CN103232351A - Preparation method of 2-amino-2-methyl-1-propyl alcohol - Google Patents
Preparation method of 2-amino-2-methyl-1-propyl alcohol Download PDFInfo
- Publication number
- CN103232351A CN103232351A CN2013101525271A CN201310152527A CN103232351A CN 103232351 A CN103232351 A CN 103232351A CN 2013101525271 A CN2013101525271 A CN 2013101525271A CN 201310152527 A CN201310152527 A CN 201310152527A CN 103232351 A CN103232351 A CN 103232351A
- Authority
- CN
- China
- Prior art keywords
- preferred
- oxide
- catalyzer
- methyl
- reaction
- 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
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- -1 2-amino-2-methyl-1-propyl Chemical group 0.000 title abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000001257 hydrogen Substances 0.000 claims abstract description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 35
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 claims description 29
- 239000000047 product Substances 0.000 claims description 23
- 239000010949 copper Substances 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 20
- 238000004821 distillation Methods 0.000 claims description 19
- 229910052802 copper Inorganic materials 0.000 claims description 17
- 125000005907 alkyl ester group Chemical group 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000706 filtrate Substances 0.000 claims description 10
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- 239000004480 active ingredient Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 150000003509 tertiary alcohols Chemical class 0.000 claims description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 229910000510 noble metal Inorganic materials 0.000 claims description 8
- 239000010948 rhodium Substances 0.000 claims description 8
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 7
- 150000003333 secondary alcohols Chemical class 0.000 claims description 7
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 6
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000007327 hydrogenolysis reaction Methods 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 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
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 2
- 229960001866 silicon dioxide Drugs 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 3
- 230000001476 alcoholic effect Effects 0.000 abstract 1
- FUOOLUPWFVMBKG-UHFFFAOYSA-N alpha-amino-isobutyric acid Natural products CC(C)(N)C(O)=O FUOOLUPWFVMBKG-UHFFFAOYSA-N 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 8
- 238000009413 insulation Methods 0.000 description 7
- 238000000576 coating method Methods 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 150000004702 methyl esters Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- FGLBSLMDCBOPQK-UHFFFAOYSA-N 2-nitropropane Chemical compound CC(C)[N+]([O-])=O FGLBSLMDCBOPQK-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000007530 organic bases Chemical group 0.000 description 2
- 229910003445 palladium oxide Inorganic materials 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- XQCUWCZUYXJXRL-UHFFFAOYSA-N copper dioxosilane Chemical compound [Si](=O)=O.[Cu] XQCUWCZUYXJXRL-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of 2-amino-2-methyl-1-propyl alcohol. According to the preparation method, an alcoholic solution of alpha-amino isobutyric acid alkyl ester has hydrogenolyzing and reducing reaction with hydrogen in the presence of metal catalyst to generate 2-amino-2-methyl-1-propyl alcohol in one step. According to the process, the raw materials are cheap in price and easily available, and the reaction step is simple. The method hardly causes environmental pollution and is low in cost and high in yield; moreover, products are easy to purify. The preparation method of 2-amino-2-methyl-1-propyl alcoho is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of 2-amino-2-methyl-1-propanol, belong to the field of organic synthesis.
Background technology
2-amino-2-methyl-1-propanol abbreviates AMP as, is white crystals or colourless viscous liquid, can be miscible with water, dissolve in ethanol.AMP is a kind of multifunction additive that is widely known by the people, and extensively applies in the industries such as coating and printing ink, metal working fluid, personal care and medicine intermediate.AMP is as a kind of primary amine, and its high pKa value makes it that higher pH be arranged, and is softer relatively because it is organic bases simultaneously, with multiple emulsion compatibleness preferably arranged all, less to other performance impact of product.With other organic bases for example ammoniacal liquor, Trimethylamine 99 and triethylamine etc. compare, the good stability of AMP is difficult for xanthochromia, simultaneously toxicity is little, and not volatile, can reduce the smell of system, reduces corrosion and dodges rust, belongs to the conditioning agent of environment-friendly type.
Main product is AMP-95 in the market
TM(95% the aqueous solution) is the trade mark of DOW chemistry.The whole world preceding ten big coatings enterprises are all being used AMP-95 at present
TMAs pH regulator agent and formulation optimization auxiliary agent, AMP-95
TMHelp them to improve the performance of product, reduced cost simultaneously.In the coating market of China, AMP-95
TMAlso be the first-selection of coating material production producer, AMP-95
TMThe market coverage greater than 80%.Domestic well-known coating material production producer brings into use this product to use AMP-95 till today from eighties of last century the nineties
TMStability and superiority get client's consistent favorable comment.
More the synthetic method of existing 2-amino-2-methyl-1-propanol adopts 2-nitropropane and formaldehyde solution to react and generates 2-nitro-2-methyl isophthalic acid-propyl alcohol, carries out hydrogenation reaction again under the metallic nickel catalyzer, separates obtaining 2-amino-2-methyl-1-propanol.US Patent No. 20110224460 also discloses same preparation method.Be that the synthetic method of raw material has its shortcoming with the 2-nitropropane, namely the raw materials cost height is dangerous big, is difficult for storing transportation, and investment of production equipment is big, and product purity is low.
Chinese patent CN1810767 discloses a kind of similar preparation method, and different with above-mentioned route is the source of 2-nitro-2-methyl isophthalic acid-propyl alcohol.This patent adopts Virahol and Sodium Nitrite, Paraformaldehyde 96 to react under 0 ~ 25 ℃, obtains 2-nitro-2-methyl isophthalic acid-propyl alcohol through extraction, washing and distillation again, and shortening obtains product again.This patent does not provide concrete reaction conditions and yield situation.The shortcoming of this route is the synthesis condition complexity, long reaction time, and post-processing difficulty is big.
Chinese patent CN1911899 discloses a preparation method who prepares 2-amino-2-methyl-1-propanol by the Ritter process of iso-butylene.Reaction in iso-butylene and the chlorine feeding acetonitrile is obtained N-[1-(chloromethyl) propyl group] acetochloroamide, add water then and make N-[1-(chloromethyl) propyl group] acetochloroamide carries out first time hydrolysis reaction and obtains N-[1-(chloromethyl) propyl group] ethanamide, N-[1-(chloromethyl) propyl group] ethanamide carries out second time hydrolysis reaction again and obtains described 2-amino-2-methyl-1-propanol.This preparation method also has its shortcoming, and namely the reaction raw materials kind is many, the preparation process complexity, and yield is lower, and yield is 50 ~ 70%.
Problem such as the method for existing preparation 2-amino-2-methyl-1-propanol exists that raw material sources limitation, raw material and intermediate are explosive, complex process, aftertreatment complexity, yield are lower.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of 2-amino-2-methyl-1-propanol, this method raw material is cheap and easy to get, and reactions steps is simple, and the yield height pollutes lowly, does not have harsh reaction conditions, and product is easily purified, and is fit to suitability for industrialized production.
For achieving the above object, the present invention adopts following technical scheme: the α-An Jiyidingsuan alkyl ester is dissolved in the solvent, under catalyst action, in temperature: 0 ~ 250 ℃, hydrogen pressure (absolute pressure, as follows): under the condition of 0.1 ~ 30MPa, the reaction of generation hydrogenolysis reducing, the one-step synthesis 2-amino-2-methyl-1-propanol, and then obtain the 2-amino-2-methyl-1-propanol product through aftertreatment, the reaction times is 1 ~ 30h.Reaction formula is as follows:
Among the present invention, the catalyzer that adopts can be noble metal catalyst, Raney's nickel catalyst and copper-based catalysts etc.; One or both of wherein said noble metal catalyst selected from rhodium, iridium, palladium, platinum, ruthenium, osmium, gold and rhenium element or its salt or its oxide compound or multiple, one or both in the oxide compound of preferred rhodium and platinum element; Described copper-based catalysts can be unsupported catalyst, it also can be loaded catalyst, unsupported catalyst is by active ingredient copper, transition metal oxide and/or rare earth oxide are formed, that is: the composition of unsupported catalyst has following three kinds: active ingredient copper and transition metal oxide, active ingredient copper and rare earth oxide, active ingredient copper and transition metal oxide and rare earth oxide, wherein transition metal oxide is selected from nickel oxide, zinc oxide, chromic oxide, ferric oxide, in cobalt oxide and the molybdenum oxide one or both or multiple, in preferred zinc oxide and the ferric oxide one or both, rare earth oxide is selected from cerium oxide, lanthanum trioxide, Samarium trioxide, in Praseodymium trioxide and the yttrium oxide one or both or multiple, one or both in preferred cerium oxide and the lanthanum trioxide; Loaded catalyst is made up of active ingredient copper and carrier, and carrier is selected from a kind of in aluminum oxide, silicon-dioxide, gac and the zeolite, and the content of active ingredient copper is 0.01 ~ 50wt% in the loaded catalyst, and preferred 1 ~ 20wt% is based on total restatement of catalyzer.
Among the present invention, when described catalyzer is selected noble metal catalyst for use, the mass ratio of catalyst consumption and α-An Jiyidingsuan alkyl ester is 1:1 ~ 20, preferred 1:5 ~ 15, more preferably 1:8 ~ 12, temperature of reaction is 0 ~ 100 ℃, preferred 20 ~ 50 ℃, hydrogen pressure is 7 ~ 20Mpa, preferred 10 ~ 15Mpa, reaction times is 1 ~ 30h, preferred 5 ~ 20h; When catalyzer is selected Raney's nickel catalyst for use, the mass ratio of catalyst consumption and α-An Jiyidingsuan alkyl ester is 1:0.1 ~ 5, preferred 1:0.5 ~ 2, temperature of reaction is 40 ~ 130 ℃, preferred 50 ~ 80 ℃, hydrogen pressure is 15 ~ 30Mpa, preferred 20 ~ 25Mpa, reaction times is 1 ~ 20h, preferred 3 ~ 10h; When catalyzer is selected copper-based catalysts for use, the mass ratio of catalyst consumption and α-An Jiyidingsuan alkyl ester is 1:0.1 ~ 5, preferred 1:0.5 ~ 2, temperature of reaction is 110 ~ 250 ℃, preferred 130 ~ 200 ℃, reaction pressure is 0.1 ~ 30Mpa, preferred 7 ~ 10Mpa, reaction times is 1 ~ 20h, preferred 3 ~ 10h.
Among the present invention, when described catalyzer was selected copper-based catalysts for use, before being used for the catalytic hydrogenolysis reduction reaction, catalyzer needed to carry out prereduction 2 ~ 6 hours earlier in reactor, and reduction temperature is 200 ~ 350 ℃, and hydrogen pressure is 0.1 ~ 3MPa.
Among the present invention, solvent is selected for use according to following principle: when catalyzer is selected noble metal catalyst or Raney's nickel catalyst for use, solvent be selected from primary alconol, secondary alcohol and the tertiary alcohol one or both or multiple, preferred primary alconol; When catalyzer is selected copper-based catalysts for use, solvent be selected from primary alconol, secondary alcohol and the tertiary alcohol one or both or multiple, the preferred tertiary alcohol.Further, primary alconol be selected from methyl alcohol, ethanol and the propyl alcohol one or both or multiple, secondary alcohol is selected from Virahol, the tertiary alcohol is selected from the trimethyl carbinol, these pure boiling points are lower, are conducive to the purifying of product in the aftertreatment.
Among the present invention, raw material α-An Jiyidingsuan alkyl ester is dissolved in after the solvent, and the massfraction of α-An Jiyidingsuan alkyl ester is 1 ~ 80%, and is preferred 10 ~ 40%, based on total restatement of solution.
Among the present invention, alkyl is the cycloalkyl of C1-C5 alkyl straight chain or side chain, C5-C12 in the reactant α-An Jiyidingsuan alkyl ester, preferred C1-C4 alkyl straight chain or side chain.Usually, α-An Jiyidingsuan alkyl ester and product 2-amino-2-methyl-1-propanol when being higher than 150 ℃ and primary alconol or secondary alcohol the N-alkylated reaction easily takes place, generate monoalkylation or two alkyl-alkyl by product, concrete reaction equation is as follows, take the bigger tertiary alcohol of steric hindrance can reduce even suppress the generation of α-An Jiyidingsuan alkyl ester and product 2-amino-2-methyl-1-propanol N-alkylated reaction as solvent, improve product selectivity and yield.
Among the present invention, described aftertreatment comprises solid-liquid separation and purifying products step; Wherein, that solid-liquid separation comprises is centrifugal, a kind of in filtering, separates the catalyzer that obtains and applies mechanically, and the filtrate that obtains is carried out purifying; Purification process is selected from a kind of technology in the distillation, preferably the low-boiling point material that boiling point is lower than 2-amino-2-methyl-1-propanol is removed in the filtrate distillation, and underpressure distillation obtains 2-amino-2-methyl-1-propanol then.
Advantage of the present invention is mainly reflected in: raw material is cheap and easy to get, and reactions steps is simple, and cost is low, and the yield height of product 2-amino-2-methyl-1-propanol can reach more than 85.0%, in the α-An Jiyidingsuan alkyl ester.Product is easily purified, and is fit to suitability for industrialized production.
Description of drawings
The nucleus magnetic hydrogen spectrum of 2-amino-2-methyl-1-propanol among Fig. 1 embodiment 1.
The infrared spectrum of 2-amino-2-methyl-1-propanol among Fig. 2 embodiment 1.
Embodiment
The present invention is further illustrated below in conjunction with embodiment, need to prove, embodiment does not constitute the restriction to the claimed scope of the present invention.
Main raw material source involved in the present invention is as follows:
Methyl alcohol, ethanol, propyl alcohol, the trimethyl carbinol: Chemical Reagent Co., Ltd., Sinopharm Group;
α-An Jiyidingsuan methyl esters, α-An Jiyidingsuan cyclohexyl, α-An Jiyidingsuan propyl ester, α-An Jiyidingsuan ring pentyl ester, the α-An Jiyidingsuan tert-butyl ester: Sigma-Aldrich;
Pt Rh oxide catalyst, Pt Rh-palladium oxide catalyzer: Aladdin;
Grace?Raney?Ni?3300、Grace?Raney?Ni?2400：Grace；
Copper-zinc catalyst, copper-SiO 2 catalyst: it is triumphant to go up Hisoon.
The testing tool that present embodiment uses is: nuclear-magnetism uses Bruker AV300 test, and the 50mg sample is dissolved in the CDCl of 0.5 mL
3In.
The KBr coating method is adopted in infrared use Nicolet Nexus 470 tests.
The 2-amino-2-methyl-1-propanol spectral data is as follows:
1H NMR (400 MHz, D
2O, TMS are interior mark): 3.33 (s, 2H ,-CH
2-), 1.09 (s, 6H, CH
3-).
FT-IR (KBr, σ/cm
-1): 3340 (N-H st and O-H st), 2966(C-H st), 1595(N-H δ) and, 1380(C-H δ), 1310(C-N st) and, 1068(C-O st).
300 g methyl alcohol, 200g α-An Jiyidingsuan methyl esters, 10 g Pt Rh oxide catalyst (Rh:14.81wt%, Pt:70.21wt%, based on the catalyzer gross weight) put in the 1 L autoclave, open to stir logical hydrogen behind the hydrogen exchange three times, the control temperature of reaction is 20 ℃, hydrogen pressure (absolute pressure, down together) 15.0MPa kept 20 hours, the reaction process discontinuous feeds hydrogen, keep-ups pressure at 15.0 MPa.Reaction finishes after-filtration, the filter cake catalyzer is applied mechanically, methyl alcohol is removed in filtrate distillation (normal pressure) earlier, (95 ~ 97 ℃/20mmHg) obtain highly purified 2-amino-2-methyl-1-propanol product 139.92 g of further underpressure distillation then, product is through nmr analysis and Infrared spectroscopy, spectrogram is respectively Fig. 1, Fig. 2, and yield is 91.97%, in the α-An Jiyidingsuan methyl esters.
Embodiment 2
400 g ethanol, 100g α-An Jiyidingsuan cyclohexyl, 5 g Pt Rh-palladium oxide catalyzer (Rh:12.60wt%, Pt:56.69wt%, Pd:13.03wt% is based on the total restatement of catalyzer) put in the 1 L autoclave, open and stir, logical hydrogen behind the hydrogen exchange three times, be warming up to 50 ℃ and insulation reaction, pressure 7.0MPa kept 9 hours, the reaction process discontinuous feeds hydrogen, keep-ups pressure at 7.0 MPa.Reaction finishes after-filtration, the filter cake catalyzer is applied mechanically, ethanol, hexalin are removed in filtrate distillation (normal pressure) successively earlier, (95 ~ 97 ℃/20mmHg) obtain highly purified 2-amino-2-methyl-1-propanol product 44.38 g of further underpressure distillation then, yield is 92.25%, in the α-An Jiyidingsuan cyclohexyl.
Embodiment 3
350 g propyl alcohol, 150g α-An Jiyidingsuan propyl ester, 75 g Grace Raney Ni 3300 put in the 1 L autoclave, open to stir, logical hydrogen behind the hydrogen exchange three times is warming up to 50 ℃ and insulation reaction, pressure 25.0MPa, kept 10 hours, the reaction process discontinuous feeds hydrogen, keep-ups pressure at 25.0 MPa.Reaction finishes after-filtration, the filter cake catalyzer is applied mechanically, and propyl alcohol is removed in filtrate distillation (normal pressure) earlier, (95 ~ 97 ℃/20mmHg) obtain highly purified 2-amino-2-methyl-1-propanol product 85.23 g of further underpressure distillation then, yield is 92.57%, in the α-An Jiyidingsuan propyl ester.
Embodiment 4
450 g methyl alcohol, 50g α-An Jiyidingsuan ring pentyl ester, 100 g Grace Raney Ni 2400 put in the 1 L autoclave, open to stir, logical hydrogen behind the hydrogen exchange three times is warming up to 80 ℃ and insulation reaction, pressure 25.0MPa, kept 3 hours, the reaction process discontinuous feeds hydrogen, keep-ups pressure at 25.0 MPa.Reaction finishes after-filtration, the filter cake catalyzer is applied mechanically, methyl alcohol, cyclopentanol are removed in filtrate distillation (normal pressure) successively earlier, (95 ~ 97 ℃/20mmHg) obtain highly purified 2-amino-2-methyl-1-propanol product 23.91 g of further underpressure distillation then, yield is 91.88%, in α-An Jiyidingsuan ring pentyl ester.
Embodiment 5
1. take by weighing 25 g copper-zinc (Cu:47.79wt%, Zn:32.58wt%, based on the total restatement of catalyzer) catalyzer is in 1 L autoclave, logical hydrogen behind the hydrogen exchange three times, be warming up to 200 ℃ and insulation reaction, pressure is 2.0MPa, keeps 3 hours, the reaction process discontinuous feeds hydrogen, keep-ups pressure at 2.0 MPa.Activation is cooled to room temperature after finishing.
2. after treating that the high pressure temperature in the kettle is down to room temperature, with the 450 g trimethyl carbinols, the 50g α-An Jiyidingsuan tert-butyl ester is put into the autoclave from opening for feed, open and stir, logical hydrogen behind the hydrogen exchange three times, be warming up to 130 ℃ and insulation reaction, pressure 10.0MPa, kept 3 hours, reaction finishes after-filtration, and the filter cake catalyzer is applied mechanically, the trimethyl carbinol is removed in filtrate distillation (normal pressure) earlier, (95 ~ 97 ℃/20mmHg) obtain highly purified 2-amino-2-methyl-1-propanol product 24.27 g, yield is 86.73%, in the α-An Jiyidingsuan tert-butyl ester in underpressure distillation then.
Embodiment 6
1. take by weighing 100 g copper-silicon-dioxide (Cu:21.55wt%, based on the total restatement of catalyzer) catalyzer is in 1 L autoclave, logical hydrogen behind the hydrogen exchange three times, keep temperature of reaction intensification most 350 ℃ and insulation reaction, pressure is 2.0MPa, kept 3 hours, the reaction process discontinuous feeds hydrogen, keep-ups pressure at 2.0 MPa.Activation is cooled to room temperature after finishing.
2. after treating that the high pressure temperature in the kettle is down to room temperature, with the 450 g trimethyl carbinols, the 50g α-An Jiyidingsuan tert-butyl ester is put into the autoclave from opening for feed, open and stir, logical hydrogen behind the hydrogen exchange three times, be warming up to 200 ℃ and insulation reaction, keeping temperature of reaction is 200 ℃, and pressure 7.0MPa kept 3 hours, reaction finishes after-filtration, the filter cake catalyzer is applied mechanically, and the trimethyl carbinol is removed in filtrate distillation (normal pressure) earlier, (95 ~ 97 ℃/20mmHg) obtain highly purified 2-amino-2-methyl-1-propanol product 24.71 g of underpressure distillation then, yield is 88.29%, in the α-An Jiyidingsuan tert-butyl ester.
Claims (14)
1. the preparation method of a 2-amino-2-methyl-1-propanol, it is characterized in that, described method comprises: the α-An Jiyidingsuan alkyl ester is dissolved in the solvent, under catalyst action, in temperature: 0 ~ 250 ℃, hydrogen pressure (absolute pressure, as follows): 0.1 ~ 30MPa, condition under, the hydrogenolysis reducing reaction takes place, the one-step synthesis 2-amino-2-methyl-1-propanol, the reaction times is 1 ~ 30h.
2. method according to claim 1 is characterized in that, described catalyzer is selected from a kind of in noble metal catalyst, Raney's nickel catalyst and the copper-based catalysts.
3. method according to claim 2, it is characterized in that, one or both of described noble metal catalyst selected from rhodium, iridium, palladium, platinum, ruthenium, osmium, gold and rhenium element or its salt or its oxide compound or multiple, one or both in the oxide compound of preferred rhodium and platinum element.
4. method according to claim 2, it is characterized in that, described copper-based catalysts is made up of active ingredient copper, transition metal oxide and/or rare earth oxide, wherein transition metal oxide be selected from nickel oxide, zinc oxide, chromic oxide, ferric oxide, cobalt oxide and the molybdenum oxide one or both or multiple, preferred zinc oxide and ferric oxide; Rare earth oxide be selected from cerium oxide, lanthanum trioxide, Samarium trioxide, Praseodymium trioxide and the yttrium oxide one or both or multiple, one or both in preferred cerium oxide and the lanthanum trioxide.
5. method according to claim 2, it is characterized in that, described copper-based catalysts is made up of active ingredient copper and carrier, carrier is selected from a kind of in aluminum oxide, silicon-dioxide, gac and the zeolite, the content of active ingredient copper is 0.01 ~ 50wt%, preferred 1 ~ 20wt% is based on total restatement of catalyzer.
6. according to claim 1 or 2 or 3 described methods, it is characterized in that when described catalyzer was selected noble metal catalyst for use, the mass ratio of catalyst consumption and α-An Jiyidingsuan alkyl ester was 1:1 ~ 20, preferred 1:5 ~ 15, more preferably 1:8 ~ 12, temperature of reaction is 0 ~ 100 ℃, preferred 20 ~ 50 ℃, hydrogen pressure is 7 ~ 20Mpa, preferred 10 ~ 15Mpa, the reaction times is 1 ~ 30h, preferred 5 ~ 20h.
7. method according to claim 1 and 2, it is characterized in that, when catalyzer was selected Raney's nickel catalyst for use, the mass ratio of catalyst consumption and α-An Jiyidingsuan alkyl ester was 1:0.1 ~ 5, preferred 1:0.5 ~ 2, temperature of reaction is 40 ~ 130 ℃, preferred 50 ~ 80 ℃, hydrogen pressure (absolute pressure) is 15 ~ 30Mpa, preferred 20 ~ 25Mpa, reaction times is 1 ~ 20h, preferred 3 ~ 10h.
8. according to claim 1 or 2 or 4 or 5 described methods, it is characterized in that, when catalyzer was selected copper-based catalysts for use, the mass ratio of catalyst consumption and α-An Jiyidingsuan alkyl ester was 1:0.1 ~ 5, preferred 1:0.5 ~ 2, temperature of reaction is 110 ~ 250 ℃, preferred 130 ~ 200 ℃, hydrogen pressure (absolute pressure) is 0.1 ~ 30Mpa, preferred 7 ~ 10Mpa, reaction times is 1 ~ 20h, preferred 3 ~ 10h.
9. method according to claim 1 and 2 is characterized in that, when described catalyzer is selected copper-based catalysts for use, before being used for catalytic hydrogenation reaction, catalyzer needs to carry out prereduction 2 ~ 6 hours earlier in reactor, and reduction temperature is 200 ~ 350 ℃, and hydrogen pressure is 0.1 ~ 3MPa.
10. according to each described method in claim 1 or 2, it is characterized in that, when described catalyzer is selected noble metal catalyst or Raney's nickel catalyst for use, solvent be selected from primary alconol, secondary alcohol and the tertiary alcohol one or both or multiple, preferred primary alconol; When catalyzer is selected copper-based catalysts for use, solvent be selected from primary alconol, secondary alcohol and the tertiary alcohol one or both or multiple, the preferred tertiary alcohol.
11. method according to claim 10 is characterized in that, described primary alconol be selected from methyl alcohol, ethanol and the propyl alcohol one or both or multiple, described secondary alcohol is selected from Virahol, the described tertiary alcohol is selected from the trimethyl carbinol.
12. method according to claim 1 is characterized in that, after the α-An Jiyidingsuan alkyl ester was dissolved in solvent, the massfraction in solution was 1 ~ 80%, and is preferred 10 ~ 40%, with total restatement of solution.
13., it is characterized in that alkyl is the cycloalkyl of C1-C5 alkyl straight chain or side chain or C5-C12 in the described α-An Jiyidingsuan alkyl ester according to each described method among the claim 1-12, preferred C1-C4 alkyl straight chain or side chain.
14. according to each described method among the claim 1-13, it is characterized in that, also comprise solid-liquid separation and purifying products step after the hydrogenolysis reducing reaction; Wherein, that solid-liquid separation is selected from is centrifugal, a kind of in filtering, separates the catalyzer that obtains and applies mechanically, and the filtrate that obtains is carried out purifying; The method of described purifying is selected from a kind of technology in the distillation, preferably the low-boiling point material that boiling point is lower than 2-amino-2-methyl-1-propanol is removed in the filtrate distillation, and underpressure distillation obtains 2-amino-2-methyl-1-propanol then.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310152527.1A CN103232351B (en) | 2013-04-27 | 2013-04-27 | Preparation method of 2-amino-2-methyl-1-propyl alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310152527.1A CN103232351B (en) | 2013-04-27 | 2013-04-27 | Preparation method of 2-amino-2-methyl-1-propyl alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103232351A true CN103232351A (en) | 2013-08-07 |
| CN103232351B CN103232351B (en) | 2014-11-05 |
Family
ID=48880435
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310152527.1A Active CN103232351B (en) | 2013-04-27 | 2013-04-27 | Preparation method of 2-amino-2-methyl-1-propyl alcohol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103232351B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106831451A (en) * | 2017-02-03 | 2017-06-13 | 荆楚理工学院 | A kind of synthetic method of 2 aminoisobutanol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1911899A (en) * | 2006-08-18 | 2007-02-14 | 临安善才科技有限公司 | Preparation method of 2-amino-2-methyl-1-propanol |
| CN101531568A (en) * | 2009-04-13 | 2009-09-16 | 烟台万华聚氨酯股份有限公司 | Method for synthesizing 1,6-hexamethylene glycol by using dimethyl adipate gas phase and hydrogen |
-
2013
- 2013-04-27 CN CN201310152527.1A patent/CN103232351B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1911899A (en) * | 2006-08-18 | 2007-02-14 | 临安善才科技有限公司 | Preparation method of 2-amino-2-methyl-1-propanol |
| CN101531568A (en) * | 2009-04-13 | 2009-09-16 | 烟台万华聚氨酯股份有限公司 | Method for synthesizing 1,6-hexamethylene glycol by using dimethyl adipate gas phase and hydrogen |
Non-Patent Citations (2)
| Title |
|---|
| MARTIN STUDER等: "Catalytic Hydrogenation of Chiral a-Amino and a-Hydroxy Esters at Room Temperature with Nishimura Catalyst without Racemization", 《ADV. SYNTH. CATAL》, vol. 343, no. 8, 31 December 2001 (2001-12-31), XP001149359, DOI: doi:10.1002/1615-4169(20011231)343:8<802::AID-ADSC802>3.0.CO;2-T * |
| MATTHEW L. CLARKE等: "Hydrogenation of Aldehydes, Esters, Imines, and Ketones Catalyzed by a Ruthenium Complex of a Chiral Tridentate Ligand", 《ORGANOMETALLICS》, vol. 26, 31 December 2007 (2007-12-31), pages 16 - 19, XP055106879, DOI: doi:10.1021/om060673b * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106831451A (en) * | 2017-02-03 | 2017-06-13 | 荆楚理工学院 | A kind of synthetic method of 2 aminoisobutanol |
| CN106831451B (en) * | 2017-02-03 | 2018-09-21 | 荆楚理工学院 | A kind of synthetic method of 2- aminoisobutanols |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103232351B (en) | 2014-11-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102285891B (en) | Method for preparing arylamine by catalytic hydrogenation of aromatic nitro compound | |
| CN103619798A (en) | Process for preparing formic acid | |
| CN102964278B (en) | Method for preparing CLT acid (2-amino-4-methyl-5-chlorobenzene sulfonic acid) by continuous catalytic hydrogenation reduction | |
| CN106866364A (en) | A kind of method that 1,3- ring pentanediols are prepared by furfuryl alcohol | |
| CN106866331A (en) | A kind of method that cyclopentadiene or dicyclopentadiene are prepared by furfuryl alcohol | |
| CN113024351A (en) | Production method of isopropanol | |
| CN106543017B (en) | A kind of preparation method of 4 aminocyclohexyl acetic acid | |
| CN102625790B (en) | Method for producing alicyclic alcohol | |
| CN103254038A (en) | Method for preparing cyclohexanol by using benzene | |
| CN103232351B (en) | Preparation method of 2-amino-2-methyl-1-propyl alcohol | |
| CN106622215B (en) | Polycondensation catalyst, preparation method and application thereof, method for synthesizing diisobutyl ketone and method for synthesizing diisobutyl alcohol | |
| CN107903146B (en) | Method for preparing 1, 2-hexanediol by catalytic oxidation of 1-hexene | |
| KR20150063058A (en) | Method for synthesising 2,5-di(hydroxymethyl)furan and 2,5-di(hydroxymethyl)tetrahydrofuran by selective hydrogenation of furan-2,5-dialdehyde | |
| CN106810459A (en) | A kind of method that amino alcohol is prepared as raw material with dihydroxylic alcohols and/or polyalcohol | |
| CN102701991A (en) | Method for preparing nonane diamine | |
| CN101863778A (en) | Production method of 4-aminodiphenylamine | |
| DE102006061535A1 (en) | Production of aminoalkylamine for use e.g. as complex former or monomer, involves adding the corresponding nitrile to a mixture of catalyst, ammonia and solvent and reacting with hydrogen under pressure | |
| CN118055918A (en) | Comprising SiO functionalized at sulfonic acid2Supported heterogeneous catalysts of transition metals and the use of such catalysts in a process for the production of ethers | |
| TWI522335B (en) | Process for preparing 2,2-difluoroethylamine by hydrogenating 1,1-difluoro-2-nitroethane | |
| CN101830789B (en) | Method for preparing cyclohexanone | |
| CN102256918A (en) | Catalytic method for the production of diol compounds | |
| CN110172029B (en) | Method for continuously synthesizing 2-amino-2-methyl-1-propanol | |
| CN102675133A (en) | Synthesis method for synthesizing p-methoxyaniline compound through hydrogenation and transposition | |
| CN107778151B (en) | Method for preparing methyl ethyl ketone by sec-butyl alcohol dehydrogenation | |
| WO2020028262A1 (en) | Processes and cataylsts for producing diethanolamine from glycolaldehyde |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C53 | Correction of patent of invention or patent application | ||
| CB02 | Change of applicant information |
Address after: 264002 Yantai City, Shandong province Zhifu District No. 7 Applicant after: Wanhua Chemical Group Co., Ltd. Applicant after: Ningbo Wanhua Polyurethane Co., Ltd. Address before: 264002 Yantai City, Shandong province Zhifu District No. 7 Applicant before: Yantai Wanhua Polyurethane Co., Ltd. Applicant before: Ningbo Wanhua Polyurethane Co., Ltd. |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: YANTAI WANHUA POLYURETHANE CO., LTD. TO: WANHUA CHEMICAL GROUP CO., LTD. |
|
| 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 City, Shandong province Zhifu District No. 7 Applicant after: Wanhua Chemical Group Co., Ltd. Applicant after: Wanhua Chemical (Ningbo) Co., Ltd. Address before: 264002 Yantai City, Shandong province Zhifu District No. 7 Applicant before: Wanhua Chemical Group Co., Ltd. Applicant before: Ningbo Wanhua Polyurethane 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 happy South Road, Zhifu District, Yantai, Shandong Province, No. 7 Co-patentee before: Wanhua Chemical (Ningbo) Co., Ltd. Patentee before: Wanhua Chemical Group Co., Ltd. |