrogenator (9) and carry out hydrogenation reaction after the ammonolysis reaction product mixes with hydrogen, wherein reactor (6) temperature is controlled at 100 ℃, the interior temperature of reactor (9) is controlled at 140 ℃, pressure-controlling is at 15Mpa, and hydrogen feed speed is 100 standard liter/h.
Sample (3) analysis at the bottom of reaction fractionating tower (2) tower, its water content is about 150ppm after tested;
From hydrogenator (9) outlet sampling (10), analyze, product composition is as shown in table 1 below.
Table 1
| Product composition | Content (wt%) |
| IPDA | 99.7 |
| Two isophorone diamines | 0.15 |
| Other | 0.15 |
Main By product IPAA and 3,3,5-cyclonol in traditional method do not detected.
After in the deduction raw material, institute adds isophorone diamine, the yield of reaction is about 98.8%.
Wherein the structure of two isophorone diamines is as follows:
Embodiment 2-4
Carry out embodiment 2-4 according to the method identical with embodiment 1, just will change respectively quadrol, hexanediamine and the aniline of same molar in the first step into as the IPDA of primary amine.
The same hydrogenation reaction product of analyzing forms, and result is as shown in table 2 below.
Table 2
Main By product IPAA and 3,3,5-cyclonol in traditional method do not detected.
Embodiment 5-7
Carry out embodiment 5-7 according to the method identical with embodiment 1, just the ammonia solution catalyzer in second step is changed to titanium dioxide bead, silicon-dioxide bead and the ion exchange resin (D72 of Nankai University) of commercially available 1mm by gama-alumina.
Each product composition in same analysis hydrogenation reaction product, result is as shown in table 3 below.
Table 3
Main By product IPAA and 3,3,5-cyclonol in traditional method do not detected.
Embodiment 8-10
Carry out embodiment 8-10 according to the method identical with embodiment 1, just by the hydrogenation catalyst in the 3rd step by the southern G62RS of Germany, be changed to respectively Raney's nickel (cat-1600), thunder Buddhist nun cobalt (GRACE-2800) and the German G-67RS of Southern Co. that catalloy company provides.
The same content of analyzing each product in hydrogenation reaction product, result is as shown in table 4 below.
Table 4
Main By product IPAA and 3,3,5-cyclonol in traditional method do not detected.
Embodiment 11-13
Carry out embodiment 11-13 according to the method identical with embodiment 1, just by the pressure reacted in second step and the 3rd step, be adjusted into respectively 10Mpa, 12Mpa, 13Mpa, other condition is identical with embodiment 1.
The same composition of analyzing each product in hydrogenation reaction product, result is as shown in table 5 below.
Table 5
Main By product IPAA and 3,3,5-cyclonol in traditional method do not detected.
Embodiment 14-16
Carry out embodiment 14-16 according to the method identical with embodiment 1, just the IPDA as primary amine in the first step is changed to quadrol, feeding rate is respectively 90g/h, 150g/h and 240g/h.
The same hydrogenation reaction product of analyzing forms, and result is as shown in table 6 below.
Table 6
Main By product IPAA and 3,3,5-cyclonol in traditional method do not detected.
Embodiment 17-19
Carry out embodiment 17-19 according to the method identical with embodiment 1, the IPDA as primary amine in the first step is changed to quadrol, the feeding rate of liquefied ammonia changes 255g/h, 340g/h, 510g/h into.
The same hydrogenation reaction product of analyzing forms, and result is as shown in table 7 below.
Table 7
Main By product IPAA and 3,3,5-cyclonol in traditional method do not detected.
As can be seen from the above embodiments, adopt method of the present invention to prepare the yield that IPDA can improve product greatly, substantially can make yield reach 98%.In addition, the method has been avoided the generation of by product IPAA and 3,3,5-cyclonol, the trouble that these by-product alcohols while having saved product purification are difficult to separate with IPDA.
Although more than by embodiment, understand in detail the present invention; but those of ordinary skills should be appreciated that; can carry out any distortion, increase or replacement and not deviate from spirit of the present invention these embodiments, and protection scope of the present invention is not subject to the restriction of specific embodiment given herein by claims explanation.
Claims (34)
1. the preparation method of a 3-aminomethyl-3,5,5-trimethyl cyclohexylamine, described method comprises the steps:
A) make 3-cyano group-3,5,5-trimethylcyclohexanone and excessive primary amine reaction, the water simultaneously generated except dereaction, make 3-cyano group-3,5, and the 5-trimethylcyclohexanone all is converted into group with imine moiety basically;
B), under ammonia solution catalyzer exists, products therefrom in step a) is mixed and makes described group with imine moiety carry out ammonolysis reaction generating 3-cyano group-3,5,5-trimethylcyclohexyl imines and described primary amine with liquefied ammonia; With
C) the 3-cyano group-3,5 under the existence of hydrogen and hydrogenation catalyst, step b) obtained, 5-trimethylcyclohexyl imines carries out hydrogenation reaction and obtains the 3-aminomethyl-3,5,5-trimethyl cyclohexylamine.
2. method according to claim 1, is characterized in that, the described primary amine in step a) is that the free C1-30 alkylamine of choosing, C3-30 Cycloalkyl amine, C6-30 arylamines and C7-30 aralkylamine form monoamine or the diamines in group.
3. method according to claim 2, is characterized in that, described primary amine is the primary amine of boiling point in 110 ℃ of-235 ℃ of scopes.
4. method according to claim 1, is characterized in that, the described primary amine in step a) is the 3-aminomethyl-3,5,5-trimethyl cyclohexylamine.
5. according to the described method of any one in claim 1-4, it is characterized in that, total amino (NH2) of primary amine described in step a) and 3-cyano group-3,5, the mol ratio of 5-trimethylcyclohexanone is in the scope of 1-20.
6. method according to claim 5, is characterized in that, total amino (NH2) of primary amine described in step a) and 3-cyano group-3,5, and the mol ratio of 5-trimethylcyclohexanone is in the scope of 1-10.
7. method according to claim 6, is characterized in that, total amino (NH2) of primary amine described in step a) and 3-cyano group-3,5, and the mol ratio of 5-trimethylcyclohexanone is in the scope of 2-8.
8. according to the described method of any one in claim 1-4, it is characterized in that, in step a), adopt absorption, extraction or distillation method to dewater.
9. method according to claim 8, is characterized in that, described distillation method is distillation under vacuum.
10. method according to claim 9, is characterized in that, step a) is carried out below 100Kpa.
11. method, is characterized in that according to claim 10, carries out under the pressure of step a) below 50Kpa.
12. according to the described method of claim 11, it is characterized in that, carry out under the pressure of step a) below 20Kpa.
13. according to the described method of any one in claim 1-4, it is characterized in that, step a) is carried out under 20-150 ℃.
14. according to the described method of claim 13, it is characterized in that, step a) is carried out under 40-120 ℃.
15. according to the described method of claim 14, it is characterized in that, step a) is carried out under 50-80 ℃.
16. according to the described method of any one in claim 1-4, it is characterized in that, the water-content in the step a) products therefrom is below 300ppm.
17. according to the described method of claim 16, it is characterized in that, the water-content in the step a) products therefrom is below 200ppm.
18. according to the described method of claim 17, it is characterized in that, the water-content in the step a) products therefrom is below 100ppm.
19. according to the described method of any one in claim 1-4, it is characterized in that, in liquefied ammonia described in step b) and step a), as the 3-cyano group-3,5 of raw material, the mol ratio of 5-trimethylcyclohexanone is 5-200.
20. according to the described method of claim 19, it is characterized in that, in liquefied ammonia described in step b) and step a), as the 3-cyano group-3,5 of raw material, the mol ratio of 5-trimethylcyclohexanone is 10-100.
21. according to the described method of claim 20, it is characterized in that, in liquefied ammonia described in step b) and step a), as the 3-cyano group-3,5 of raw material, the mol ratio of 5-trimethylcyclohexanone is 15-30.
22. according to the described method of any one in claim 1-4, it is characterized in that, step c) adopts fixed-bed reactor, wherein, the mol ratio of hydrogen and cyan-3,5,5-trimethyl cyclohexanone imines is 10-100.
23. according to the described method of claim 22, it is characterized in that, step c) adopts fixed-bed reactor, wherein, the mol ratio of hydrogen and cyan-3,5,5-trimethyl cyclohexanone imines is 20-80.
24. according to the described method of claim 23, it is characterized in that, step c) adopts fixed-bed reactor, wherein, the mol ratio of hydrogen and cyan-3,5,5-trimethyl cyclohexanone imines is 30-50.
25. method, is characterized in that according to claim 4, and the 3-aminomethyl-3,5,5-trimethyl cyclohexylamine of at least a portion step c) gained is turned back in step a) as described primary amine and 3-cyano group-3,5, the 5-trimethylcyclohexanone carries out imidization.
26. according to the described method of any one in claim 1-3, it is characterized in that, described primary amine is not 3-aminomethyl-3,5, the 5-trimethyl cyclohexylamine, and described method also further comprises step d): the 3-aminomethyl-3,5 in the product that step c) is obtained by rectifying, the 5-trimethyl cyclohexylamine separates with described primary amine, and separated primary amine is turned back in step a) and recycles.
27. according to the described method of any one in claim 1-4, it is characterized in that, step b) is carried out under the pressure of the temperature of 20-200 ℃ and 10-30MPa.
28. want 27 described methods according to right, it is characterized in that, step b) is carried out under the pressure of the temperature of 50-150 ℃ and 10-20Mpa.
29. want 28 described methods according to right, it is characterized in that, step b) is carried out under the pressure of the temperature of 80-120 ℃ and 10-15Mpa.
30. according to the described method of any one in claim 1-4, it is characterized in that, the ammonia solution catalyzer that step b) adopts is to select to be formed the acidic metal oxide in group by gama-alumina, titanium dioxide, zirconium dioxide, silicon-dioxide and zeolite.
31. according to the described method of any one in claim 1-4, it is characterized in that, step c) is carried out under the pressure of the temperature of 100-200 ℃ and 10-30Mpa.
32. according to the described method of claim 31, it is characterized in that, step c) is carried out under the pressure of the temperature of 100-150 ℃ and 10-20MPa.
33. according to the described method of claim 32, it is characterized in that, step c) is carried out under the pressure of the temperature of 120-150 ℃ and 10-15Mpa.
34. according to the described method of any one in claim 1-4, it is characterized in that, the described hydrogenation catalyst in step c) is selected from Raney metal type catalyzer.
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| CN103464162B (en) * | 2013-09-03 | 2015-03-11 | 万华化学集团股份有限公司 | Preparation method and application of Co and Al2O3 compound nanotube array membrane catalyst |
| CN103664638B (en) * | 2013-12-31 | 2016-04-13 | 张锦碧 | A kind of simple method for preparing of isophorone diamine |
| CN104056646B (en) * | 2014-06-19 | 2016-01-20 | 万华化学集团股份有限公司 | The preparation method of a kind of Co/Ni and aluminum pyrophosphate composite hollow microballoon and application thereof |
| EP3255035B1 (en) * | 2016-06-10 | 2018-09-19 | Evonik Degussa GmbH | 2- (3,3,5-trimethylcyclohexyl) propane-1,3-diamine, a method for their preparation and use |
| CN108017547B (en) | 2017-12-22 | 2019-07-02 | 浙江新和成股份有限公司 | A kind of method of cyan-3,5,5-trimethyl cyclohexanone imines hydrogenating reduction preparation isophorone diamine |
| CN115433095B (en) * | 2021-06-01 | 2023-08-11 | 万华化学集团股份有限公司 | Cyclohexylamine derivative, preparation method, epoxy resin composition, preparation method and application |
| CN113493397B (en) * | 2021-07-30 | 2023-06-30 | 山东新和成维生素有限公司 | Preparation method of isophorone imine and preparation method of IPDA containing isophorone imine |
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