CN102030657A - Synthesizing method of 3,3'-dimethyl-4,4'-diamido-dicyclohexyl methane - Google Patents
Synthesizing method of 3,3'-dimethyl-4,4'-diamido-dicyclohexyl methane Download PDFInfo
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Abstract
The invention relates to a synthesizing method of 3,3'-dimethyl-4,4'-diamido-dicyclohexyl methane (MACM), belonging to the technical field of fine chemical synthesis. The synthesizing method comprises the following steps of: placing the MACM and 3,3'-dimethyl-4,4'-diamido-diphenyl methane (MDT) in a hydrogenation kettle according to the ratio of 1.0:(1.0-4.0), adding a Ru compound catalyst, adding trace alkaline earth metal assistant, performing hydrogenation reaction at the temperature of 120-190 DEG C and the pressure of 2.0-10.0MPa, cooling, discharging and filtering and rectifying to obtain pure MACM product. The invention has the advantages of low reaction temperature, low pressure, low requirement for devices, easy and simple operation, good product purity, high yield, good economical efficiency of reaction atom and no process waste water and gas in the whole technical process, technically and greatly reduces the generation source of three wastes, is environmental-friendly and has better industrial application prospect.
Description
Technical field
The invention belongs to technical field of fine chemical synthesis, be specifically related to a kind of 3,3 '-dimethyl-4, the synthetic method of 4 '-diamino-dicyclohexyl methane.
Background technology
3, it is synthetic that 3 '-dimethyl-4,4 '-diamino-dicyclohexyl methane are widely used in high-quality urethane, Resins, epoxy and polymeric amide, as space industry, and industries such as wind-power electricity generation.The elasticity of the existing rubber of MACM synthetic urethane has the intensity of plastics and excellent processing characteristics again, especially at aspects such as sound insulation, heat insulation, wear-resisting, oil resistant, elasticity the incomparable advantage of other synthetic materialss is arranged; That its synthetic polymeric amide has is nontoxic, light weight, good physical strength, wear resistance and erosion resistance preferably; Be applied to Resins, epoxy and have that agglutinating value(of coal) is strong, electrical insulating property is good, a series of excellent properties such as stable chemical performance and processing characteristics are good.
3,3 '-dimethyl-4, the synthetic method of 4 '-diamino-dicyclohexyl methane is by to 3,3 ' dimethyl-4, the hydrogenation of 4 '-diaminodiphenyl-methane obtains.At present main method has: 1 under pressure 200 crust, temperature 30-280 ℃, 3,3 ' dimethyl-4, hydrogenation takes place and obtains 3 containing under the catalyzer of Ru (hydrate of Ru oxide compound and silicon-dioxide hydrogenation make) in the liquid melts of 4 '-diaminodiphenyl-methane, 3 ' dimethyl-4,4 '-diamino-dicyclohexyl methane; 2, with fused 3,3 ' dimethyl-4,4 '-diaminodiphenyl-methane and hydrogen feed in the tubular reactor of the catalyzer that CoO, yellow soda ash, hexanedial and water are housed, in temperature is 220-255 ℃, hydrogenation obtains 3 under the pressure 250-300 normal atmosphere, 3 ' dimethyl-4,4 '-diamino-dicyclohexyl methane; 3, under 30-250 ℃, pressure 300atm, be solvent with the dioxan, 3,3 ' dimethyl-4,4 '-diaminodiphenyl-methane are done at the oxyhydroxide of Ru hydrogenation preparation 3,3 ' dimethyl-4,4 '-diamino-dicyclohexyl methane are taken place under the catalyzer; 4, at temperature 210-230 ℃, 250atm pressure, the homemade Co catalyzer of BASF exist down, and 3,3 ' dimethyl-4,4 '-diaminodiphenyl-methane obtain 3,3 ' dimethyl-4 in hydrogen generation catalytic hydrogenation, 4 '-diamino-dicyclohexyl methane.
Although prior art can both obtain the MACM product, the result is very dissatisfied.As: 1, the hydrogenation of above four kinds of methods all carries out under High Temperature High Pressure, to having relatively high expectations of equipment; 2, catalyzer is by its patent of invention company self-control, and application has limitation;
Such as; Patent WO2009090179 discloses the water of ru oxide and thing and water drain silica and has obtained containing the suspension of ruthenium as catalyzer behind hydrogenation, under the pressure of 200 crust, hydrogenation takes place in MDT liquid melts in the presence of catalyzer, reaction is cooled to 230-240 ℃ and obtains target product.Carrying out under high temperature and high pressure of this patent, to having relatively high expectations of equipment, and reaction easily makes the by product of generation increase under the high temperature.
German Patent DB 2132547 discloses at 150 ℃, under 300 normal atmosphere, with Ru(OH) 4 be catalyzer, with the dioxan is solvent, 3, and 3 '-dimethyl-4,4 '-diaminodiphenyl-methane makes 3 by shortening, 3 '-dimethyl-4,4 '-diamino-dicyclohexyl methane.This patent pressure reaches 300 normal atmosphere, and is very high to the requirement of equipment.
Summary of the invention
At the above-mentioned problems in the prior art, the object of the present invention is to provide a kind of product with himself is solvent, adopt pickling process to make the loading type composite catalyst, and the interpolation trace assistant, to 3,3 '-dimethyl-4,4 '-diaminodiphenyl-methane (MDT) carries out shortening, provide a kind of synthetic 3,3 ' dimethyl-4, the novel method of 4 '-diamino-dicyclohexyl methane (MACM).
Described a kind of 3,3 '-dimethyl-4, the synthetic method of 4 '-diamino-dicyclohexyl methane is characterized in that described synthetic method is: with 3, and 3 '-dimethyl-4,4 '-diaminodiphenyl-methane is a raw material, with product 3,3 '-dimethyl-4,4 '-diamino-dicyclohexyl methane are solvent, the molar ratio of raw material and solvent is 1.0:1.0-4.0, adopting Ru catalyst based, add micro-base earth metal promoter, is 120-190 ℃ in temperature of reaction, pressure-controlling is at 2.0-10.0MPa, obtain thick product through catalytic hydrogenation, obtain 3 by rectifying then, 3 ' dimethyl-4,4 '-diamino-dicyclohexyl methane product, its structural formula is shown in formula I
（I） 。
Described a kind of 3,3 '-dimethyl-4, the synthetic method of 4 '-diamino-dicyclohexyl methane, its feature is 1.0:1.0-2.5 at the molar ratio of described raw material and solvent.
Described a kind of 3,3 '-dimethyl-4, the synthetic method of 4 '-diamino-dicyclohexyl methane is characterized in that described Ru is catalyst based for adopting pickling process to make the composite catalyst Ru/SiO of loading type
2Catalyzer or Ru/C catalyzer, charging capacity are 3,3 '-dimethyl-4, the 5-10% of 4 '-diaminodiphenyl-methane raw material.
Described a kind of 3,3 '-dimethyl-4, the synthetic method of 4 '-diamino-dicyclohexyl methane is characterized in that described Ru/SiO
2The Preparation of catalysts method is: with carrier S iO
2Make specific surface area and be about 250-300m through pulverizing, screening
2/ g crude product 150-200 ℃ of activation down, is cooled to 30 ℃ then, add the ruthenium solution chlorate and flood 3-5h,, decompose at 170-250 ℃ of following calcination for activation then 80-110 ℃ of oven dry down, 300-500 ℃ of activation, feed hydrogen reducing and obtain activity Ru/Si0 preferably at last
2
Described a kind of 3,3 '-dimethyl-4, the synthetic method of 4 '-diamino-dicyclohexyl methane is characterized in that described Ru/C Preparation of catalysts method is: take by weighing 10.0 gram RuCL
3, add among the entry 150ml, be heated to 80 ℃, add activated carbon 103 grams through nitric acid treatment, stirred 3-6 hour, then at 110-115 ℃ of dry 7-9 hour, get activated carbon loaded RuCL
3, under 180-210 ℃ of temperature, fed hydrogen reducing 5-8 hour at last, obtain the Ru/C catalyzer.
Described a kind of 3,3 '-dimethyl-4, the synthetic method of 4 '-diamino-dicyclohexyl methane, it is characterized in that described in order to regulate catalyst activity, the trace assistant that prolongs catalyst life really is a kind of among MgO, CaO or the BaO, charging capacity is 3,3 '-dimethyl-4, the 0.5-1.0% of 4 '-diaminodiphenyl-methane raw material.
Described a kind of 3,3 '-dimethyl-4, the synthetic method of 4 '-diamino-dicyclohexyl methane is characterized in that described temperature of reaction is controlled between 120-190 ℃, is preferably 140-160 ℃, preferred pressure is 4.0-6.0MPa.
Described a kind of 3,3 '-dimethyl-4, the synthetic method of 4 '-diamino-dicyclohexyl methane, it is characterized in that described synthetic method step specific as follows carries out: is that the feed liquid of 1.0:1.0-4.0 drops in the hydrogenation still with raw material and solvent by molar ratio, add pickling process and be worth the loading type composite catalyst, and add micro-base earth metal promoter, finishing in temperature is 120-190 ℃, carry out catalytic hydrogenation between the pressure 2.0-10.0MPa, inhale hydrogen and finish follow-up continuation of insurance temperature 1.5-2.5h, cooling discharging filters, and obtains pure 3 by rectifying then, 3 ' dimethyl-4,4 '-diamino-dicyclohexyl methane product.
Described a kind of 3,3 '-dimethyl-4, the synthetic method of 4 '-diamino-dicyclohexyl methane is characterized in that described Ru is catalyst based for adopting pickling process to make the composite catalyst Ru/SiO of loading type
2Catalyzer or Ru/C catalyzer.
Described a kind of 3,3 '-dimethyl-4, the synthetic method of 4 '-diamino-dicyclohexyl methane is characterized in that described rectification temperature is 160-180 ℃, pressure is 10mmHg.
Its chemical equation is:
Compared with prior art, innovation part of the present invention is with 3,3 '-dimethyl-4,4 '-diaminodiphenyl-methane is a raw material, adopts pickling process to make loading type Ru composite catalyst, adds micro-base earth metal promoter, with product this as solvent, the catalytic hydrogenation sintetics.Its beneficial effect is as follows:
1) adopt pickling process to make loading type Ru composite catalyst, the auxiliary agent that adds trace is to regulate catalyst activity, the reduction that prolongs the technology cost of applying mechanically continuously of catalyzer;
2) with the MACM product solvent as hydrogenation, separated from solvent when avoiding rectifying is stopped the wasting of resources that solvent loss causes, energy consumption and the environmental influence that solvent recuperation is brought;
3) by selecting catalyzer efficiently, control reaction conditionss such as suitable temperature, pressure, proportioning, the molar product yield reaches more than 99.7%, content〉99%.Quality product meets or exceeds international most advanced level;
4) this patent adopts the reaction of mesohigh catalytic hydrogenating reduction, the reaction of atomic good economy performance, and whole technological process does not have processing wastewater and technology waste gas, has reduced three wastes generation source significantly on technology, for environmentally friendly technology, is suitable for suitability for industrialized production.
Embodiment
The invention will be further described below in conjunction with specific embodiment, but protection scope of the present invention is not limited thereto:
3,3 '-dimethyl-4,4 '-diaminodiphenyl-methane is called for short MDT, 3,3 ' dimethyl-4,4 '-diamino-dicyclohexyl methane is called for short MACM.
Embodiment 1 drops into 226g MDT, 226g MACM, 11.3g Ru/SiO in the hydrogenation still
2, and add 0.11gCaO, feeding intake finishes with nitrogen, hydrogen exchange.Open stirring, temperature is risen to 120 ℃, and controlled temperature between the pressure 2.0-4.0MPa, reacts and inhaled the hydrogen end in 32 hours between 120-140 ℃, continue insulation 2h, be cooled to 40 ℃, discharging is filtered, distillage under the 10mmHg vacuum obtains product 219g then, content 99.6%, yield 92%.
Embodiment 2 drops into 226g MDT, 226g MACM, 11.3g Ru/SiO in the hydrogenation still
2, and add 0.09gBaO, feeding intake finishes with nitrogen, hydrogen exchange.Open stirring, temperature is risen to 135 ℃, and controlled temperature is between 140-160 ℃, between the pressure 2.0-4.0MPa, react and inhaled the hydrogen end in 22 hours, continue insulation 1.5h, be cooled to 40 ℃, discharging, filter, distillage under the 10mmHg vacuum obtains product 226.6g then, content 99.5%, yield 99.5%.
Embodiment 3 drops into 226g MDT, 271g MACM, 18.1g Ru/SiO in the hydrogenation still
2, and add 0.12gMgO, feeding intake finishes with nitrogen, hydrogen exchange.Open stirring, temperature is risen to 135 ℃, and controlled temperature is between 140-160 ℃, between the pressure 4.0-6.0MPa, react and inhaled the hydrogen end in 17 hours, continue insulation 2.5h, be cooled to 40 ℃, discharging, filter, distillage under the 10mmHg vacuum obtains product 236.1g then, content 99.7%, yield 99.2%.
Embodiment 4 drops into 226g MDT, 271g MACM, 22.6g Ru/SiO in the hydrogenation still
2, and add 0.22gMgO, feeding intake finishes with nitrogen, hydrogen exchange.Open stirring, temperature is risen to 135 ℃, and controlled temperature is between 140-160 ℃, between the pressure 4.0-6.0MPa, react and inhaled the hydrogen end in 13 hours, continue insulation 2.5h, be cooled to 40 ℃, discharging, filter, distillage under the 10mmHg vacuum obtains product 236.81g then, content 99.7%, yield 99.4%.
Embodiment 5 drops into 226g MDT, 316g MACM, 22.6g Ru/C in the hydrogenation still, and adds 0.11gMgO, feeds intake to finish with nitrogen, hydrogen exchange.Open stirring, temperature is risen to 135 ℃, and controlled temperature is between 140-160 ℃, between the pressure 4.0-6.0MPa, react and inhaled the hydrogen end in 14 hours, continue insulation 2h, be cooled to 40 ℃, discharging, filter, distillage under the 10mmHg vacuum obtains product 236.1g then, content 99.7%, yield 99.2%.
Embodiment 6 drops into 226g MDT, 316g MACM, 22.6g Ru/C in the hydrogenation still, and adds 0.11gCaO, feeds intake to finish with nitrogen, hydrogen exchange.Open stirring, temperature is risen to 160 ℃, and controlled temperature is between 170-190 ℃, between the pressure 6.0-8.0MPa, react and inhaled the hydrogen end in 8 hours, continue insulation 2h, be cooled to 40 ℃, discharging, filter, distillage under the 10mmHg vacuum obtains product 217.3g then, content 99.4%, yield 91.3%.
Embodiment 7 drops into 226g MDT, 339g MACM, 18g Ru/SiO in the hydrogenation still
2, and add 0.18gCaO, feeding intake finishes with nitrogen, hydrogen exchange.Open stirring, temperature is risen to 120 ℃, and controlled temperature is between 120-140 ℃, between the pressure 4.0-6.0MPa, react and inhaled the hydrogen end in 29 hours, continue insulation 2h, be cooled to 40 ℃, discharging, filter, distillage under the 10mmHg vacuum obtains product 223.7g then, content 99.5%, yield 94%.
Embodiment 8 drops into 226g MDT, 339g MACM, 18g Ru/SiO in the hydrogenation still
2, and add 0.18gBaO, feeding intake finishes with nitrogen, hydrogen exchange.Open stirring, temperature is risen to 133 ℃, and controlled temperature is between 140-160 ℃, between the pressure 4.0-6.0MPa, react and inhaled the hydrogen end in 18 hours, continue insulation 1.5h, be cooled to 40 ℃, discharging, filter, distillage under the 10mmHg vacuum obtains product 236.3g then, content 99.5%, yield 99.3%.
Embodiment 9 drops into 226g MDT, 384g MACM, 22.6g Ru/SiO in the hydrogenation still
2, and add 0.22gBaO, feeding intake finishes with nitrogen, hydrogen exchange.Open stirring, temperature is risen to 136 ℃, and controlled temperature is between 140-160 ℃, between the pressure 4.0-6.0MPa, react and inhaled the hydrogen end in 12 hours, continue insulation 1.5h, be cooled to 40 ℃, discharging, filter, distillage under the 10mmHg vacuum obtains product 237.3g then, content 99.8%, yield 99.7%.
Embodiment 10 drops into 226g MDT, 384g MACM, 22.6g Ru/C in the hydrogenation still, and adds 0.22g MgO, feeds intake to finish with nitrogen, hydrogen exchange.Open stirring, temperature is risen to 135 ℃, and controlled temperature is between 140-160 ℃, between the pressure 4.0-6.0MPa, react and inhaled the hydrogen end in 13.5 hours, continue insulation 1.5h, be cooled to 40 ℃, discharging, filter, distillage under the 10mmHg vacuum obtains product 236.8g then, content 99.6%, yield 99.5%.
Embodiment 11 drops into 226g MDT, 452g MACM, 22.6g Ru/SiO in the hydrogenation still
2, and add 0.22g MgO, feeding intake finishes with nitrogen, hydrogen exchange.Open stirring, temperature is risen to 136 ℃, and controlled temperature is between 140-160 ℃, between the pressure 6.0-8.0MPa, react and inhaled the hydrogen end in 10 hours, continue insulation 2.5h, be cooled to 40 ℃, discharging, filter, distillage under the 10mmHg vacuum obtains product 234.67g then, content 99.5%, yield 98.6%.
Embodiment 12 drops into 226g MDT, 452g MACM, 22.6g Ru/SiO in the hydrogenation still
2, and add 0.22g MgO, feeding intake finishes with nitrogen, hydrogen exchange.Open stirring, temperature is risen to 152 ℃, and controlled temperature is between 160-190 ℃, between the pressure 6.0-8.0MPa, react and inhaled the hydrogen end in 8 hours, continue insulation 2.5h, be cooled to 40 ℃, discharging, filter, distillage under the 10mmHg vacuum obtains product 210.6g then, content 99.6%, yield 88.5%.
Embodiment 13 drops into 226g MDT, 475g MACM, 11.3g Ru/SiO in the hydrogenation still
2, and add 0.11g BaO, feeding intake finishes with nitrogen, hydrogen exchange.Open stirring, temperature is risen to 134 ℃, and controlled temperature is between 140-160 ℃, between the pressure 2.0-4.0MPa, react and inhaled the hydrogen end in 19 hours, continue insulation 1.5h, be cooled to 40 ℃, discharging, filter, distillage under the 10mmHg vacuum obtains product 229.2g then, content 99.6%, yield 96.3%.
Embodiment 14 drops into 226g MDT, 475g MACM, 22.6g Ru/SiO in the hydrogenation still
2, and add 0.18g BaO, feeding intake finishes with nitrogen, hydrogen exchange.Open stirring, temperature is risen to 137 ℃, and controlled temperature is between 140-160 ℃, between the pressure 4.0-6.0MPa, react and inhaled the hydrogen end in 7 hours, continue insulation 1.5h, be cooled to 40 ℃, discharging, filter, distillage under the 10mmHg vacuum obtains product 236.6g then, content 99.8%, yield 99.4%.
Embodiment 15 drops into 226g MDT, 520g MACM, 18.1g Ru/SiO in the hydrogenation still
2, and add 0.18g MgO, feeding intake finishes with nitrogen, hydrogen exchange.Open stirring, temperature is risen to 136 ℃, and controlled temperature is between 140-160 ℃, between the pressure 6.0-8.0MPa, react and inhaled the hydrogen end in 8 hours, continue insulation 1.5h, be cooled to 40 ℃, discharging, filter, distillage under the 10mmHg vacuum obtains product 234.4g then, content 99.5%, yield 98.5%.
Embodiment 16 drops into 226g MDT, 520g MACM, 18.1g Ru/SiO in the hydrogenation still
2, and add 0.18g MgO, feeding intake finishes with nitrogen, hydrogen exchange.Open stirring, temperature is risen to 132 ℃, and controlled temperature is between 160-190 ℃, between the pressure 6.0-8.0MPa, react and inhaled the hydrogen end in 5 hours, continue insulation 1.5h, be cooled to 40 ℃, discharging, filter, distillage under the 10mmHg vacuum obtains product 212.3g then, content 99.5%, yield 89.2%.
Embodiment 17 drops into 226g MDT, 565g MACM, 18.1g Ru/C in the hydrogenation still, and adds 0.18g CaO, feeds intake to finish with nitrogen, hydrogen exchange.Open stirring, temperature is risen to 136 ℃, and controlled temperature is between 140-160 ℃, between the pressure 4.0-6.0MPa, react and inhaled the hydrogen end in 10 hours, continue insulation 1.5h, be cooled to 40 ℃, discharging, filter, distillage under the 10mmHg vacuum obtains product 235.9g then, content 99.7%, yield 99.1%.
Embodiment 18 drops into 226g MDT, 565g MACM, 22.6g Ru/C in the hydrogenation still, and adds 0.18g CaO, feeds intake to finish with nitrogen, hydrogen exchange.Open stirring, temperature is risen to 134 ℃, and controlled temperature is between 140-160 ℃, between the pressure 4.0-6.0MPa, react and inhaled the hydrogen end in 9 hours, continue insulation 1.5h, be cooled to 40 ℃, discharging, filter, distillage under the 10mmHg vacuum obtains product 236.6g then, content 99.7%, yield 99.4%.
Embodiment 19 drops into 226g MDT, 565g MACM, 22.6g Ru/C in the hydrogenation still, and adds 0.18g CaO, feeds intake to finish with nitrogen, hydrogen exchange.Open stirring, temperature is risen to 152 ℃, and controlled temperature is between 160-190 ℃, between the pressure 4.0-6.0MPa, react and inhaled the hydrogen end in 6 hours, continue insulation 1.5h, be cooled to 40 ℃, discharging, filter, distillage under the 10mmHg vacuum obtains product 209g then, content 99.7%, yield 87.8%.
Embodiment 20 drops into 226g MDT, 678g MACM, 18.1g Ru/SiO in the hydrogenation still
2, and add 0.18g BaO, feeding intake finishes with nitrogen, hydrogen exchange.Open stirring, temperature is risen to 130 ℃, and controlled temperature is between 140-160 ℃, between the pressure 2.0-4.0MPa, react and inhaled the hydrogen end in 11 hours, continue insulation 1.5h, be cooled to 40 ℃, discharging, filter, distillage under the 10mmHg vacuum obtains product 236.6g then, content 99.8%, yield 99.4%.
Embodiment 21 drops into 226g MDT, 630g MACM, 18.1g Ru/C in the hydrogenation still, and adds 0.18g MgO, feeds intake to finish with nitrogen, hydrogen exchange.Open stirring, temperature is risen to 138 ℃, and controlled temperature is between 140-160 ℃, between the pressure 2.0-4.0MPa, react and inhaled the hydrogen end in 16 hours, continue insulation 1.5h, be cooled to 40 ℃, discharging, filter, distillage under the 10mmHg vacuum obtains product 232g then, content 99.7%, yield 97.5%.
Embodiment 22 drops into 226g MDT, 630g MACM, 22.6g Ru/SiO in the hydrogenation still
2, and add 0.23g BaO, feeding intake finishes with nitrogen, hydrogen exchange.Open stirring, temperature is risen to 138 ℃, and controlled temperature is between 140-160 ℃, between the pressure 4.0-6.0MPa, react and inhaled the hydrogen end in 10 hours, continue insulation 2h, be cooled to 40 ℃, discharging, filter, distillage under the 10mmHg vacuum obtains product 235.6g then, content 99.7%, yield 99.0%.
Embodiment 23 drops into 226g MDT, 678g MACM, 22.6g Ru/SiO in the hydrogenation still
2, and add 0.23g BaO, feeding intake finishes with nitrogen, hydrogen exchange.Open stirring, temperature is risen to 138 ℃, and controlled temperature is between 140-160 ℃, between the pressure 6.0-8.0MPa, react and inhaled the hydrogen end in 9.5 hours, continue insulation 2h, be cooled to 40 ℃, discharging, filter, distillage under the 10mmHg vacuum obtains product 235.1g then, content 99.7%, yield 98.8%.
Embodiment 24 drops into 226g MDT, 678g MACM, 18.1g Ru/SiO in the hydrogenation still
2, and add 0.18g BaO, feeding intake finishes with nitrogen, hydrogen exchange.Open stirring, temperature is risen to 138 ℃, and controlled temperature between the pressure 4.0-6.0MPa, reacts and inhaled the hydrogen end in 8 hours between 170-190 ℃, continue insulation 2h, be cooled to 40 ℃, discharging is filtered, distillage under the 10mmHg vacuum obtains product 211.8g then, content 99.7%, yield 89%.
Embodiment 25 drops into 226g MDT, 678g MACM, 22.6g Ru/SiO in the hydrogenation still
2, and add 0.23g BaO, feeding intake finishes with nitrogen, hydrogen exchange.Open stirring, temperature is risen to 138 ℃, and controlled temperature is between 170-190 ℃, between the pressure 6.0-8.0MPa, react and inhaled the hydrogen end in 5 hours, continue insulation 2h, be cooled to 40 ℃, discharging, filter, distillage under the 10mmHg vacuum obtains product 203.25g then, content 99.7%, yield 85.4%.
Embodiment 26 drops into 226g MDT, 904g MACM, 11.3g Ru/SiO in the hydrogenation still
2, and add 0.11g BaO, feeding intake finishes with nitrogen, hydrogen exchange.Open stirring, temperature is risen to 138 ℃, and controlled temperature is between 140-160 ℃, between the pressure 4.0-6.0MPa, react and inhaled the hydrogen end in 17.5 hours, continue insulation 2h, be cooled to 40 ℃, discharging, filter, distillage under the 10mmHg vacuum obtains product 234.7g then, content 99.7%, yield 98.6%.
Embodiment 27 drops into 226g MDT, 790g MACM, 18.1g Ru/C in the hydrogenation still, and adds 0.18g BaO, feeds intake to finish with nitrogen, hydrogen exchange.Open stirring, temperature is risen to 138 ℃, and controlled temperature is between 140-160 ℃, between the pressure 4.0-6.0MPa, react and inhaled the hydrogen end in 15 hours, continue insulation 2h, be cooled to 40 ℃, discharging, filter, distillage under the 10mmHg vacuum obtains product 235.6g then, content 99.4%, yield 99.0%.
Embodiment 28 drops into 226g MDT, 790g MACM, 22.6g Ru/ SiO in the hydrogenation still
2, and add 0.23g BaO, feeding intake finishes with nitrogen, hydrogen exchange.Open stirring, temperature is risen to 138 ℃, and controlled temperature is between 140-160 ℃, between the pressure 4.0-6.0MPa, react and inhaled the hydrogen end in 12 hours, continue insulation 2h, be cooled to 40 ℃, discharging, filter, distillage under the 10mmHg vacuum obtains product 236.8g then, content 99.6%, yield 99.5%.
Embodiment 29 drops into 226g MDT, 904g MACM, 22.6g Ru/ C in the hydrogenation still, and adds 0.23g BaO, feeds intake to finish with nitrogen, hydrogen exchange.Open stirring, temperature is risen to 138 ℃, and controlled temperature is between 140-160 ℃, between the pressure 4.0-6.0MPa, react and inhaled the hydrogen end in 14 hours, continue insulation 2h, be cooled to 40 ℃, discharging, filter, distillage under the 10mmHg vacuum obtains product 235.6g then, content 99.6%, yield 99.0%.
Embodiment 30 drops into 226g MDT, 904g MACM, 22.6g Ru/ C in the hydrogenation still, and adds 0.23g BaO, feeds intake to finish with nitrogen, hydrogen exchange.Open stirring, temperature is risen to 168 ℃, and controlled temperature is between 170-190 ℃, between the pressure 4.0-6.0MPa, react and inhaled the hydrogen end in 7 hours, continue insulation 2h, be cooled to 40 ℃, discharging, filter, distillage under the 10mmHg vacuum obtains product 209.9g then, content 99.4%, yield 88.2%.
Embodiment 31 drops into 226g MDT, 904g MACM, 22.6g Ru/ C in the hydrogenation still, and adds 0.23g BaO, feeds intake to finish with nitrogen, hydrogen exchange.Open stirring, temperature is risen to 168 ℃, and controlled temperature is between 170-190 ℃, between the pressure 6.0-8.0MPa, react and inhaled the hydrogen end in 5.5 hours, continue insulation 2h, be cooled to 40 ℃, discharging, filter, distillage under the 10mmHg vacuum obtains product 204.7g then, content 99.4%, yield 86%.
Claims (10)
1. one kind 3,3 '-dimethyl-4, the synthetic method of 4 '-diamino-dicyclohexyl methane is characterized in that described synthetic method is: with 3, and 3 '-dimethyl-4,4 '-diaminodiphenyl-methane is a raw material, with product 3,3 '-dimethyl-4,4 '-diamino-dicyclohexyl methane are solvent, the molar ratio of raw material and solvent is 1.0:1.0-4.0, adopting Ru catalyst based, add micro-base earth metal promoter, is 120-190 ℃ in temperature of reaction, pressure-controlling is at 2.0-10.0MPa, obtain thick product through catalytic hydrogenation, obtain 3 by rectifying then, 3 ' dimethyl-4,4 '-diamino-dicyclohexyl methane product, its structural formula is shown in formula I:
（I） 。
2. according to claim 1 a kind of 3,3 '-dimethyl-4, the synthetic method of 4 '-diamino-dicyclohexyl methane, its feature is 1.0:1.0-2.5 at the molar ratio of described raw material and solvent.
3. according to claim 1 a kind of 3,3 '-dimethyl-4, the synthetic method of 4 '-diamino-dicyclohexyl methane is characterized in that described Ru is catalyst based for adopting pickling process to make the composite catalyst Ru/SiO of loading type
2Catalyzer or Ru/C catalyzer, charging capacity are 3,3 '-dimethyl-4, the 5-10% of 4 '-diaminodiphenyl-methane raw material.
4. according to claim 3 a kind of 3,3 '-dimethyl-4, the synthetic method of 4 '-diamino-dicyclohexyl methane is characterized in that described Ru/SiO
2The Preparation of catalysts method is: with carrier S iO
2Make specific surface area and be about 250-300m through pulverizing, screening
2/ g crude product 150-200 ℃ of activation down, is cooled to 30 ℃ then, add the ruthenium solution chlorate and flood 3-5h,, decompose at 170-250 ℃ of following calcination for activation then 80-110 ℃ of oven dry down, 300-500 ℃ of activation, feed hydrogen reducing and obtain activity Ru/Si0 preferably at last
2
5. according to claim 3 a kind of 3,3 '-dimethyl-4, the synthetic method of 4 '-diamino-dicyclohexyl methane is characterized in that described Ru/C Preparation of catalysts method is: take by weighing 10.0 gram RuCL
3, add among the entry 150ml, be heated to 80 ℃, add activated carbon 103 grams through nitric acid treatment, stirred 3-6 hour, then at 110-115 ℃ of dry 7-9 hour, get activated carbon loaded RuCL
3, under 180-210 ℃ of temperature, fed hydrogen reducing 5-8 hour at last, obtain the Ru/C catalyzer.
6. according to claim 1 a kind of 3,3 '-dimethyl-4, the synthetic method of 4 '-diamino-dicyclohexyl methane, it is characterized in that described in order to regulate catalyst activity, the trace assistant that prolongs catalyst life really is a kind of among MgO, CaO or the BaO, charging capacity is 3,3 '-dimethyl-4, the 0.5-1.0% of 4 '-diaminodiphenyl-methane raw material.
7. according to claim 1 a kind of 3,3 '-dimethyl-4, the synthetic method of 4 '-diamino-dicyclohexyl methane is characterized in that described temperature of reaction is controlled between 120-190 ℃, is preferably 140-160 ℃, preferred pressure is 4.0-6.0MPa.
8. according to claim 1 a kind of 3,3 '-dimethyl-4, the synthetic method of 4 '-diamino-dicyclohexyl methane, it is characterized in that described synthetic method step specific as follows carries out: is that the feed liquid of 1.0:1.0-4.0 drops in the hydrogenation still with raw material and solvent by molar ratio, add pickling process and be worth the loading type composite catalyst, and add micro-base earth metal promoter, finishing in temperature is 120-190 ℃, carry out catalytic hydrogenation between the pressure 2.0-10.0MPa, inhale hydrogen and finish follow-up continuation of insurance temperature 1.5-2.5h, cooling discharging filters, and obtains pure 3 by rectifying then, 3 ' dimethyl-4,4 '-diamino-dicyclohexyl methane product.
9. according to claim 8 a kind of 3,3 '-dimethyl-4, the synthetic method of 4 '-diamino-dicyclohexyl methane is characterized in that described Ru is catalyst based for adopting pickling process to make the composite catalyst Ru/SiO of loading type
2Catalyzer or Ru/C catalyzer.
10. according to claim 8 a kind of 3,3 '-dimethyl-4, the synthetic method of 4 '-diamino-dicyclohexyl methane is characterized in that described rectification temperature is 160-180 ℃, pressure is 10mmHg.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102627569A (en) * | 2012-03-01 | 2012-08-08 | 江苏清泉化学有限公司 | Method for synthesizing 3,3'-dimethyl-4,4'-diamino dicyclohexyl methane |
| US9045381B2 (en) | 2010-10-19 | 2015-06-02 | Yeda Research And Development Co. Ltd. | Ruthenium complexes and their uses in processes for formation and/or hydrogenation of esters, amides and derivatives thereof |
| CN106622220A (en) * | 2016-10-28 | 2017-05-10 | 南京工业大学 | Hydrogenation catalyst, preparation method and application |
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| US10533028B2 (en) | 2014-09-04 | 2020-01-14 | Yeda Research And Development Co. Ltd. | Ruthenium complexes and their uses as catalysts in processes for formation and/or hydrogenation of esters, amides and related reactions |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5550294A (en) * | 1992-02-05 | 1996-08-27 | Olin Corporation | Method of increasing hydrogenation rate of aromatic amines |
| TW200944498A (en) * | 2008-01-18 | 2009-11-01 | Basf Se | Process for preparing cycloaliphatic amines |
| WO2010005859A2 (en) * | 2008-07-07 | 2010-01-14 | Albemarle Corporation | Processes for hydrogenating aromatic amines |
-
2010
- 2010-11-25 CN CN2010105584129A patent/CN102030657A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5550294A (en) * | 1992-02-05 | 1996-08-27 | Olin Corporation | Method of increasing hydrogenation rate of aromatic amines |
| TW200944498A (en) * | 2008-01-18 | 2009-11-01 | Basf Se | Process for preparing cycloaliphatic amines |
| WO2010005859A2 (en) * | 2008-07-07 | 2010-01-14 | Albemarle Corporation | Processes for hydrogenating aromatic amines |
Non-Patent Citations (2)
| Title |
|---|
| HOON SIK KIM ET AL.: "Ru-catalyzed hydrogenation of aromatic diamines: The effect of alkali metal salts", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
| 张继光: "《催化剂制备过程技术》", 30 June 2004, 中国石化出版社 * |
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