CN102040524B - Separation processing method for isomer mixture of 4,4'-methylenebis(cyclohexylamine) - Google Patents
Separation processing method for isomer mixture of 4,4'-methylenebis(cyclohexylamine) Download PDFInfo
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Abstract
The invention relates to a separation processing method for an isomer mixture of 4,4'-methylenebis(cyclohexylamine), which belongs to the technical field of fine chemical and physical separation. The method comprises the following steps of: adding a molten raw-material mixture and a solvent into a reaction bottle, stirring until dissolving, cooling to the temperature of 0-10 DEG C through an ice-water bath, standing and crystallizing for 0.2-2 hours, then filtering, and processing a filter cake to obtain a product, wherein the content of the product is determined to be not less than 99.8 percent with HPLC (High Performance Liquid Chromatography), a trans-trans isomer is larger than 74 percent by weight, and the yield is 41-47 percent; and processing a mother liquid to obtain a product, wherein the content of the product is determined to be not less than 99.5 percent with the HPLC, the trans-trans isomer is smaller than 24 percent by weight, and the yield is 47-53 percent. In the invention, PACM50 (4,4'-methylenebiscyclohexylamine) is separated into two products of PACM20 and PACM70 by utilizing a solvent and adopting a physical crystallizing and separating method, the separating method is simple, has the advantages of mild condition, strong operability, good separating effect, high product purity, high yield, convenience in operation, solvent recyclability and less environment pollution and is suitable for industrialized production.
Description
Technical field
The invention belongs to fine chemistry industry Physical Separation Technology field, be specifically related to one 4, the method for separating and processing of the isomer mixt of 4 '-diamino, two cyclohexane methane.
Background technology
4, anti-, suitable anti-, the suitable three kinds of steric isomers that thermodynamic property is different of 4 '-diamino-dicyclohexyl methane (being called for short PACM) existence, its common thermodynamic(al)equilibrium content is: the anti-50wt% that accounts for, along the anti-43wt% that accounts for, along the suitable 7wt% that accounts for, anti-4,4-diamino, two cyclohexyl methane are stable structures on thermodynamic significance in three kinds of isomer.The proportion of composing of three kinds of isomer has determined character and the purposes of PACM product and subsequent product thereof, and be difficult to obtain by separation means the PACM that single or specific isomer forms, therefore industrial PACM product is specification and the purposes of the mixing of various steric isomers and the content definition PACM of anti-4,4-diamino, the two cyclohexyl methane of custom.Anti-4,4-diamino, two cyclohexyl methane content 24wt%, hereinafter referred to as PACM20, are the important intermediate in polyamine ester and polymeric amide industry, and the transparent polyurethane that is applied to high-quality is synthetic, has unique resistance to xanthochromia and the feature of weather resisteant.Anti-4,4-diamino two cyclohexyl methane content 50wt% left and right are called PACM50, mainly for the preparation of fatty polyamide resin.Anti-4, more than 4-diamino two cyclohexyl methane content 70wt% be called PACM70, be mainly used to manufacture the raw material of fiber Kui Ana, Kui Ana (Qiana) is the trade(brand)name that du pont company produces, by two a pair of aminocyclohexyl methane and dicarboxylic acid polycondensation, the fiber making through melt-spinning, belong to the tynex of fatty ring, intensity, elongation and the water absorbability of fiber is slightly low compared with nylon 6, nylon 66, but Young's modulus is high, and elasticity, photostabilization are good, proportion is little, covering power is strong, and gloss is good, has the title of class silky fibre.Anti-crease property, dimensional stability, dyeing behavior and the wash and wear performance of Kui Ana fiber are all fine.
PACM product synthetic route is generally synthetic in High Temperature High Pressure catalytic hydrogenation with 4,4'-diaminodiphenyl-methane (MDA).Anti-, suitable anti-, the suitable three kinds of isomer of synthetic PACM existence, its common thermodynamic(al)equilibrium content is the anti-50wt% that accounts for, along the anti-43wt% that accounts for, along along accounting for 7wt%, anti-4,4-diamino, two cyclohexyl methane are stable structures on thermodynamic significance in three kinds of isomer, above synthetic route, by improving temperature of reaction, in the product that this synthetic route obtains, the ratio of anti-4,4-diamino, two cyclohexyl methane can only reach 50wt% left and right.
By the PACM of common thermodynamic(al)equilibrium anti-anti-, along anti-, along the mixture along three kinds of isomer, through specific separation method, can make the high PACM70 of anti-4,4-diamino, two cyclohexyl methane content.Mainly contain following two kinds of modes: 1, by PACM and aldehyde, ketone (as phenyl aldehyde, cyclopentanone, acetone etc.) formation imines, imines tautomerizes to high anti-4,4-diamino, two cyclohexyl methane imines under alkaline condition, then can obtain anti-4 through acid hydrolysis, 4-diamino two cyclohexyl methane are up to the PACM (US4026943A of 90wt%, US4020104A, DE4334790, JP47038438); But this method reactions steps is many, and condition harshness, and cost is high; 2, by PACM and suitable acid (example hydrochloric acid, sulfuric acid, acetic acid, 1,10-sebacic acid etc.) salify, then through recrystallization, alkalization, can obtain instead 4, and 4-diamino two cyclohexyl methane are up to the PACM(FR2012261 of 90wt%, FR1566051, JP50037759); But the method still needs multistep operation.
Summary of the invention
For the above-mentioned problems in the prior art, the object of the present invention is to provide a kind of technology to adopt physical separation method separating treatment 4 simple to operate, the isomer mixt of 4 '-diamino, two cyclohexane methane.
Described one 4, the method for separating and processing of the isomer mixt of 4 '-diamino, two cyclohexane methane, is characterized in that described method for separating and processing is as follows:
1), using as 4 of raw mixture, the isomer mixt of 4 '-diamino, two cyclohexane methane is heated to fusing;
2) raw mixture after fusing in step 1) is dropped in reaction flask together with solvent, be stirred to completely and dissolve, under ice-water bath, stir and be cooled to 0～10 ℃ of crystallization, there is crystallisate to separate out, standing crystallization was filtered after 0.2～2 hour, and described raw mixture contains suitable anti-4 of anti-4,4-diamino two cyclohexyl methane that weight fraction is 50wt%, 41wt%, the product mixtures along suitable 4,4-diamino, two cyclohexyl methane of 4-diamino two cyclohexyl methane and 9wt%; Described solvent is the one in ethyl acetate, ethyl formate, dioxane, 2-methyltetrahydrofuran, tetramethylene sulfide, isopropyl ether, and raw mixture and the solvent weight ratio that feeds intake is 1.0:1.0～2.5, and described raw material is called for short PACM50;
3) by step 2) filter the filter cake crystallisate air distillation obtaining except desolventizing, underpressure distillation obtains containing anti-4 of 74wt%-82wt% again, suitable anti-4 of 4-diamino two cyclohexyl methane, 17wt%-21wt%, suitable 4 of 4-diamino two cyclohexyl methane and 3wt%-5wt%, the product mixtures of 4-diamino two cyclohexyl methane, is called for short PACM70; Mother liquor air distillation is except desolventizing, underpressure distillation obtains containing anti-4 of 18wt%-24wt%, suitable anti-4 of 4-diamino two cyclohexyl methane, 60wt%-65 wt%, suitable 4 of 4-diamino two cyclohexyl methane and 14wt%-20 wt%, the product mixtures of 4-diamino two cyclohexyl methane, is called for short PACM20.
Described one 4, the method for separating and processing of the isomer mixt of 4 '-diamino, two cyclohexane methane, is characterized in that step 2) described in raw mixture and the solvent weight ratio that feeds intake be 1.0:1.5～1.9.
Described one 4, the method for separating and processing of the isomer mixt of 4 '-diamino, two cyclohexane methane, is characterized in that step 2) described crystallization time is 0.5～1 hour.
Described one 24, the method for separating and processing of the isomer mixt of 4 '-amino bicyclic hexane methane, is characterized in that step 2) described crystallization time is 0.5 hour.
Described one 4, the method for separating and processing of the isomer mixt of 4 '-diamino, two cyclohexane methane, is characterized in that step 2) described in Tc be 2～5 ℃.
Described one 4, the method for separating and processing of the isomer mixt of 4 '-diamino, two cyclohexane methane, it is characterized in that the filter cake crystallisate described in step 3) reclaims solvent 80～170 ℃ of air distillations, underpressure distillation again after being cooled to 150 ℃, collect 172 ℃, the cut of 25mmHg, obtain containing anti-4 of 74wt%-82wt%, suitable anti-4 of 4-diamino two cyclohexyl methane, 17wt%-21wt%, the product mixtures along suitable 4,4-diamino, two cyclohexyl methane of 4-diamino two cyclohexyl methane and 3wt%-5wt%.
Described one 4, the method for separating and processing of the isomer mixt of 4 '-diamino, two cyclohexane methane, it is characterized in that the mother liquor described in step 3) reclaims solvent at 80～170 ℃ of normal pressures, underpressure distillation again while being cooled to 150 ℃, collect 180 ℃, the cut of 35mmHg, obtain containing anti-4 of 18wt%-24wt%, suitable anti-4 of 4-diamino two cyclohexyl methane, 60wt%-65wt%, the product mixtures along suitable 4,4-diamino, two cyclohexyl methane of 4-diamino two cyclohexyl methane and 14wt%-20wt%.
Described one 4, the method for separating and processing of the isomer mixt of 4 '-diamino, two cyclohexane methane, is characterized in that described product mixtures HPLC >=99.8%, anti-4,4-diamino two cyclohexyl methane are 74wt%-82wt%, and yield is 41%-47%.
Described one 4, the method for separating and processing of the isomer mixt of 4 '-diamino, two cyclohexane methane, is characterized in that described product mixtures HPLC >=99.5wt%, anti-4,4-diamino two cyclohexyl methane are 18wt%-24wt%, and yield is 47%-53%.
Described one 4, the method for separating and processing of the isomer mixt of 4 '-diamino, two cyclohexane methane, is characterized in that the recovery solvent described in step 3) can repeat to apply mechanically.
Described crystallisate air distillation is except desolventizing, and the product that underpressure distillation obtains is PACM70.Mother liquor air distillation is except desolventizing, and the product that underpressure distillation obtains is PACM20.
Compared with prior art, innovation of the present invention is to utilize a kind of solvent, the method that adopts physical crystal to separate, make PACM50 be separated into PACM20 and two kinds of products of PACM70, separation method is simple, mild condition, workable, and good separating effect, product purity is high, yield is high, treated product mixtures HPLC >=99.8% that obtains of filter cake crystallisate, anti-4, 4-diamino two cyclohexyl methane are 74wt%-82wt%, for PAMC70, yield is 41%-47%, treated product mixtures HPLC >=99.5% that obtains of mother liquor, anti-4, 4-diamino two cyclohexyl methane are 18wt%-24wt%, for PAMC20, yield is 47%-53%, total recovery is high, the PAMC70 purposes obtaining is wide, be worth high, product price per ton is approximately the twice of PACM50, greatly improved economic benefit, and solvent used is simple and easy to get, easily recovery and the rate of recovery are high, can reuse, greatly reduce production cost.In sum, beneficial effect of the present invention is embodied in: adopt the method for PACM50 Crystallization Separation in single solvent can obtain PACM70 and two kinds of products of PACM20.Crystallization yield is high, and PACM70 and PACM20 purity are more than 99.5%, easy and simple to handle, and recycled solvent, low in the pollution of the environment, is suitable for suitability for industrialized production.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but protection scope of the present invention is not limited in this:
Embodiment 1: the weight ratio that feeds intake PACM50: ethyl acetate is 1.0:1.5,5 ℃ of Tcs
At one, mechanical stirring is housed, the PACM50 and the 75g ethyl acetate that in tri-mouthfuls of reaction flasks of 250 mL of thermometer, add 50g to melt, be stirred to completely and dissolve, under ice-water bath, stir and be cooled to 5 ℃, then crystallization insulation 0.5 hour, suction strainer, filter cake crystallisate is poured in the there-necked flask of 100mL, in with simple distillation device, at 80～170 ℃ of normal pressures, reclaim ethyl acetate, when without flow, be cooled to 150 ℃ of left and right, with oil-sealed rotary pump, underpressure distillation is collected 172 ℃, the cut of 25mmHg obtains 23.2gPACM70, yield 46.4%, liquid phase purity 99.86%, anti-4, 4-diamino two cyclohexyl methane content 74.32wt%.Mother liquor is poured in the there-necked flask of 100mL, in simple distillation device, normal pressure reclaims ethyl acetate, when without flow, while being cooled to 150 ℃ of left and right, with oil-sealed rotary pump, the cut of 180 ℃ of underpressure distillation collections, 35mmHg, obtains 24.1gPACM20, yield 48.2%, liquid phase purity 99.48%, the content of anti-4,4-diamino, two cyclohexyl methane is 23.58wt%, reclaims ethyl acetate 70g, yield is 93.3%, capable of circulation the applying mechanically of ethyl acetate of recovery.
For the present embodiment, ethyl formate, dioxane, 2-methyltetrahydrofuran, tetramethylene sulfide, isopropyl ether also can obtain same effect.
Embodiment 2: the weight ratio that feeds intake PACM50: ethyl formate is 1.0:1.7,0 ℃ of Tc
At one, mechanical stirring is housed, the PACM50 and the 85g ethyl formate that in tri-mouthfuls of reaction flasks of 250mL of thermometer, add 50g to melt, be stirred to completely and dissolve, under ice-water bath, stir and be cooled to 0 ℃, then crystallization insulation 2 hours, suction strainer, filter cake crystallisate is poured in the there-necked flask of 100mL, in with simple distillation device, at 80～170 ℃ of normal pressures, reclaim ethyl formate, when without flow, while being cooled to 150 ℃ of left and right, with oil-sealed rotary pump, underpressure distillation is collected 172 ℃, the cut of 25mmHg obtains 23.2gPACM70, yield 46.4%, liquid phase purity 99.84%, anti-4, 4-diamino two cyclohexyl methane content 74.35wt%.Mother liquor is poured in the there-necked flask of 100mL, in simple distillation device, normal pressure reclaims ethyl formate.When without flow, while being cooled to 150 ℃ of left and right, with oil-sealed rotary pump, the cut of 180 ℃ of underpressure distillation collections, 35mmHg, obtain 24.1gPACM20, yield 48.2%, liquid phase purity 99.52%, anti-4,4-diamino two cyclohexyl methane content 23.54wt%, reclaim ethyl formate 78g, yield is 91.8%, capable of circulation the applying mechanically of ethyl formate of recovery.
Embodiment 3: the weight ratio that feeds intake PACM50: ethyl acetate is 1.0:1.9,10 ℃ of Tcs
At one, mechanical stirring is housed, the PACM50 and the 95g ethyl acetate that in tri-mouthfuls of reaction flasks of 250mL of thermometer, add 50g to melt, be stirred to completely and dissolve, under ice-water bath, stir and be cooled to 10 ℃, then crystallization insulation 0.2 hour, suction strainer, crystallisate is poured in the there-necked flask of 100mL, in with simple distillation device, at 80～170 ℃ of normal pressures, reclaim ethyl acetate, when without flow, while being cooled to 150 ℃ of left and right, with oil-sealed rotary pump, underpressure distillation is collected 172 ℃, the cut of 25mmHg obtains 22.9gPACM70, yield 45.8%, liquid phase purity 99.81%, anti-4, 4-diamino two cyclohexyl methane content 75.12wt%.Mother liquor is poured in the there-necked flask of 100mL, in simple distillation device, normal pressure reclaims ethyl acetate, and when without flow, while being cooled to 150 ℃ of left and right, with oil-sealed rotary pump, the cut of 180 ℃ of underpressure distillation collections, 35mmHg, obtains PACM20.Obtain 24.1gPACM20, yield 47.6wt%, liquid phase purity 99.54wt%, anti-4,4-diamino, two cyclohexyl methane content 23.20wt%, reclaim ethyl acetate 92g, and yield is 96.8%, capable of circulation the applying mechanically of ethyl acetate of recovery.
Embodiment 4: the weight ratio that feeds intake PACM50: tetramethylene sulfide is 1.0:2.0,2 ℃ of Tcs
At one, mechanical stirring is housed, the PACM50 and the 100g tetramethylene sulfide that in tri-mouthfuls of reaction flasks of 250mL of thermometer, add 50g to melt, be stirred to completely and dissolve, under ice-water bath, stir and be cooled to 5 ℃, then crystallization insulation 1 hour, suction strainer, crystallisate is poured in the there-necked flask of 100mL, in with simple distillation device, at 80～170 ℃ of normal pressures, reclaim tetramethylene sulfide, when without flow, while being cooled to 150 ℃ of left and right, with oil-sealed rotary pump, underpressure distillation is collected 172 ℃, the cut of 25mmHg obtains 21.7gPACM70, yield 43.4%, liquid phase purity 99.89%, anti-4, 4-diamino two cyclohexyl methane content 76.42wt%.Mother liquor is poured in the there-necked flask of 100mL, in simple distillation device, normal pressure reclaims tetramethylene sulfide, when without flow, while being cooled to 150 ℃ of left and right, with oil-sealed rotary pump, the cut of 180 ℃ of underpressure distillation collections, 35mmHg, obtains 25.2gPACM20, yield 50.4%, liquid phase purity 99.53%, anti-4,4-diamino, two cyclohexyl methane content 21.78wt%, reclaim tetramethylene sulfide 93.3g, yield is 93.3%, capable of circulation the applying mechanically of tetramethylene sulfide of recovery.
Embodiment 5: the weight ratio that feeds intake PACM50: ethyl acetate is 1.0:2.3,5 ℃ of Tcs
At one, mechanical stirring is housed, the PACM50 and the 115g ethyl acetate that in tri-mouthfuls of reaction flasks of 250 mL of thermometer, add 50g to melt, stir, treat to dissolve completely, under ice-water bath, stir and be cooled to 5 ℃, then crystallization insulation 0.5 hour, suction strainer, crystallisate is poured in the there-necked flask of 100mL, in with simple distillation device, at 80～170 ℃ of normal pressures, reclaim ethyl acetate, when without flow, while being cooled to 150 ℃ of left and right, with oil-sealed rotary pump, underpressure distillation is collected 172 ℃, the cut of 25mmHg obtains 21.4gPACM70, yield 42.8%, liquid phase purity 99.85%, anti-4, 4-diamino two cyclohexyl methane content 76.84wt%.Mother liquor is poured in the there-necked flask of 100mL, in simple distillation device, normal pressure reclaims ethyl acetate, while being cooled to 150 ℃ of left and right when without flow, with oil-sealed rotary pump, the cut of 180 ℃ of underpressure distillation collections, 35mmHg, obtain 25.2gPACM20, yield 50.4%, liquid phase purity 99.50%, anti-4,4-diamino two cyclohexyl methane content 21.21wt%, reclaim ethyl acetate 105g, yield is 91.3%, capable of circulation the applying mechanically of ethyl acetate of recovery.
Embodiment 6: the weight ratio that feeds intake PACM50: ethyl acetate is 1.0:2.5,5 ℃ of Tcs
At one, mechanical stirring is housed, the PACM50 and the 125g ethyl acetate that in tri-mouthfuls of reaction flasks of 250 mL of thermometer, add 50g to melt, stir, treat to dissolve completely, under ice-water bath, stir and be cooled to 5 ℃, then crystallization insulation 0.5 hour, suction strainer, crystallisate is poured in the there-necked flask of 100mL, in with simple distillation device, at 80～170 ℃ of normal pressures, reclaim ethyl acetate, when without flow, while being cooled to 150 ℃ of left and right, with oil-sealed rotary pump, underpressure distillation is collected 172 ℃, the cut of 25mmHg obtains 21gPACM70, yield 42%, liquid phase purity 99.87%, anti-4, 4-diamino two cyclohexyl methane content 77.54wt%.Mother liquor is poured in the there-necked flask of 100mL, in simple distillation device, normal pressure reclaims ethyl acetate, when without flow, while being cooled to 150 ℃ of left and right, with oil-sealed rotary pump, the cut of 180 ℃ of underpressure distillation collections, 35mmHg, obtains 25.7gPACM20, yield 51.4%, liquid phase purity 99.54%, anti-4,4-diamino, two cyclohexyl methane content 20.79wt%, reclaim ethyl acetate 116g, yield is 92.8%, capable of circulation the applying mechanically of ethyl acetate of recovery.
Embodiment 7: the weight ratio that feeds intake PACM50: ethyl acetate is 1.0:2.0,0 ℃ of Tc
At one, mechanical stirring is housed, the PACM50 and the 100g ethyl acetate that in tri-mouthfuls of reaction flasks of 250 mL of thermometer, add 50g to melt, be stirred to completely and dissolve, under ice-water bath, stir and be cooled to 0 ℃, then crystallization insulation 0.5 hour, suction strainer, crystallisate is poured in the there-necked flask of 100mL, at 80～170 ℃ of normal pressures, reclaim ethyl acetate, when without flow, while being cooled to 150 ℃ of left and right, with oil-sealed rotary pump, underpressure distillation is collected 172 ℃, the cut of 25mmHg obtains 20.6gPACM70, yield 41.2%, liquid phase purity 99.83%, anti-4, 4-diamino two cyclohexyl methane content 80.15wt%.Mother liquor is poured in the there-necked flask of 100mL, in simple distillation device, normal pressure reclaims ethyl acetate, while being cooled to again 150 ℃ of left and right, with oil-sealed rotary pump, the cut of 180 ℃ of underpressure distillation collections, 35mmHg, obtain 26.2gPACM20, yield 52.8%, liquid phase purity 99.50%, anti-4,4-diamino two cyclohexyl methane content 19.70wt%, reclaim ethyl acetate 91g, yield is 91.0%, capable of circulation the applying mechanically of ethyl acetate of recovery.
Embodiment 8: the weight ratio that feeds intake PACM50:2-methyltetrahydrofuran 1.0:2.0,10 ℃ of Tcs
At one, mechanical stirring is housed, the PACM50 and the 100g2-methyltetrahydrofuran that in tri-mouthfuls of reaction flasks of 250mL of thermometer, add 50g to melt, stir, treat to dissolve completely, under ice-water bath, stir and be cooled to 10 ℃, then crystallization insulation 0.5 hour, suction strainer, crystallisate is poured in the there-necked flask of 100mL, in with simple distillation device, at 80～170 ℃ of normal pressures, reclaim 2-methyltetrahydrofuran, while being cooled to 150 ℃ of left and right, with oil-sealed rotary pump, underpressure distillation is collected 172 ℃, the cut of 25mmHg obtains 23.0gPACM70, yield 46.0%, liquid phase purity 99.84%, anti-4, 4-diamino two cyclohexyl methane content 74.5wt%.Mother liquor is poured in the there-necked flask of 100mL, normal pressure reclaims 2-methyltetrahydrofuran, while being cooled to 150 ℃ of left and right, with oil-sealed rotary pump, the cut of 180 ℃ of underpressure distillation collections, 35mmHg, obtains 24.3gPACM20, yield 48.6%, liquid phase purity 99.50%, anti-4,4-diamino, two cyclohexyl methane content 23.12wt%, reclaim 2-methyltetrahydrofuran 90g, yield is 90.0%, capable of circulation the applying mechanically of 2-methyltetrahydrofuran of recovery.
Embodiment 9: the weight ratio that feeds intake PACM50: dioxane is 1.0:2.0,5 ℃ of Tcs
At PACM50 and a 100g dioxane that adds 50g to melt during tri-mouthfuls of reaction flasks of 250 mL of mechanical stirring, thermometer are housed, be stirred to completely and dissolve, under ice-water bath, stir and be cooled to 5 ℃, then crystallization insulation 0.5 hour, suction strainer, crystallisate is poured in the there-necked flask of 100mL, at 80～170 ℃ of normal pressures, reclaim dioxane, the cut of 172 ℃ of underpressure distillation collections, 25mmHg obtains 21.7gPACM70 again, yield 43.4%, liquid phase purity 99.89%, anti-4,4-diamino, two cyclohexyl methane content 76.42wt%.Mother liquor is poured in the there-necked flask of 100mL, normal pressure reclaims dioxane, when without flow, while being cooled to 150 ℃ of left and right, with oil-sealed rotary pump, the cut of 180 ℃ of underpressure distillation collections, 35mmHg, obtain 25.2gPACM20, yield 50.4%, liquid phase purity 99.53%, anti-4,4-diamino two cyclohexyl methane content 21.78wt%, reclaim dioxane 92g, yield is 92.0%, capable of circulation the applying mechanically of dioxane of recovery.
Embodiment 10: the weight ratio that feeds intake PACM50: isopropyl ether is 1.0:2.0,5 ℃ of Tcs
At one, mechanical stirring is housed, the PACM50 and the 100g isopropyl ether that in tri-mouthfuls of reaction flasks of 250mL of thermometer, add 50g to melt, stir completely and dissolve, under ice-water bath, stir and be cooled to 5 ℃, then crystallization insulation 0.5 hour, suction strainer, crystallisate is poured in the there-necked flask of 100mL, at 80～170 ℃ of normal pressures, reclaim isopropyl ether, when without flow, while being cooled to 150 ℃ of left and right, with oil-sealed rotary pump, underpressure distillation is collected 172 ℃, the cut of 25mmHg obtains 21.5gPACM70, yield 43.0%, liquid phase purity 99.85%, anti-4, 4-diamino two cyclohexyl methane content 76.72wt%.Mother liquor is poured in the there-necked flask of 100mL, normal pressure reclaims isopropyl ether, while being cooled to 150 ℃ of left and right, with oil-sealed rotary pump, the cut of 180 ℃ of underpressure distillation collections, 35mmHg, obtains 25.2gPACM20, yield 50.4%, liquid phase purity 99.50%, anti-4,4-diamino, two cyclohexyl methane content 21.37wt%, reclaim isopropyl ether 93g, yield is 93.0%, capable of circulation the applying mechanically of isopropyl ether of recovery.
Embodiment 11: the weight ratio that feeds intake PACM50:2-methyltetrahydrofuran 1.0:2.0,2 ℃ of Tcs
At one, mechanical stirring is housed, the PACM50 and the 100g 2-methyltetrahydrofuran that in tri-mouthfuls of reaction flasks of 250mL of thermometer, add 50g to melt, stir completely and dissolve, under ice-water bath, stir and be cooled to 5 ℃, then crystallization insulation 0.5 hour, suction strainer, crystallisate is poured in the there-necked flask of 100mL, in with simple distillation device, at 80～170 ℃ of normal pressures, reclaim 2-methyltetrahydrofuran, while being cooled to 150 ℃ of left and right, with oil-sealed rotary pump, underpressure distillation is collected 172 ℃, the cut of 25mmHg obtains 23.5gPACM70, yield 47%, liquid phase purity 99.82%, anti-4, 4-diamino two cyclohexyl methane content 73.95wt%.Mother liquor is poured in the there-necked flask of 100mL, normal pressure reclaims 2-methyltetrahydrofuran, while being cooled to 150 ℃ of left and right, with oil-sealed rotary pump, the cut of 180 ℃ of underpressure distillation collections, 35mmHg, obtains 23.8gPACM20, yield 47.6%, liquid phase purity 99.50%, anti-4,4-diamino, two cyclohexyl methane content 23.78wt%, reclaim 2-methyltetrahydrofuran 94g, yield is 94.0%, capable of circulation the applying mechanically of 2-methyltetrahydrofuran of recovery.
Claims (10)
1. one kind 4, the method for separating and processing of the isomer mixt of 4 '-diamino, two cyclohexane methane, is characterized in that
Described method for separating and processing is as follows:
1), using as 4 of raw mixture, the isomer mixt of 4 '-diamino, two cyclohexane methane is heated to fusing;
2) raw mixture after fusing in step 1) is dropped in reaction flask together with solvent, be stirred to completely and dissolve, at ice
Under water-bath, stir and be cooled to 0～10 ℃ of crystallization, there is crystallisate to separate out, standing crystallization was filtered after 0.2～2 hour, it is anti-4 of 50wt% that described raw mixture contains weight fraction, suitable anti-4 of 4-diamino two cyclohexyl methane, 41wt%, the product mixtures along suitable 4,4-diamino, two cyclohexyl methane of 4-diamino two cyclohexyl methane and 9wt%; Described solvent is the one in ethyl acetate, ethyl formate, dioxane, 2-methyltetrahydrofuran, tetramethylene sulfide, isopropyl ether, and raw mixture and the solvent weight ratio that feeds intake is 1.0:1.0～2.5;
3) by step 2) filter the filter cake crystallisate air distillation obtaining except desolventizing, underpressure distillation obtains containing anti-4 of 74wt%-82wt% again, suitable anti-4 of 4-diamino two cyclohexyl methane, 17wt%-21%, suitable 4 of 4-diamino two cyclohexyl methane and 3wt%-5wt%, the product mixtures of 4-diamino two cyclohexyl methane, in this product mixtures anti-4,4-diamino two cyclohexyl methane, suitable anti-4, the weight percentage sum of 4-diamino two cyclohexyl methane and suitable 4,4-diamino, two cyclohexyl methane is 100%; Mother liquor air distillation is except desolventizing, underpressure distillation obtains containing anti-4 of 18wt%-24wt%, suitable anti-4 of 4-diamino two cyclohexyl methane, 60wt%-65 wt%, the product mixtures along suitable 4,4-diamino, two cyclohexyl methane of 4-diamino two cyclohexyl methane and 14wt%-20 wt%.
2. according to the one 4 described in claim 1, the isomer mixt of 4 '-diamino, two cyclohexane methane point
From treatment process, it is characterized in that step 2) described in raw mixture and the solvent weight ratio that feeds intake be 1.0:1.5～1.9.
3. according to the one 4 described in claim 1, the isomer mixt of 4 '-diamino, two cyclohexane methane point
From treatment process, it is characterized in that step 2) described crystallization time is 0.5～1 hour.
4. according to the one 24 described in claim 1, the isomer mixt of 4 '-amino bicyclic hexane methane point
From treatment process, it is characterized in that step 2) described crystallization time is 0.5 hour.
5. according to the one 4 described in claim 1, the isomer mixt of 4 '-diamino, two cyclohexane methane point
From treatment process, it is characterized in that step 2) described in Tc be 2～5 ℃.
6. according to claim 1 a kind of 4, the separation of the isomer mixt of 4 '-diamino, two cyclohexane methane
Treatment process, it is characterized in that the filter cake crystallisate described in step 3) reclaims solvent 80～170 ℃ of air distillations, underpressure distillation again after being cooled to 150 ℃, collect 172 ℃, the cut of 25mmHg, obtain containing anti-4 of 74wt%-82wt%, 4-diamino two cyclohexyl methane, suitable anti-4 of 17wt%-21wt%, suitable 4 of 4-diamino two cyclohexyl methane and 3wt%-5wt%, the product mixtures of 4-diamino two cyclohexyl methane, in this product mixtures anti-4, 4-diamino two cyclohexyl methane, along anti-4, 4-diamino two cyclohexyl methane and suitable 4, the weight percentage sum of 4-diamino two cyclohexyl methane is 100%.
7. according to the one 4 described in claim 1, the isomer mixt of 4 '-diamino, two cyclohexane methane point
From treatment process, it is characterized in that the mother liquor described in step 3) reclaims solvent at 80～170 ℃ of normal pressures, underpressure distillation again while being cooled to 150 ℃, collect 180 ℃, the cut of 35mmHg, obtain containing anti-4 of 18wt%-24wt%, 4-diamino two cyclohexyl methane, 60wt%-65wt%'s is suitable anti-4,4-diamino two cyclohexyl methane and 14wt%-20wt% along the product mixtures along 4,4-diamino, two cyclohexyl methane.
8. according to the one 4 described in claim 6, the isomer mixt of 4 '-diamino, two cyclohexane methane point
From treatment process, it is characterized in that described product mixtures HPLC >=99.8%, anti-4,4-diamino, two cyclohexyl methane are 74wt%-82wt%, yield is 41%-47%.
9. according to the one 4 described in claim 7, the isomer mixt of 4 '-diamino, two cyclohexane methane point
From treatment process, it is characterized in that described product mixtures HPLC >=99.5%, anti-4,4-diamino, two cyclohexyl methane are 18wt%-24wt%, yield is 47%-53%.
10. according to the one 4 described in claim 1, the method for separating and processing of the isomer mixt of 4 '-diamino, two cyclohexane methane, is characterized in that the recovery solvent described in step 3) can repeat to apply mechanically.
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| DE1468855A1 (en) * | 1964-12-28 | 1969-04-17 | Du Pont | Process for the preparation of bis (p-amonocyclohexyl) methane alcoholates |
| US4026943A (en) * | 1976-09-20 | 1977-05-31 | The Upjohn Company | Novel process |
| CN101050184A (en) * | 2007-05-23 | 2007-10-10 | 宁波万华聚氨酯有限公司 | Method for producing H12MDA through hydrogenation reaction |
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