CN101417952B - Method for preparing 3-aminomethyl-3,5,5-trimethyl cyclohexylamine - Google Patents
Method for preparing 3-aminomethyl-3,5,5-trimethyl cyclohexylamine Download PDFInfo
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- CN101417952B CN101417952B CN2008101784646A CN200810178464A CN101417952B CN 101417952 B CN101417952 B CN 101417952B CN 2008101784646 A CN2008101784646 A CN 2008101784646A CN 200810178464 A CN200810178464 A CN 200810178464A CN 101417952 B CN101417952 B CN 101417952B
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- oxyammonia
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- trimethylcyclohexanone
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Abstract
The invention discloses a method for preparing 3-aminomethyl-3, 5, 5-trimethyl cyclohexylamine (isophorone diamine, IPDA) by 3-cyano-3, 5, 5-trimethyl cyclohexanone (IPN, isophorone nitrile), which comprises the following steps: a) 3-cyano-3, 5, 5-trimethyl cyclohexanone and oxyammonia are arranged in an organic solvent for reaction under a temperature ranging from 40 DEG C to 80 DEG C, and 3-cyano-3, 5, 5-trimethyl cyclohexanone oxime is generated; b) 3-cyano-3, 5, 5-trimethyl cyclohexanone oxime, hydrogen and liquid ammonia are arranged in an organic solvent for reaction under a temperature ranging from 50 DEG C to 120 DEG C, a total pressure ranging from 5 MPa to 15 MPa and the effect of a hydrogenation catalyst, and 3-aminomethyl-3, 5, 5-trimethyl cyclohexylamine is obtained. The method has the advantages that, the production of a by-product 3-aminomethyl-3, 5, 5-trimethyl cyclohexanol (IPAA) which is hard to be separated from IPDA is avoided; simultaneously, the amount of liquid ammonia is largely decreased.
Description
Technical field
The present invention relates to a kind of preparation method of fatty amine, more specifically relate to a kind of 3-aminomethyl-3,5, the preparation method of 5-trimethyl cyclohexylamine (IPDA, i.e. isophorone diamine).
Background technology
3-aminomethyl-3,5,5-trimethyl cyclohexylamine (isophorone diamine is called for short IPDA) is the raw material of preparation isophorone diisocyanate (IPDI), polymeric amide etc., it can also be as the stiffening agent of epoxy resin.IPDA is usually by 3-cyanic acid-3,5, and 5-trimethylcyclohexanone (cyan-3,5,5-trimethyl cyclohexanone is called for short IPN), ammonia, hydrogen pass through amination, hydrogenation and makes under the hydrogenation catalyst effect.Prior art has been introduced the method for the multiple IPDA of preparation.
U.S. Pat 3,352,913 disclose the method for a kind of IPN and ammonia, hydrogen prepared in reaction IPDA under the metal load type catalyst effect of the 8th family.The mol ratio of ammonia and IPN in this method (to call the cyanamide ratio in the following text) is 10 to 30, and temperature of reaction is 70 to 130 ℃, and hydrogen pressure is 150atm.The yield of this method gained IPDA has only 80%, and contains in the product and be difficult to the isolating 3-aminomethyl-3,5 with IPDA in a large number, 5-cyclonol (being called for short IPAA).
Patent US5166396,5166444 discloses the method for manufacture of a kind of IPDA.This method obtains IPN-azine for earlier IPN and Hydrazine Hydrate 80 being reacted; IPN-azine carries out hydrogenation under the effect of ammonia, hydrogenation catalyst, catalyst adjuvant then, obtains IPDA.This method and technology defective is to have introduced hypertoxic reactant hydration hydrazine.
Summary of the invention
To above technological deficiency, it is a kind of new for 3-cyanic acid-3,5 that the present invention provides, and the 5-trimethylcyclohexanone prepares 3-aminomethyl-3,5, the method for 5-trimethyl cyclohexylamine.
The method of the invention comprises:
A) 3-cyanic acid-3,5,5-trimethylcyclohexanone and oxyammonia react generation 3-cyanic acid-3,5,5-3-methyl cyclohexanol ketoxime (abbreviation: the IPN-oxime) in 40 ℃～80 ℃ in organic solvent;
B) 3-cyanic acid-3,5,5-3-methyl cyclohexanol ketoxime, hydrogen and liquefied ammonia is in 50～120 ℃, under 5～15Mpa total pressure, and the hydrogenation catalyst effect under in organic solvent, react, generate 3-aminomethyl-3,5, the 5-trimethyl cyclohexylamine.
In the inventive method; After total pressure in the said step b) is meant that reaction vessel feeds hydrogen; The summation of the pressure that all gases is produced in the reaction vessel, said total pressure not only comprise the dividing potential drop that feeds hydrogen in the reaction vessel, also comprise the dividing potential drop like ammonia; And the dividing potential drop of other gas, for example include but not limited to the dividing potential drop of gas organic solvent.
In the method for the invention, 3-cyanic acid-3,5 in the step a), the mol ratio of 5-trimethylcyclohexanone and oxyammonia is 0.2～1:1.5, is preferably 0.5～1:1; Liquefied ammonia and 3-cyanic acid-3,5 in the step b), the ratio of the quality of 5-3-methyl cyclohexanol ketoxime is 1～5:1, is preferably 2～3:1.
In the method for the invention, the oxyammonia in the said step a) is sour oxyammonia, and wherein said sour oxyammonia includes but not limited to oxammonium hydrochloride, oxyammonia sulfate, nitric acid oxyammonia or phosphoric acid oxyammonia.
In the methods of the invention, said oxyammonia uses alkali to be neutralized to the pH value to be 6-8 before use; Preferred pH value is 6.5-7.5, and more preferably the pH value is 7.
Used alkali can be solid alkali in the inventive method, for example includes but not limited to the oxyhydroxide of basic metal or earth alkali metal, or the carbonate of basic metal or earth alkali metal or supercarbonate, alkali-metal oxide compound, or aqua ammonia; Can also be the aqueous solution of alkali.Alkali according to the invention is preferably saturated or unsaturated aqueous sodium carbonate, for example 1～2M aqueous sodium carbonate.
Among the preparation method of the present invention, the hydrogenation catalyst in the said step b) can wherein be preferably load hydrogenation catalyst for the conventional hydrogenation catalyst in this area, for example includes but not limited to Co/Al
2O
3Or Raney metal type catalyzer, for example include but not limited to thunder Buddhist nun cobalt or Raney's nickel.
Hydrogenation catalyst in the step b) according to the invention is thunder Buddhist nun cobalt or Raney's nickel.
In the inventive method, the temperature of reaction in the said step a) further is preferably 50～70 ℃; Temperature of reaction in the said step b) further is preferably 60～110 ℃, and more preferably 80～100 ℃, reaction pressure further is preferably 10～15Mpa total pressure.
In the inventive method, the organic solvent in said step a) and the step b) is independently selected from the alcohols of 1-4 carbon atom respectively or/and the ethers of 1-4 carbon atom, and said ethers comprises but is limited to ether or methyl ethyl ether; Said alcohols includes but not limited to methyl alcohol, ethanol or propyl alcohol.In the inventive method, step a) neutralization procedure b) organic solvent in can be with a kind of organic solvent, as is all ethanol or methyl alcohol; Also can be different organic solvents, be that organic solvent in ethanol and the step b) is a methyl alcohol like the organic solvent in the step a).
Among the preparation method of the present invention, the organic solvent in said step a) and the step b) is methyl alcohol or ethanol respectively independently.
In the inventive method, the purpose that adds organic solvent is dissolving raw material, for example IPN, IPN-oxime, and therefore, the amount that adds organic solvent should guarantee raw material is dissolved fully.The usage quantity of organic solvent is a 3-cyanic acid-3,5 in the step a) according to the invention, and the 1-5 of 5-trimethylcyclohexanone quality times, preferred 2-3 doubly; The usage quantity of organic solvent is a 3-cyanic acid-3,5 in the step b), the 1-5 of 5-3-methyl cyclohexanol ketoxime quality times, and preferred 2-3 times, wherein, and 3-cyanic acid-3,5, the quality of 5-3-methyl cyclohexanol ketoxime is calculated with dry weight.
The inventive method does not produce with IPDA and is difficult to isolating by product 3-aminomethyl-3,5,5-cyclonol (IPAA); And the present invention has significantly reduced the usage quantity of liquefied ammonia.
Embodiment
The present invention further explains the present invention through following examples, but the present invention is not limited to this.
Wherein, the condition of carrying out gas chromatographic analysis in following examples is: Agilent HP-5 chromatographic column, 280 ℃ of injector temperatures, 280 ℃ of detector temperatures, H
2Flow 35ml/min; Air flow quantity 350ml/min.
Embodiment 1
With 200g95% ethanol and 80g3-cyanic acid-3,5, the 5-trimethylcyclohexanone joins in the there-necked flask that has whisking appliance and TM, loads onto tap funnel.Get 120g oxammonium hydrochloride and 105g yellow soda ash and join in the container that 200ml water is housed, stirring and dissolving, treat that the no bubble of dissolving produces after, it is changed in the tap funnel, stir and descend slowly to be added drop-wise in the there-necked flask; After dropwising, temperature of reaction is risen to 60～65 ℃, constant temperature 1 hour is poured reactant in the ice-water bath into then; The adularescent deposition is separated out, and uses distilled water wash, and natural air drying gets 3-cyanic acid-3; 5,5-3-methyl cyclohexanol ketoxime (being the IPN-oxime) obtains the IPN-oxime, and quality is 86.4g.
Embodiment 2
In the autoclave of 1L, add the 80gIPN-oxime, 200g methyl alcohol, and 15gT-1 type Raney's nickel catalyst, 22g liquefied ammonia, reaching total pressure at 90～100 ℃ of following feeding hydrogen is 10MPa, reacts 1 hour.Through gas chromatographic analysis, 3-aminomethyl-3,5 in the product, the content of 5-trimethyl cyclohexylamine (being IPDA) is 96.1%, does not have the generation of IPAA.
Embodiment 3
Except that the catalyzer among the embodiment 2 being changed into T-1 type thunder Buddhist nun cobalt catalyst, other experiment condition is identical with embodiment 2.Gc analysis test product, wherein the content of IPDA is 96.5%, does not have the generation of IPAA.
Embodiment 4
Except that the total pressure with the hydrogenation reaction among the embodiment 2 changes into the 12MPa, other test conditions is identical with embodiment 2.Gc analysis test product, wherein the content of IPDA is 96.8%, does not have the generation of IPAA.
Embodiment 5
Except that the usage quantity with the liquefied ammonia among the embodiment 2 changes into the 32g, other test conditions is identical with embodiment 2.Gc analysis test product, wherein the content of IPDA is 96.3%, does not have the generation of IPAA.
Claims (16)
1. one kind by 3-cyanic acid-3,5, and the 5-trimethylcyclohexanone prepares 3-aminomethyl-3,5, and the method for 5-trimethyl cyclohexylamine is characterized in that, said method comprises:
A) 3-cyanic acid-3,5,5-trimethylcyclohexanone and oxyammonia react generation 3-cyanic acid-3,5,5-3-methyl cyclohexanol ketoxime in 40 ℃～80 ℃ in organic solvent;
B) 3-cyanic acid-3,5,5-3-methyl cyclohexanol ketoxime, hydrogen and liquefied ammonia is in 50～120 ℃, under 5～15Mpa total pressure, and the hydrogenation catalyst effect under in organic solvent, react, generate 3-aminomethyl-3,5, the 5-trimethyl cyclohexylamine.
2. method according to claim 1 is characterized in that, 3-cyanic acid-3,5 in the said step a), and the mol ratio of 5-trimethylcyclohexanone and oxyammonia is 0.2～1: 1.5; Liquefied ammonia and 3-cyanic acid-3,5 in the step b), the ratio of the quality of 5-3-methyl cyclohexanol ketoxime is 1～5: 1.
3. method according to claim 1 is characterized in that, 3-cyanic acid-3,5 in the said step a), and the mol ratio of 5-trimethylcyclohexanone and oxyammonia is 0.5～1: 1; Liquefied ammonia and 3-cyanic acid-3,5 in the step b), the ratio of the quality of 5-3-methyl cyclohexanol ketoxime is 2～3: 1.
4. according to claim 2 or 3 described methods, oxyammonia is oxammonium hydrochloride, oxyammonia sulfate, nitric acid oxyammonia or phosphoric acid oxyammonia in the said step a).
5. method according to claim 4 is characterized in that, oxyammonia used alkali to be neutralized to the pH value before using to be 6-8 in the said step a).
6. method according to claim 5 is characterized in that, oxyammonia used alkali to be neutralized to the pH value before using to be 6.5-7.5 in the said step a).
7. method according to claim 6 is characterized in that, before using, to use alkali to be neutralized to the pH value be 7 to oxyammonia in the said step a).
8. method according to claim 5 is characterized in that, said alkali is saturated or unsaturated aqueous sodium carbonate.
9. method according to claim 8 is characterized in that, catalyzer is load hydrogenation catalyst or Raney metal type catalyzer in the said step b).
10. method according to claim 9 is characterized in that, catalyzer is Raney's nickel or thunder Buddhist nun cobalt in the said step b).
11., it is characterized in that temperature of reaction is 50 ℃～70 ℃ in the said step a) according to claim 9 or 10 described methods; Temperature of reaction is 60 ℃～110 ℃ in the said step b), and reaction pressure is 10～15Mpa total pressure.
12. method according to claim 11 is characterized in that, temperature of reaction is 80 ℃～100 ℃ in the said step b).
13. method according to claim 11 is characterized in that, organic solvent in said step a) and the step b) is respectively that the alcohols of 1-4 carbon atom is or/and the ethers of 1-4 carbon atom independently.
14. method according to claim 13 is characterized in that, the usage quantity of organic solvent is a 3-cyanic acid-3,5 in the said step a), and the 1-5 of 5-trimethylcyclohexanone quality doubly; The usage quantity of organic solvent is a 3-cyanic acid-3,5 in the step b), and the 1-5 of 5-3-methyl cyclohexanol ketoxime quality doubly.
15. method according to claim 14 is characterized in that, the usage quantity of organic solvent is a 3-cyanic acid-3,5 in the said step a), and the 2-3 of 5-trimethylcyclohexanone quality doubly; The usage quantity of organic solvent is a 3-cyanic acid-3,5 in the step b), and the 2-3 of 5-3-methyl cyclohexanol ketoxime quality doubly.
16., it is characterized in that the organic solvent in said step a) and the step b) is methyl alcohol or ethanol respectively independently according to claim 14 or 15 described methods.
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| CN104761455B (en) * | 2014-01-08 | 2017-07-21 | 浙江新化化工股份有限公司 | A kind of method for preparing IPD |
| CN105218380B (en) * | 2014-06-12 | 2017-05-17 | 连云港手性化学有限公司 | Preparation method for (+/-)-1,2-diphenylethanediamine |
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| Title |
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| 邓勇等.反式-4-甲基环己基异氰酸酯的合成.《中国医药工业杂志》.2001,第32卷(第8期),369-370. * |
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Address after: 315812 Zhejiang province Ningbo Daxie Economic Development Zone North Island Wanhua Industrial Park Patentee after: Wanhua Chemical (Ningbo) Co., Ltd. Address before: 315812 Zhejiang province Ningbo Daxie Economic Development Zone North Island Wanhua Industrial Park Patentee before: Ningbo Wanhua Polyurethane Co., Ltd. |