CN103232351B - 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
- CN103232351B CN103232351B CN201310152527.1A CN201310152527A CN103232351B CN 103232351 B CN103232351 B CN 103232351B CN 201310152527 A CN201310152527 A CN 201310152527A CN 103232351 B CN103232351 B CN 103232351B
- Authority
- CN
- China
- Prior art keywords
- oxide
- catalyzer
- methyl
- copper
- 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.)
- Active
Links
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, referred to as AMP, is white crystals or colourless viscous liquid, can be miscible with water, dissolve in ethanol.AMP is a kind of multifunction additive being widely known by the people, and is widely used 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 have higher pH value, meanwhile, because it is organic bases, relatively soft, all has good compatibleness with multiple emulsion, less to other performance impact of product.Compare with other organic bases such as ammoniacal liquor, Trimethylamine 99 and triethylamine etc., the good stability of AMP, is difficult for xanthochromia, and toxicity is little simultaneously, 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 front ten large coatings enterprises are all being used AMP-95 at present
tMas pH adjusting agent and formulation optimization auxiliary agent, AMP-95
tMhelp them to improve the performance of product, reduced cost simultaneously.In Chinese Coating Market, AMP-95
tMthe first-selection of Ye Shi coating material production producer, AMP-95
tMthe market coverage be greater than 80%.Domestic well-known coating material production producer brings into use this product to use till today from eighties of last century the nineties, AMP-95
tMstability and superiority get client's consistent favorable comment.
More the synthetic method of existing 2-amino-2-methyl-1-propanol, adopt 2-nitropropane and formaldehyde solution to react and generate 2-nitro-2-methyl isophthalic acid-propyl alcohol, then under metalNicatalyst, carry out hydrogenation reaction, and separation obtains 2-amino-2-methyl-1-propanol.US Patent No. 20110224460 also discloses same preparation method.The synthetic method that the 2-nitropropane of take is raw material has its shortcoming, and raw materials cost is high, dangerous large, is difficult for storing transportation, and investment of production equipment is large, and product purity is low.
Chinese patent CN1810767 discloses a kind of similar preparation method, and different from above-mentioned route is the source of 2-nitro-2-methyl isophthalic acid-propyl alcohol.This patent adopts Virahol and Sodium Nitrite, paraformaldehyde to react at 0 ~ 25 ℃, then obtains 2-nitro-2-methyl isophthalic acid-propyl alcohol through extraction, washing and distillation, then shortening obtains product.This patent does not provide concrete reaction conditions and yield situation.The shortcoming of this route is that synthesis condition is complicated, long reaction time, and post-processing difficulty is large.
Chinese patent CN1911899 discloses a preparation method who prepares 2-amino-2-methyl-1-propanol by the Ritter process of iso-butylene.Iso-butylene and chlorine are passed into reaction in acetonitrile and obtain N-[1-(chloromethyl) propyl group] acetochloroamide, then add water to make N-[1-(chloromethyl) propyl group] acetochloroamide carries out hydrolysis reaction for the first time and obtains N-[1-(chloromethyl) propyl group] ethanamide, N-[1-(chloromethyl) propyl group] ethanamide carries out hydrolysis reaction for the second time again and obtains described 2-amino-2-methyl-1-propanol.This preparation method also has its shortcoming, and reaction raw materials kind is many, and preparation process is complicated, and yield is lower, and yield is 50 ~ 70%.
There is the problems such as raw material sources limitation, raw material and intermediate are explosive, complex process, aftertreatment is complicated, yield is lower in the existing method of preparing 2-amino-2-methyl-1-propanol.
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, the method raw material is cheap and easy to get, and reactions steps is simple, and yield is high, pollutes lowly, and without harsh reaction conditions, product is easily purified, and is applicable to suitability for industrialized production.
For achieving the above object, the present invention adopts following technical scheme: α-aminoacid alkyl ester is dissolved in 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, one-step synthesis 2-amino-2-methyl-1-propanol, and then obtain 2-amino-2-methyl-1-propanol product through aftertreatment, the reaction times is 1 ~ 30h.Reaction formula is as follows:
。
In the present invention, the catalyzer adopting can be noble metal catalyst, Raney's nickel catalyst and copper-based catalysts etc., the one or two or more 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, preferably one or both in the oxide compound of rhodium and platinum element, described copper-based catalysts can be unsupported catalyst, also can be loaded catalyst, unsupported catalyst is by active ingredient copper, transition metal oxide and/or rare earth oxide form, 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, one or two or more in cobalt oxide and molybdenum oxide, one or both in preferential oxidation zinc and ferric oxide, rare earth oxide is selected from cerium oxide, lanthanum trioxide, Samarium trioxide, one or two or more in Praseodymium trioxide and yttrium oxide, one or both in preferential oxidation cerium and lanthanum trioxide, loaded catalyst is comprised of active ingredient copper and carrier, and carrier is selected from a kind of in aluminum oxide, silicon-dioxide, gac and zeolite, and in loaded catalyst, the content of active ingredient copper is 0.01 ~ 50wt%, preferred 1 ~ 20wt%, the total restatement based on catalyzer.
In the present invention, when described catalyzer is selected noble metal catalyst, the mass ratio of the consumption of catalyzer and α-aminoacid alkyl ester is 1:1 ~ 20, preferably 1:5 ~ 15, more preferably 1:8 ~ 12, temperature of reaction is 0 ~ 100 ℃, preferably 20 ~ 50 ℃, hydrogen pressure is 7 ~ 20Mpa, preferably 10 ~ 15Mpa, reaction times is 1 ~ 30h, preferably 5 ~ 20h; When catalyzer is selected Raney's nickel catalyst, the mass ratio of the consumption of catalyzer and α-aminoacid alkyl ester is 1:0.1 ~ 5, preferred 1:0.5 ~ 2, temperature of reaction is 40 ~ 130 ℃, preferably 50 ~ 80 ℃, hydrogen pressure is 15 ~ 30Mpa, preferably 20 ~ 25Mpa, reaction times is 1 ~ 20h, preferably 3 ~ 10h; When catalyzer is selected copper-based catalysts, the mass ratio of the consumption of catalyzer and α-aminoacid alkyl ester is 1:0.1 ~ 5, preferred 1:0.5 ~ 2, temperature of reaction is 110 ~ 250 ℃, preferably 130 ~ 200 ℃, reaction pressure is 0.1 ~ 30Mpa, preferably 7 ~ 10Mpa, reaction times is 1 ~ 20h, preferably 3 ~ 10h.
In the present invention, when described catalyzer is selected copper-based catalysts, before for catalytic hydrogenolysis reduction reaction, catalyzer needs first in reactor, to carry out prereduction 2 ~ 6 hours, and reduction temperature is 200 ~ 350 ℃, and hydrogen pressure is 0.1 ~ 3MPa.
In the present invention, solvent is selected according to following principle: when catalyzer is selected noble metal catalyst or Raney's nickel catalyst, solvent is selected from one or two or more in primary alconol, secondary alcohol and the tertiary alcohol, preferably primary alconol; When catalyzer is selected copper-based catalysts, solvent is selected from one or two or more in primary alconol, secondary alcohol and the tertiary alcohol, preferably the tertiary alcohol.Further, primary alconol is selected from the one or two or more in methyl alcohol, ethanol and propyl alcohol, and secondary alcohol is selected from Virahol, and the tertiary alcohol is selected from the trimethyl carbinol, and the boiling point of these alcohol is lower, is conducive to the purifying of product in aftertreatment.
In the present invention, after raw material α-aminoacid alkyl ester is dissolved in solvent, the massfraction of α-aminoacid alkyl ester is 1 ~ 80%, preferably 10 ~ 40%, and the total restatement based on solution.
In the present invention, the cycloalkyl of alkyl C1-C5 alkyl that be straight chain or side chain, C5-C12 in reactant α-aminoacid alkyl ester, preferably C1-C4 alkyl straight chain or side chain.Conventionally, α-aminoacid alkyl ester and product 2-amino-2-methyl-1-propanol when higher than 150 ℃ and primary alconol or secondary alcohol easily there is N-alkylated reaction, generate monoalkylation or two alkyl-alkyl by product, concrete reaction equation is as follows, take the tertiary alcohol that steric hindrance is larger can reduce as solvent the generation that even suppresses α-aminoacid alkyl ester and product 2-amino-2-methyl-1-propanol N-alkylated reaction, improve selectivity and the yield of product.
In 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, and the catalyzer that separation obtains is applied mechanically, and the filtrate obtaining is carried out purifying; Purification process is selected from a kind of technique in distillation, preferably filtrate distillation is removed to boiling point lower than the low-boiling point material of 2-amino-2-methyl-1-propanol, and then underpressure distillation obtains 2-amino-2-methyl-1-propanol.
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 of product 2-amino-2-methyl-1-propanol is high, can reach more than 85.0%, in α-aminoacid alkyl ester.Product is easily purified, and is applicable to suitability for industrialized production.
Accompanying drawing explanation
The nucleus magnetic hydrogen spectrum of 2-amino-2-methyl-1-propanol in Fig. 1 embodiment 1.
The infrared spectrum of 2-amino-2-methyl-1-propanol in Fig. 2 embodiment 1.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated, it should be noted that, embodiment does not form 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-aminoacid methyl esters, α-aminoacid cyclohexyl, α-aminoacid propyl ester, α-aminoacid ring pentyl ester, the α-aminoacid 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: upper Hisoon is triumphant.
The testing tool that the present embodiment is used is: nuclear-magnetism is used Bruker AV300 test, and 50mg sample is dissolved in the CDCl of 0.5 mL
3in.
Infrared use Nicolet Nexus 470 tests, adopt KBr coating method.
2-amino-2-methyl-1-propanol spectral data is as follows:
1h NMR (400 MHz, D
2o, TMS is 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).
Embodiment 1
300 g methyl alcohol, 200g α-aminoacid methyl esters, 10 g Pt Rh oxide catalyst (Rh:14.81wt%, Pt:70.21wt%, based on catalyzer gross weight) put in 1 L autoclave, to open and stir, hydrogen exchange leads to hydrogen three times afterwards, controlling temperature of reaction is 20 ℃, hydrogen pressure (absolute pressure, lower same) 15.0MPa, keeps 20 hours, reaction process discontinuous passes into hydrogen, keeps pressure at 15.0 MPa.Reaction finishes rear filtration, filter cake catalyzer is applied mechanically, methyl alcohol is first removed in filtrate distillation (normal pressure), then further underpressure distillation (95 ~ 97 ℃/20mmHg) obtains highly purified 2-amino-2-methyl-1-propanol product 139.92 g, product is through nmr analysis and Infrared spectroscopy, spectrogram is respectively Fig. 1, Fig. 2, and yield is 91.97%, in α-aminoacid methyl esters.
Embodiment 2
400 g ethanol, 100g α-aminoacid cyclohexyl, 5 g Pt Rh-palladium oxide catalyzer (Rh:12.60wt%, Pt:56.69wt%, Pd:13.03wt%, based on the total restatement of catalyzer) put in 1 L autoclave, open and stir, hydrogen exchange leads to hydrogen three times afterwards, be warming up to 50 ℃ and insulation reaction, pressure 7.0MPa, keeps 9 hours, reaction process discontinuous passes into hydrogen, keeps pressure at 7.0 MPa.Reaction finishes rear filtration, filter cake catalyzer is applied mechanically, ethanol, hexalin are first removed in filtrate distillation (normal pressure) successively, then further underpressure distillation (95 ~ 97 ℃/20mmHg) obtains highly purified 2-amino-2-methyl-1-propanol product 44.38 g, yield is 92.25%, in α-aminoacid cyclohexyl.
Embodiment 3
350 g propyl alcohol, 150g α-aminoacid propyl ester, 75 g Grace Raney Ni 3300 put in 1 L autoclave, open and stir, hydrogen exchange leads to hydrogen three times afterwards, is warming up to 50 ℃ and insulation reaction, pressure 25.0MPa, keep 10 hours, reaction process discontinuous passes into hydrogen, keeps pressure at 25.0 MPa.Reaction finishes rear filtration, filter cake catalyzer is applied mechanically, and propyl alcohol is first removed in filtrate distillation (normal pressure), and then further underpressure distillation (95 ~ 97 ℃/20mmHg) obtains highly purified 2-amino-2-methyl-1-propanol product 85.23 g, yield is 92.57%, in α-aminoacid propyl ester.
Embodiment 4
450 g methyl alcohol, 50g α-aminoacid ring pentyl ester, 100 g Grace Raney Ni 2400 put in 1 L autoclave, open and stir, hydrogen exchange leads to hydrogen three times afterwards, is warming up to 80 ℃ and insulation reaction, pressure 25.0MPa, keep 3 hours, reaction process discontinuous passes into hydrogen, keeps pressure at 25.0 MPa.Reaction finishes rear filtration, filter cake catalyzer is applied mechanically, methyl alcohol, cyclopentanol are first removed in filtrate distillation (normal pressure) successively, then further underpressure distillation (95 ~ 97 ℃/20mmHg) obtains highly purified 2-amino-2-methyl-1-propanol product 23.91 g, yield is 91.88%, in α-aminoacid ring pentyl ester.
Embodiment 5
1. take 25 g copper-zinc (Cu:47.79wt%, Zn:32.58wt%, based on the total restatement of catalyzer) catalyzer is in 1 L autoclave, hydrogen exchange leads to hydrogen three times afterwards, be warming up to 200 ℃ and insulation reaction, pressure is 2.0MPa, keeps 3 hours, reaction process discontinuous passes into hydrogen, keeps pressure at 2.0 MPa.After finishing, activation is cooled to room temperature.
2. until high pressure temperature in the kettle, be down to after room temperature, by the 450 g trimethyl carbinols, the 50g α-aminoacid tert-butyl ester is put into autoclave from opening for feed, open and stir, hydrogen exchange leads to hydrogen three times afterwards, be warming up to 130 ℃ and insulation reaction, pressure 10.0MPa, keep 3 hours, reaction finishes rear filtration, and filter cake catalyzer is applied mechanically, the trimethyl carbinol is first removed in filtrate distillation (normal pressure), then underpressure distillation (95 ~ 97 ℃/20mmHg) obtains highly purified 2-amino-2-methyl-1-propanol product 24.27 g, and yield is 86.73%, in the α-aminoacid tert-butyl ester.
Embodiment 6
1. take 100 g copper-silicon-dioxide (Cu:21.55wt%, based on the total restatement of catalyzer) catalyzer is in 1 L autoclave, hydrogen exchange leads to hydrogen three times afterwards, maintain temperature of reaction intensification most 350 ℃ and insulation reaction, pressure is 2.0MPa, keep 3 hours, reaction process discontinuous passes into hydrogen, keeps pressure at 2.0 MPa.After finishing, activation is cooled to room temperature.
2. until high pressure temperature in the kettle, be down to after room temperature, by the 450 g trimethyl carbinols, the 50g α-aminoacid tert-butyl ester is put into autoclave from opening for feed, open and stir, hydrogen exchange leads to hydrogen three times afterwards, be warming up to 200 ℃ and insulation reaction, maintaining temperature of reaction is 200 ℃, pressure 7.0MPa, keep 3 hours, reaction finishes rear filtration, filter cake catalyzer is applied mechanically, the trimethyl carbinol is first removed in filtrate distillation (normal pressure), then underpressure distillation (95 ~ 97 ℃/20mmHg) obtains highly purified 2-amino-2-methyl-1-propanol product 24.71 g, yield is 88.29%, in the α-aminoacid tert-butyl ester.
Claims (13)
1. the preparation method of a 2-amino-2-methyl-1-propanol, it is characterized in that, described method comprises: α-aminoacid alkyl ester is dissolved in solvent, under catalyst action, in temperature: 0～250 ℃, hydrogen absolute pressure: 0.1～30MPa, condition under, the reaction of generation hydrogenolysis reducing, one-step synthesis 2-amino-2-methyl-1-propanol, the reaction times is 1～30h;
Described catalyzer is copper-based catalysts, described copper-based catalysts is comprised of active ingredient copper, transition metal oxide and/or rare earth oxide, and wherein transition metal oxide is selected from the one or two or more in nickel oxide, zinc oxide, chromic oxide, ferric oxide, cobalt oxide and molybdenum oxide; Rare earth oxide is selected from the one or two or more in cerium oxide, lanthanum trioxide, Samarium trioxide, Praseodymium trioxide and yttrium oxide;
Or described copper-based catalysts is comprised of active ingredient copper and carrier, carrier is selected from a kind of in aluminum oxide, silicon-dioxide, gac and zeolite, and the content of active ingredient copper is 0.01～50wt%, the total restatement based on catalyzer.
2. method according to claim 1, it is characterized in that, described catalyzer is copper-based catalysts, and described copper-based catalysts is comprised of active ingredient copper, transition metal oxide and/or rare earth oxide, and wherein transition metal oxide is selected from zinc oxide and ferric oxide; Rare earth oxide is selected from one or both in cerium oxide and lanthanum trioxide;
Or described copper-based catalysts is comprised of active ingredient copper and carrier, carrier is selected from a kind of in aluminum oxide, silicon-dioxide, gac and zeolite, and the content of active ingredient copper is 1～20wt%, the total restatement based on catalyzer.
3. method according to claim 1 and 2, is characterized in that, the mass ratio of the consumption of catalyzer and α-aminoacid alkyl ester is 1:0.1～5, and temperature of reaction is 110～250 ℃, and hydrogen absolute pressure is 0.1～30Mpa, and the reaction times is 1～20h.
4. method according to claim 3, is characterized in that, the mass ratio of the consumption of catalyzer and α-aminoacid alkyl ester is 1:0.5～2, and temperature of reaction is 130～200 ℃, and hydrogen absolute pressure is 7～10Mpa, and the reaction times is 3～10h.
5. method according to claim 1 and 2, is characterized in that, when described catalyzer is before for catalytic hydrogenation reaction, catalyzer needs first in reactor, to carry out prereduction 2～6 hours, and reduction temperature is 200～350 ℃, and hydrogen pressure is 0.1～3MPa.
6. method according to claim 1 and 2, is characterized in that, solvent is selected from one or two or more in primary alconol, secondary alcohol and the tertiary alcohol.
7. method according to claim 6, is characterized in that, described primary alconol is selected from the one or two or more in methyl alcohol, ethanol and propyl alcohol, and described secondary alcohol is selected from Virahol, and the described tertiary alcohol is selected from the trimethyl carbinol.
8. method according to claim 1 and 2, is characterized in that, α-aminoacid alkyl ester is dissolved in after solvent, and the massfraction in solution is 1～80%, with total restatement of solution.
9. method according to claim 8, is characterized in that, α-aminoacid alkyl ester is dissolved in after solvent, and the massfraction in solution is 10～40%, with total restatement of solution.
10. method according to claim 1 and 2, is characterized in that, the cycloalkyl of alkyl C1-C5 alkyl that be straight chain or side chain or C5-C12 in described α-aminoacid alkyl ester.
11. methods according to claim 10, is characterized in that, alkyl C1-C4 alkyl that be straight chain or side chain in described α-aminoacid alkyl ester.
12. methods according to claim 1 and 2, is characterized in that, after hydrogenolysis reducing reaction, also comprise solid-liquid separation and purifying products step; Wherein, that solid-liquid separation is selected from is centrifugal, a kind of in filtering, and the catalyzer that separation obtains is applied mechanically, and the filtrate obtaining is carried out purifying; The method of described purifying is selected from a kind of technique in distillation.
13. methods according to claim 12, is characterized in that, described distil process is for removing boiling point lower than the low-boiling point material of 2-amino-2-methyl-1-propanol by filtrate distillation, and then underpressure distillation obtains 2-amino-2-methyl-1-propanol.
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 CN103232351A (en) | 2013-08-07 |
| CN103232351B true 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) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106831451B (en) * | 2017-02-03 | 2018-09-21 | 荆楚理工学院 | A kind of synthetic method of 2- aminoisobutanols |
Family Cites Families (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 |
| CN101531568B (en) * | 2009-04-13 | 2011-12-07 | 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
Also Published As
| Publication number | Publication date |
|---|---|
| CN103232351A (en) | 2013-08-07 |
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 | |
| CN105399940A (en) | Preparation method of polyether amine | |
| CN106513002B (en) | It is a kind of for being catalyzed the catalyst and its preparation method and application of primary amine or secondary amine and fatty alcohol synthctic fat tertiary amine | |
| CN106543017B (en) | A kind of preparation method of 4 aminocyclohexyl acetic acid | |
| CN103232351B (en) | Preparation method of 2-amino-2-methyl-1-propyl alcohol | |
| CN102625790A (en) | Method for producing alicyclic alcohol | |
| WO2017134139A1 (en) | A method of preparing glycolic acid (hoch2cooh) | |
| CN107903146B (en) | Method for preparing 1, 2-hexanediol by catalytic oxidation of 1-hexene | |
| CN106622215A (en) | A polycondensation catalyst, a preparing method thereof, applications of the catalyst, a diisobutyl ketone preparing method and a diisobutyl carbinol preparing method | |
| CN103254038A (en) | Method for preparing cyclohexanol by using benzene | |
| CN110818571A (en) | Method for synthesizing p-phenylenediamine anti-aging agent by adopting Pt/C catalyst | |
| CN102701991A (en) | Method for preparing nonane diamine | |
| KR20150063058A (en) | Method for synthesising 2,5-di(hydroxymethyl)furan and 2,5-di(hydroxymethyl)tetrahydrofuran by selective hydrogenation of furan-2,5-dialdehyde | |
| CN101863778A (en) | Production method of 4-aminodiphenylamine | |
| TWI522335B (en) | Process for preparing 2,2-difluoroethylamine by hydrogenating 1,1-difluoro-2-nitroethane | |
| CN115197048B (en) | Preparation method of hydrogenated bisphenol A | |
| CN110172029B (en) | Method for continuously synthesizing 2-amino-2-methyl-1-propanol | |
| CN110799519B (en) | Method for preparing bile acid derivative by continuous flow reaction | |
| CN102675133A (en) | Synthesis method for synthesizing p-methoxyaniline compound through hydrogenation and transposition | |
| CN102603473A (en) | Method for preparing corresponding alcohol through carbonyl compound selective hydrogenation | |
| CN103450028B (en) | Method for preparing cyclohexylamine and dicyclohexylamine from nitrobenzene through one-step catalytic hydrogenation | |
| CN105820054A (en) | Preparation method of 3-methoxy-2-nitrobenzoate | |
| CN112574016A (en) | Method for synthesizing alpha-methyl cinnamaldehyde from phenylpropyl aldehyde | |
| CN107778151B (en) | Method for preparing methyl ethyl ketone by sec-butyl alcohol dehydrogenation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C53 | Correction of patent for 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 for 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. |