CN102976956A - Method for preparing 3-aminomethyl-3,5,5-trimethyl cyclohexylamine - Google Patents
Method for preparing 3-aminomethyl-3,5,5-trimethyl cyclohexylamine Download PDFInfo
- Publication number
- CN102976956A CN102976956A CN2012104408472A CN201210440847A CN102976956A CN 102976956 A CN102976956 A CN 102976956A CN 2012104408472 A CN2012104408472 A CN 2012104408472A CN 201210440847 A CN201210440847 A CN 201210440847A CN 102976956 A CN102976956 A CN 102976956A
- Authority
- CN
- China
- Prior art keywords
- primary amine
- described method
- ipda
- reaction
- ipn
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 68
- 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 54
- 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 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 150000002466 imines Chemical class 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 8
- -1 Cycloalkyl amine Chemical class 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 7
- 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
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-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
- 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 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
- 150000004982 aromatic amines Chemical class 0.000 claims description 6
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 6
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 6
- 150000003973 alkyl amines Chemical class 0.000 claims description 5
- 238000005915 ammonolysis reaction Methods 0.000 claims description 5
- 150000003974 aralkylamines Chemical class 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 3
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 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
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 claims description 2
- 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
- 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
- 125000002924 primary amino group Chemical group [H]N([H])* 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
- 238000007098 aminolysis reaction Methods 0.000 abstract 2
- NNGAQKAUYDTUQR-UHFFFAOYSA-N cyclohexanimine Chemical compound N=C1CCCCC1 NNGAQKAUYDTUQR-UHFFFAOYSA-N 0.000 abstract 2
- 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 1
- 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
- 239000011541 reaction mixture Substances 0.000 description 5
- 238000007255 decyanation reaction Methods 0.000 description 4
- 239000011324 bead Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- OITMBHSFQBJCFN-UHFFFAOYSA-N 2,5,5-trimethylcyclohexan-1-one Chemical compound CC1CCC(C)(C)CC1=O OITMBHSFQBJCFN-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
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-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
- 150000002431 hydrogen Chemical class 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
- 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
- 238000005070 sampling Methods 0.000 description 2
- 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
- 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
- 239000004593 Epoxy Substances 0.000 description 1
- 241000282326 Felis catus Species 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
- 238000004458 analytical method 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
- 230000002950 deficient Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000005516 engineering process Methods 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
- 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
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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 Resins, epoxy.
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 with catalytic way in the presence of ammonia with hydrogen subsequently that reductive amination process makes.Its reaction process is as follows:
US3,352,913 disclose a kind of IPN and ammonia, hydrogen react the method for preparing IPDA 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 that separates 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 the incoming flow that contains IPNI and hydrogen and ammonia are reacted in the presence of hydrogenation catalyst, 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 with 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 among the affiliation 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 then generates by product 3,3, the 5-cyclonol, and the yield of IPDA is also undesirable.
All there is following defective in the method for the present industrialized IPDA of preparation:
1) because the reaction of IPN and excess of ammonia generates the reaction of IPNI is reversible reaction, IPN can't be converted into IPNI fully, causes part IPN to enter the hydrogenation reaction system and by direct hydrogenation generation IPAA.
2) cyano group among the IPN is extremely unstable under alkaline condition, take off easily to 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 to can produce free CN-in the process of decyanation reaction, this will cause the reduction of activity of hydrocatalyst in addition.
The reaction of IPN and excess of ammonia generates IPNI and water in traditional preparation method, and the water that generates and remaining ammonia combine so that reaction system is alkalescence, therefore, can't avoid the generation of IPN decyanation reaction.
Although disclosed method passes through to improve the alkalescence of IPNI reaction solution among the CN101568516A, so that the generation ratio of IPAA reduces, owing to the adding of extra alkali, so that reacting, aggravates the decyanation 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 be avoided above-mentioned two by products 3,5, the generation of the pure and mild IPAA of 5-3-methyl cyclohexanol, 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 that generates except dereaction simultaneously makes IPN basically all be converted into group with imine moiety; B) in the presence of ammonia solution catalyzer, with 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) in the presence 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 both can being that aliphatic amide also can be aromatic amine.According to a kind of embodiment, so long as can separate with IPDA, and all not can be used for the present invention with any alkyl primary amine of reactant or product generation side reaction.Such as being selected from alkylamine, Cycloalkyl amine, arylamines, aralkylamine etc.Described primary amine can be mono amino amine, can be polyamino amine also, such 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 such as methylamine, ethamine, propylamine, butylamine, quadrol, propylene diamine, butanediamine, hexanediamine, aniline etc., but are not limited to this.A kind of preferred embodiment according to the present invention preferably selects boiling point at those primary amine of 110 ℃-235 ℃.Another embodiment of the present invention also is most preferred embodiment, and adopting does not need the IPDA that separates, and namely 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 ℃, preferably 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 the 100Kpa, below the preferred 50Kpa, more preferably below the 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 of described primary amine (NH2) with the mol ratio of IPN 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, the method that water is separated with reaction mixture that step adopts in a) can be any known suitable method, such as absorption, extraction, distillation etc.The preferred employing distilled, and 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 to be higher than those primary amine of 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 ℃, separates with IPDA being convenient to.
According to preferred implementation of the present invention, a) water-content in the 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 the products therefrom should be below 300ppm, preferably at 200ppm, more preferably below 100ppm.
According to preferred implementation of the present invention, reaction and tripping device that step adopts in a) can be any existing suitable devices, can select according to actual needs and assemble.Such as but not limited to reactor, the fixed bed with water-retaining agent, also can be 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 that adopts 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) consumption of liquefied ammonia is more much more favourable in.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 20-200 ℃ temperature and 10-30MPa, carries out, preferably under the pressure of 50-150 ℃ temperature and 10-20Mpa, carry out, more preferably under the pressure of 80-120 ℃ temperature and 10-15Mpa, carry out.
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 the catalyzer of loading type for example, such as Co/Al2O3, also can be 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 100-200 ℃ temperature and 10-30Mpa, carry out, preferably under the pressure of 100-150 ℃ temperature and 10-20MPa, carry out, more preferably under the pressure of 120-150 ℃ temperature and 10-15Mpa, carry out.
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 in fixed-bed reactor, carry out.Do not repeat them here.
According to preferred implementation 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 used primary amine when being IPDA, the IPDA of the final gained of at least a portion is turned back to step carries out imidization as primary amine and IPN in a).
When step a) in used primary amine when 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 separates returns step and recycles in a).
Prepare as raw material in the method for IPDA take IPN in the present invention, the imidization of carrying out take primary amine as raw material, thus can impel the balance of imidization constantly to move to the product direction by dehydration 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 separate with IPDA.And primary amine can easily separate with IPDA after reaction finishes, and reclaims substantially fully, carries out recycle.Special in the most preferred embodiment of IPDA as primary amine, operate simpler.
Description of drawings
Fig. 1 is the synoptic diagram according to the used reactive system of a kind of embodiment the inventive method.
Embodiment
Now by reference to the accompanying drawings, and by embodiment the present invention is done 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.Compare with the method that generates IPNI with ammonia and IPN reaction in the existing method, method of the present invention adopts primary amine and the corresponding group with imine moiety of IPN reaction generation.Owing to adopt primary amine, therefore can easily from reaction mixture, remove the water that reaction generates, thereby impel reaction constantly to move to the product direction, make at last 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 IPNI, carry out again 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 synoptic diagram according to the used conversion unit of the inventive method of one embodiment of the present invention system.At first, IPN and excessive primary amine (1) enter in the reaction fractionating tower (2) and react in step (a), and water is realized separating in rectifying tower with reaction mixture.Water (4) is discharged from cat head, and dewatered product (3) is drawn at the bottom of tower.
Dewatered product (3) mainly contains described group with imine moiety, unreacted primary amine and Trace water and divides.For making the IPN complete reaction, the amount of moisture need be as far as possible low in the dewatered product (3), for example is 300ppm or lower, preferred 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 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.
At last, in step (c), the mixture (7) that step (b) obtains is introduced in the hydrogenator (9) with hydrogen (8) and is carried out hydrogenation reaction, generates IPDA mother liquor (10).This step can adopt the reaction conditions identical with the IPNI hydrogenation reaction of routine.The preferred Raney's nickel of hydrogenation catalyst or thunder Buddhist nun cobalt, more preferably Raney's nickel.The preferred fixed bed that adopts is as reactor, and at this moment, 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 by any conventional separation/purification and obtain IPDA.When being other primary amine except IPDA for used primary amine, can IPDA be separated with primary amine by (not shown)s such as rectifier units.
Further specify 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 in Agilent-7980 type gas-chromatography, and analytical conditions for gas chromatography is as follows:
(specification is 30m * 0.32mm * 0.25mm) to chromatographic column: Agilent HP-5
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 present embodiment.
Reaction fractionating tower (2) is internal diameter 40mm, long 1000mm, in the θ ring filler of 2mm specification is housed, 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 the reactor.Reactor (9) is long 400mm, internal diameter 25mm, in the German G62RS of the Southern Co. hydrogenation catalyst of 1mm diameter is housed.
The first step, IPN is with 165g/h, and IPDA enters in the 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, about 200 ℃ of tower reactor temperature, about 81 ℃ of tower top temperature.
Second step, rectifying tower bottom product and liquefied ammonia enter in the reactor (6) by high-pressure pump and carry out ammonolysis reaction, 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 the hydrogenator (9) after the ammonolysis reaction product mixes with hydrogen and carry out hydrogenation reaction, 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.
Sampling (3) is analyzed at the bottom of reaction fractionating tower (2) tower, and its water content is about 150ppm after tested;
Analyze from hydrogenator (9) outlet sampling (10), 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 |
Do not detect Main By product IPAA and 3,3,5-cyclonol in the traditional method.
Institute adds after the isophorone diamine in the deduction raw material, and 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 the result is as shown in table 2 below.
Table 2
Do not detect Main By product IPAA and 3,3,5-cyclonol in the traditional method.
Embodiment 5-7
Carry out embodiment 5-7 according to the method identical with embodiment 1, just the ammonia solution catalyzer in the 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 the same analysis hydrogenation reaction product, the result is as shown in table 3 below.
Table 3
Do not detect Main By product IPAA and 3,3,5-cyclonol in the traditional method.
Embodiment 8-10
Carry out embodiment 8-10 according to the method identical with embodiment 1, hydrogenation catalyst in just going on foot the 3rd is 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 by the southern G62RS of Germany.
The same content of analyzing each product in the hydrogenation reaction product, the result is as shown in table 4 below.
Table 4
Do not detect Main By product IPAA and 3,3,5-cyclonol in the traditional method.
Embodiment 11-13
Carry out embodiment 11-13 according to the method identical with embodiment 1, just with the pressure of second step and reaction in 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 the hydrogenation reaction product, the result is as shown in table 5 below.
Table 5
Do not detect Main By product IPAA and 3,3,5-cyclonol in the traditional method.
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 the result is as shown in table 6 below.
Table 6
Do not detect Main By product IPAA and 3,3,5-cyclonol in the traditional method.
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 the result is as shown in table 7 below.
Table 7
Do not detect Main By product IPAA and 3,3,5-cyclonol in the traditional method.
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 when having saved product purification and IPDA are difficult to separate.
Although more than understand in detail the present invention by embodiment; 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 subjected to the restriction of specific embodiment given herein by claims explanation.
Claims (18)
1. the preparation method of a 3-aminomethyl-3,5,5-trimethyl cyclohexylamine (IPDA), described method comprises the steps:
A) make 3-cyano group-3,5,5-trimethylcyclohexanone (IPN) and excessive primary amine reaction, the water that generates except dereaction simultaneously makes IPN basically all be converted into group with imine moiety;
B) in the presence of ammonia solution catalyzer, with step a) in products therefrom mix with liquefied ammonia and make described group with imine moiety carry out ammonolysis reaction generation 3-cyano group-3,5,5-trimethylcyclohexyl imines (IPNI) and described primary amine; With
C) in the presence of hydrogen and hydrogenation catalyst to step b) IPNI that obtains carries out hydrogenation reaction and obtains IPDA.
2. described method according to claim 1 is characterized in that, the described primary amine of step in a) is to be selected from by C 1-30 alkylamine, C3-30 Cycloalkyl amine, C6-30 arylamines and C7-30 aralkylamine to be formed monoamine or diamines in the group; Preferred described primary amine is to be selected from by C1-10 alkylamine, C3-10 cycloalkyl base amine and C6-10 arylamines and C7-10 aralkylamine to be formed monoamine or diamines in the group; More preferably be selected from the group that is formed by methylamine, ethamine, propylamine, butylamine, quadrol, propylene diamine, butanediamine, hexanediamine and aniline.
3. described 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. described method according to claim 1 is characterized in that, the described primary amine of step in a) is IPDA.
5. the described method of any one is characterized in that according to claim 1-4, step a) described in primary amine total amino (NH2) with the mol ratio of IPN in the scope of 1-20, preferably in the scope of 1-10, more preferably in the scope of 2-8.
6. the described method of any one is characterized in that according to claim 1-5, and step a) middle absorption, extraction or the distillation method of adopting dewaters.
7. described method according to claim 6 is characterized in that described distillation method is distillation under vacuum.
8. described method according to claim 7 is characterized in that, step below the preferred 50Kpa, is more preferably carried out under the following pressure of 20Kpa a) below 100Kpa.
9. the described method of any one is characterized in that according to claim 1-8, and step is a) at 20-150 ℃, preferred 40-120 ℃, more preferably carries out under 50-80 ℃.
10. the described method of any one is characterized in that according to claim 1-9, step a) water-content in the products therefrom below 300ppm, preferably at 200ppm, more preferably below 100ppm.
11. the described method of any one is characterized in that step b according to claim 1-10) described in liquefied ammonia and step be 5-200 as the mol ratio of the IPN of raw material in a), be preferably 10-100, more preferably 15-30.
12. the described method of any one is characterized in that step c according to claim 1-11) adopt fixed-bed reactor, wherein, the mol ratio of hydrogen and cyan-3,5,5-trimethyl cyclohexanone imines is 10-100, is preferably 20-80, more preferably 30-50.
13. described method is characterized in that according to claim 4, with at least a portion step c) IPDA of gained turns back to step and carries out imidization as described primary amine and IPN in a).
14. the described method of any one according to claim 1-3, it is characterized in that, described primary amine is not IPDA, and described method also further comprises steps d): make step c by rectifying) IPDA in the product that obtains separates with described primary amine, and the primary amine that separates is turned back to step recycle in a).
15. the described method of any one according to claim 1-14, it is characterized in that, step b) under the pressure of 20-200 ℃ temperature and 10-30MPa, carries out, preferably under the pressure of 50-150 ℃ temperature and 10-20Mpa, carry out, more preferably under the pressure of 80-120 ℃ temperature and 10-15Mpa, carry out.
16. the described method of any one is characterized in that step b according to claim 1-15) the ammonia solution catalyzer that adopts is to select to be formed acidic metal oxide in the group by gama-alumina, titanium dioxide, zirconium dioxide, silicon-dioxide and zeolite.
17. the described method of any one according to claim 1-16, it is characterized in that, step c) under the pressure of 100-200 ℃ temperature and 10-30Mpa, carries out, preferably under the pressure of 100-150 ℃ temperature and 10-20MPa, carry out, more preferably under the pressure of 120-150 ℃ temperature and 10-15Mpa, carry out.
18. the described method of any one is characterized in that step c according to claim 1-18) in described hydrogenation catalyst be selected from Raney metal type catalyzer, preferred thunder Buddhist nun cobalt or Raney's nickel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012104408472A CN102976956B (en) | 2013-01-07 | 2013-01-07 | Method for preparing 3-aminomethyl-3,5,5-trimethyl cyclohexylamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012104408472A CN102976956B (en) | 2013-01-07 | 2013-01-07 | Method for preparing 3-aminomethyl-3,5,5-trimethyl cyclohexylamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102976956A true CN102976956A (en) | 2013-03-20 |
| CN102976956B CN102976956B (en) | 2013-12-11 |
Family
ID=47851361
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012104408472A Active CN102976956B (en) | 2013-01-07 | 2013-01-07 | Method for preparing 3-aminomethyl-3,5,5-trimethyl cyclohexylamine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102976956B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103464162A (en) * | 2013-09-03 | 2013-12-25 | 万华化学集团股份有限公司 | Preparation method and application of a nanotube array membrane catalyst composited with Co and Al2O3 |
| CN103664638A (en) * | 2013-12-31 | 2014-03-26 | 张锦碧 | Simple preparation method of isophorone diamine |
| CN104056646A (en) * | 2014-06-19 | 2014-09-24 | 万华化学集团股份有限公司 | Preparation method and application of Co/Ni and aluminum pyrophosphate composite hollow microsphere |
| CN104119233A (en) * | 2013-04-27 | 2014-10-29 | 万华化学集团股份有限公司 | A method for preparing 3-aminomethyl-3,5,5-trimethylcyclohexylamine |
| CN107488115A (en) * | 2016-06-10 | 2017-12-19 | 赢创德固赛有限公司 | 2- (3,3, 5-trimethylcyclohexyl) propane-1, 3-diamine, preparation method and application thereof |
| WO2019120064A1 (en) | 2017-12-22 | 2019-06-27 | 浙江新和成股份有限公司 | Method for preparing isophorone diamine by means of hydrogenation reduction of isophorone nitrile imine |
| CN113493397A (en) * | 2021-07-30 | 2021-10-12 | 山东新和成维生素有限公司 | Preparation method of isophorone imine and preparation method of IPDA (isophorone diisocyanate) containing isophorone imine |
| CN115433095A (en) * | 2021-06-01 | 2022-12-06 | 万华化学集团股份有限公司 | A kind of cyclohexylamine derivative and its preparation method, a kind of epoxy resin composition and its preparation method and application |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA969316A (en) * | 1970-11-04 | 1975-06-17 | Ewald Forster | Process for the manufacture of thermosetting plastic moulded articles having a glossy stain resistant surface |
| US6011179A (en) * | 1997-10-30 | 2000-01-04 | Degussa-Huls Ag | Process for the production of amines from imines of nitriles |
| DE10236675A1 (en) * | 2002-08-09 | 2004-02-19 | Basf Ag | Production of isophoronediamine with a high cis content, useful e.g. in polymer production, involves making crude diamine with a low cis content, purifying and fractionating, and recycling the fraction with a low cis content |
| CN1561260A (en) * | 2001-08-31 | 2005-01-05 | 巴斯福股份公司 | Preparation method of isophorone diamine (IPDA, 3-aminomethyl-3,5,5-trimethylcyclohexylamine) |
| CN1729162A (en) * | 2002-12-19 | 2006-02-01 | 巴斯福股份公司 | Improved neutralization of isophorone nitrile synthesis products |
| CN101066930A (en) * | 2007-06-12 | 2007-11-07 | 中国药科大学 | Preparation method of 2-[2-(2,2,2-trifluoroethoxy)]phenoxyethylamine |
-
2013
- 2013-01-07 CN CN2012104408472A patent/CN102976956B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA969316A (en) * | 1970-11-04 | 1975-06-17 | Ewald Forster | Process for the manufacture of thermosetting plastic moulded articles having a glossy stain resistant surface |
| US6011179A (en) * | 1997-10-30 | 2000-01-04 | Degussa-Huls Ag | Process for the production of amines from imines of nitriles |
| CN1561260A (en) * | 2001-08-31 | 2005-01-05 | 巴斯福股份公司 | Preparation method of isophorone diamine (IPDA, 3-aminomethyl-3,5,5-trimethylcyclohexylamine) |
| DE10236675A1 (en) * | 2002-08-09 | 2004-02-19 | Basf Ag | Production of isophoronediamine with a high cis content, useful e.g. in polymer production, involves making crude diamine with a low cis content, purifying and fractionating, and recycling the fraction with a low cis content |
| CN1729162A (en) * | 2002-12-19 | 2006-02-01 | 巴斯福股份公司 | Improved neutralization of isophorone nitrile synthesis products |
| CN101066930A (en) * | 2007-06-12 | 2007-11-07 | 中国药科大学 | Preparation method of 2-[2-(2,2,2-trifluoroethoxy)]phenoxyethylamine |
Non-Patent Citations (1)
| Title |
|---|
| 张兴亮等: "异佛尔酮二异氰酸酯的生产技术及展望", 《聚氨酯工业》 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119233A (en) * | 2013-04-27 | 2014-10-29 | 万华化学集团股份有限公司 | A method for preparing 3-aminomethyl-3,5,5-trimethylcyclohexylamine |
| WO2014173044A1 (en) * | 2013-04-27 | 2014-10-30 | 万华化学集团股份有限公司 | Method for preparing 3-aminomethyl-3,5,5-trimethylcyclohexylamine |
| CN103464162A (en) * | 2013-09-03 | 2013-12-25 | 万华化学集团股份有限公司 | Preparation method and application of a nanotube array membrane catalyst composited with Co and Al2O3 |
| CN103664638B (en) * | 2013-12-31 | 2016-04-13 | 张锦碧 | A kind of simple method for preparing of isophorone diamine |
| CN103664638A (en) * | 2013-12-31 | 2014-03-26 | 张锦碧 | Simple preparation method of isophorone diamine |
| CN104056646A (en) * | 2014-06-19 | 2014-09-24 | 万华化学集团股份有限公司 | Preparation method and application of Co/Ni and aluminum pyrophosphate composite hollow microsphere |
| 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 |
| CN107488115A (en) * | 2016-06-10 | 2017-12-19 | 赢创德固赛有限公司 | 2- (3,3, 5-trimethylcyclohexyl) propane-1, 3-diamine, preparation method and application thereof |
| WO2019120064A1 (en) | 2017-12-22 | 2019-06-27 | 浙江新和成股份有限公司 | Method for preparing isophorone diamine by means of hydrogenation reduction of isophorone nitrile imine |
| US11180440B2 (en) | 2017-12-22 | 2021-11-23 | Zhejiang Nhu Company Ltd. | Method for preparing isophorone diamine by means of hydrogenation reduction of isophorone nitrile imine |
| CN115433095A (en) * | 2021-06-01 | 2022-12-06 | 万华化学集团股份有限公司 | A kind of cyclohexylamine derivative and its preparation method, a kind of epoxy resin composition and its preparation method and application |
| 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 |
| CN113493397A (en) * | 2021-07-30 | 2021-10-12 | 山东新和成维生素有限公司 | Preparation method of isophorone imine and preparation method of IPDA (isophorone diisocyanate) containing isophorone imine |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102976956B (en) | 2013-12-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102976956A (en) | Method for preparing 3-aminomethyl-3,5,5-trimethyl cyclohexylamine | |
| KR101732431B1 (en) | Method for preparing 3-aminomethyl-3,5,5-trimethyl cyclohexylamine | |
| EP2743251B1 (en) | 3-aminomethyl-3, 5, 5-trimethyl cyclohexylamine preparation method | |
| EP1519912B1 (en) | Process for increasing the selectivity of the hydrogenation of 4,4'-diaminodiphenylmethane to 4,4'-diaminodicyclohexylmethane in the presence of an n-alkyl-4,4'-diaminodiphenylmethane | |
| EP2459513B1 (en) | A process for the conversion of aliphatic cyclic amines to aliphatic diamines | |
| US8884063B2 (en) | Continuous process for the hydrogenation of 3-cyano-3,5,5-trimethyl-cyclohexylimine | |
| CN102093227B (en) | Method for producing 4,4'-diamino dicyclohexyl methane with low trans-trans isomer content | |
| CN1304110C (en) | Method for the production of isophorondiamine (IPDA,3-aminomethyl-3,5,5-trimethylcyclohexylamine) | |
| CN104230721B (en) | The preparation method of 3-aminomethyl-3,5,5-trimethyl cyclohexylamine | |
| CN113620813B (en) | Preparation method of N, N-dimethyl-1, 3-propanediamine | |
| CN101386579B (en) | Preparation method of 3-aminomethyl-3, 5, 5-trimethylcyclohexylamine | |
| JP2015519354A (en) | Process for producing mono-N-alkyl-piperazine | |
| CN107857704B (en) | Method for preparing 3-aminomethyl-3, 5, 5-trimethylcyclohexylamine and catalyst used in method | |
| US8981093B2 (en) | Process for preparing piperazine | |
| CN104119233B (en) | A kind of method preparing 3-aminomethyl-3,5,5-trimethyl cyclohexylamine | |
| US20250304525A1 (en) | Method for manufacture of isophoronediamine | |
| CN108017547A (en) | A kind of method that cyan-3,5,5-trimethyl cyclohexanone imines hydrogenating reduction prepares isophorone diamine | |
| RU2588498C2 (en) | Method of producing 3-aminomethyl-3,5,5-trimethylcyclohexylamine | |
| CN117069593A (en) | A method for manufacturing 3-aminomethyl-3,5,5-trimethylcyclohexylamine | |
| JPH06329605A (en) | Production of serine or its derivative | |
| KR100613404B1 (en) | Method for producing xylenediamine using imidazoles | |
| CN120303241A (en) | Process for the manufacture of isophoronediamine | |
| HK1215018A1 (en) | Process for preparing 3-aminomethyl-3,5,5-trimethylcyclohexylamine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent of invention or patent application | ||
| CB02 | Change of applicant information |
Address after: 264002 Yantai, South Road, Shandong, No. 7 Applicant after: Wanhua Chemical Group Co.,Ltd. Applicant after: NINGBO WANHUA POLYURETHANES Co.,Ltd. Address before: 264002 Yantai, South Road, Shandong, No. 7 Applicant before: YANTAI WANHUA POLYURETHANES Co.,Ltd. Applicant before: NINGBO WANHUA POLYURETHANES Co.,Ltd. |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: YANTAI WANHUA POLYURETHANE CO., LTD. TO: WANHUA CHEMICAL GROUP CO., LTD. |
|
| C53 | Correction of patent of invention or patent application | ||
| CB02 | Change of applicant information |
Address after: 264002 Yantai, South Road, Shandong, No. 7 Applicant after: Wanhua Chemical Group Co.,Ltd. Applicant after: Wanhua chemical (Ningbo) Co.,Ltd. Address before: 264002 Yantai, South Road, Shandong, No. 7 Applicant before: Wanhua Chemical Group Co.,Ltd. Applicant before: NINGBO WANHUA POLYURETHANES Co.,Ltd. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: 264006 17 Tianshan Road, Yantai economic and Technological Development Zone, Shandong Co-patentee after: Wanhua chemical (Ningbo) Co.,Ltd. Patentee after: Wanhua Chemical Group Co.,Ltd. Address before: 264002 No. 7 happy South Road, Shandong, Yantai Co-patentee before: Wanhua chemical (Ningbo) Co.,Ltd. Patentee before: Wanhua Chemical Group Co.,Ltd. |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Preparation of 3-aminomethyl-3,5,5-trimethylcyclohexylamine Effective date of registration: 20211123 Granted publication date: 20131211 Pledgee: Bank of China Limited by Share Ltd. Yantai branch Pledgor: Wanhua Chemical Group Co.,Ltd. Registration number: Y2021980013026 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20220622 Granted publication date: 20131211 Pledgee: Bank of China Limited by Share Ltd. Yantai branch Pledgor: Wanhua Chemical Group Co.,Ltd. Registration number: Y2021980013026 |