CN110981753A - Preparation of diphenyl ethane diisocyanate by dimethyl carbonate method and application thereof - Google Patents
Preparation of diphenyl ethane diisocyanate by dimethyl carbonate method and application thereof Download PDFInfo
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- dimethyl carbonate
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- ADYVCZCQSVYNPQ-UHFFFAOYSA-N N=C=O.N=C=O.C=1C=CC=CC=1C(C)C1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C=1C=CC=CC=1C(C)C1=CC=CC=C1 ADYVCZCQSVYNPQ-UHFFFAOYSA-N 0.000 title claims 10
- 238000000034 method Methods 0.000 title claims 10
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 title claims 9
- 238000002360 preparation method Methods 0.000 title claims 4
- 125000001424 substituent group Chemical group 0.000 claims 6
- BOJZPUPAXYETRK-UHFFFAOYSA-N 1,1-diphenylethane-1,2-diamine Chemical compound C=1C=CC=CC=1C(N)(CN)C1=CC=CC=C1 BOJZPUPAXYETRK-UHFFFAOYSA-N 0.000 claims 4
- 238000007112 amidation reaction Methods 0.000 claims 3
- 239000003054 catalyst Substances 0.000 claims 3
- 238000004519 manufacturing process Methods 0.000 claims 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 claims 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 238000000197 pyrolysis Methods 0.000 claims 2
- 239000011701 zinc Substances 0.000 claims 2
- 229910052725 zinc Inorganic materials 0.000 claims 2
- LTPIMWHLZKJSCI-UHFFFAOYSA-N (1,2-dinitro-1-phenylethyl)benzene Chemical compound C=1C=CC=CC=1C([N+]([O-])=O)(C[N+](=O)[O-])C1=CC=CC=C1 LTPIMWHLZKJSCI-UHFFFAOYSA-N 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 238000004587 chromatography analysis Methods 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 claims 1
- 230000008025 crystallization Effects 0.000 claims 1
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- -1 diphenylethane diisocyanate compound Chemical class 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 238000000605 extraction Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 239000002808 molecular sieve Substances 0.000 claims 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 239000011347 resin Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 239000011787 zinc oxide Substances 0.000 claims 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/10—Preparation of derivatives of isocyanic acid by reaction of amines with carbonyl halides, e.g. with phosgene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a method for preparing diphenylethane diisocyanate by a dimethyl carbonate method and application thereof, relating to the technical field of preparation of high polymer material monomers; dinitrodiphenylethane is used as an initiator, nitrogen is introduced for protection, a catalyst is added, hydrogen is introduced for reaction to prepare diaminodiphenylethane, the diaminodiphenylethane is dissolved in dimethyl carbonate, amidation reaction is carried out at 0-150 ℃ under the action of the catalyst, pyrolysis reaction is carried out at 80-200 ℃ after reaction for a certain time to the end point, and a diphenylethane diisocyanate compound is obtained by separation and purification; the EDI is prepared by adopting a dimethyl carbonate method, and the dimethyl carbonate has the characteristics of safe and convenient use, little pollution, convenient metering and the like, and has the advantages of low toxicity, environmental protection, convenient use and the like. The dimethyl carbonate method not only improves the working condition, but also improves the quality and the yield of the EDI product.
Description
Technical Field
The invention discloses diphenylethane diisocyanate prepared by a dimethyl carbonate method and application thereof, and relates to the technical field of preparation of high polymer material monomers.
Background
Polyurethane can be synthesized into a plurality of synthetic materials with great use value, such as polyurethane foam, and is mainly used for heat preservation and transportation, detachable heat insulation boards, hard foam boards and the like. The polyurethane semi-rigid foam can bear high load, is used for cushions and mattresses in transportation tools such as airplanes, automobiles, trains and the like, and various products with good buffering and anti-seismic performance and impact energy absorption, and is widely applied in the transportation industry. The products of the polyurethane flexible foam mainly comprise high-resilience flexible foam, fabric linings, automobile seat cushions and the like. The polyurethane monomer can also be used as an adhesive, and can be applied to daily necessities adhesives, building adhesives, emulsion adhesives, aluminum-plastic composite film adhesives and the like. Compared with the traditional PVC artificial leather, the polyurethane leather has the advantages of washing resistance, folding resistance, good air permeability, good hand feeling, fresh color, good cold resistance and natural artificial leather effect, and is a high-grade finishing material in the industries of clothing, shoes, hats, furniture decoration and the like. The polyurethane can also be used for preparing elastomers, thermoplastic polyurethane elastomers, mixing polyurethane elastomers and microporous elastomers, and can be used as various rubber rollers, shoe sole materials, sealing products, cable sheaths, automobile bumpers, instrument panels, steering wheels, medical materials, damping materials and the like.
Isocyanates are the main raw materials for the synthesis of polyurethanes, and have recently become the most promising chemically synthesized materials worldwide. In the 30 s of the 20 th century, a synthetic method and a processing technology of diisocyanate were developed for the first time by German chemist O.B eye and colleagues thereof, and the synthetic method is a phosgenation method utilizing the reaction of diamine and phosgene. Industrial production of isocyanates was achieved in 1995 in the United states. At present, China is also a big country for producing and using polyurethane. Generally, isocyanate is mainly produced by a phosgene method, but phosgene is extremely toxic, potential safety hazards are high, hydrochloric acid serving as a byproduct is high in corrosivity and high in equipment requirement, and residual chlorine in the product is difficult to remove, so that the application performance of the product is influenced.
Disclosure of Invention
The invention provides a preparation method of Diphenylethane diisocyanate (EDI) by a dimethyl carbonate method and an application thereof, aiming at the problems of the prior art, and the invention also aims to provide an application of the EDI in preparing a polyurethane material.
The specific scheme provided by the invention is as follows:
a dimethyl carbonate method for preparing diphenyl ethane diisocyanate comprises the following steps: dinitrodiphenylethane is used as an initiator, nitrogen is introduced for protection, a catalyst is added, hydrogen is introduced for reaction to prepare diaminodiphenylethane,
dissolving diaminodiphenylethane in dimethyl carbonate, performing amidation reaction at 0-150 ℃ under the action of a catalyst, performing pyrolysis reaction at 80-200 ℃ to the end point after reacting for a certain time, and separating and purifying to obtain the diphenylethane diisocyanate compound.
The reaction formula for the preparation of diaminodiphenylethane can be:
wherein R is H or a hydrocarbyl group; the substituent R is positioned at the 2(2 ') position or the 3 (3') position; -NO2The substituent is positioned at the 4(4 ') position, the 5(5 ') position or the 6(6 ') position; -NH2The substituent is located at the 4(4 ') position, or the 5(5 ') position, or the 6(6 ') position. Preferably, wherein R is H or methyl or ethyl or n-propyl.
The reaction formula of amidation reaction in preparing diphenylethane diisocyanate by using a dimethyl carbonate method can be as follows:
wherein R is H or a hydrocarbyl group; the substituent R is positioned at the 2(2 ') position or the 3 (3') position; -NH2The substituent is positioned at the 4(4 ') position, the 5(5 ') position or the 6(6 ') position; -NHCOOCH3The substituent is located at the 4(4 ') position, or the 5(5 ') position, or the 6(6 ') position.
The reaction formula of the pyrolysis reaction in the preparation of the diphenylethane diisocyanate by the dimethyl carbonate method is as follows:
wherein R is H or a hydrocarbyl group; the substituent R is positioned at 2 (2') Bit or 3 (3') bit; -NHCOOCH3The substituent is positioned at the 4(4 ') position, the 5(5 ') position or the 6(6 ') position; the-NCO substituent is located at the 4(4 ') position or the 5(5 ') position or the 6(6 ') position. Preferred substituents R are H or methyl or ethyl or n-propyl.
Preferably, the starting reactant is dinitrodiphenylethane selected from 6,6 '-dinitrodiphenylethane, 5' -dinitrodiphenylethane, 4 '-dinitrodiphenylethane, 2' -dimethyl-6, 6 '-dinitrodiphenylethane, 2' -dimethyl-5, 5 '-dinitrodiphenylethane, 2' -dimethyl-4, 4 '-dinitrodiphenylethane, 2' -dimethyl-4, 5 '-dinitrodiphenylethane, 2' -dimethyl-4, 6 '-dinitrodiphenylethane, 2' -dimethyl-5, 6 '-dinitrodiphenylethane, 2' -diethyl-6, 6 '-dinitrodiphenylethane, 2' -diethyl-5, 5 '-dinitrodiphenylethane, 2' -diethyl-4, 4 '-dinitrodiphenylethane, 2' -diethyl-4, 5 '-dinitrodiphenylethane, 2' -diethyl-4, 6 '-dinitrodiphenylethane, 2' -diethyl-5, 6 '-dinitrodiphenylethane, 2' -di-n-propyl-6, 6 '-dinitrodiphenylethane, 2' -di-n-propyl-5, 5 '-dinitrodiphenylethane, 2' -di-n-propyl-4, 4 '-dinitrodiphenylethane, 2' -di-n-propyl-4, 5 '-dinitrodiphenylethane, 2' -di-n-propyl-4, 6 '-dinitrodiphenylethane, 2' -di-n-propyl-5, 6 '-dinitrodiphenylethane, 3' -dimethyl-6, 6 '-dinitrodiphenylethane, 3' -dimethyl-5, 5 '-dinitrodiphenylethane, 3' -dimethyl-4, 4 '-dinitrodiphenylethane, 3' -diethyl-6, 6 '-dinitrodiphenylethane, 3' -diethyl-5, 5 '-dinitrodiphenylethane, 3' -diethyl-4, 4 '-dinitrodiphenylethane, 3' -di-n-propyl-6, 6' -dinitrodiphenylethane, 3' -di-n-propyl-5, 5' -dinitrodiphenylethane, 3' -di-n-propyl-4, 4' -dinitrodiphenylethane.
The dosage of the dimethyl carbonate in the preparation of the diphenylethane diisocyanate by the dimethyl carbonate method is that each kilogram of diaminodiphenylethane is dissolved in 1L-100L of dimethyl carbonate.
Preferably, the ratio of diaminodiphenylethane to dimethyl carbonate is 1 kg: 2.0L-50.0L. More preferably 1 kg: 5.0L-10.0L.
The preferable amidation reaction temperature is 20-80 ℃, and the reaction time is 0.1-72 h; the pyrolysis reaction is carried out at 80-200 ℃, and the chromatographic detection reaction is carried out until the end point.
The catalyst for amidation reaction in preparation of diphenylethane diisocyanate by using a dimethyl carbonate method comprises but is not limited to one or a combination of organic zinc, nano zinc oxide and a zinc organic complex. The catalyst is preferably zinc acetate or zinc fumarate.
The separation and purification method in the preparation of the diphenylethane diisocyanate by the dimethyl carbonate method comprises but is not limited to the combination of one or more of filtration, resin treatment, water washing, distillation, crystallization, extraction, activated carbon treatment, molecular sieve treatment and chromatography.
The invention also provides a diphenyl ethane diisocyanate obtained by the process for preparing the diphenyl ethane diisocyanate by the dimethyl carbonate method.
The EDI prepared by the invention can have the structure:
r is H or alkyl; the substituent R is positioned at the 2(2 ') position or the 3 (3') position; the substituent-NCO is located at the 4(4 ') position, or the 5(5 ') position, or the 6(6 ') position. Preferably, wherein R is H or methyl or ethyl or n-propyl.
EDI in the present invention is preferably selected from diphenylethane-6, 6' -diisocyanate, diphenylethane-5, 5' -diisocyanate, diphenylethane-4, 4' -diisocyanate, 2' -dimethyldiphenylethane-6, 6' -diisocyanate, 2' -dimethyldiphenylethane-5, 5' -diisocyanate, 2' -dimethyldiphenylethane-4, 4' -diisocyanate, 2' -dimethyldiphenylethane-4, 5' -diisocyanate, 2' -dimethyldiphenylethane-4, 6' -diisocyanate, 2' -dimethyldiphenylethane-5, 6' -diisocyanate, mixtures thereof, and mixtures thereof, 2,2' -diethyldiphenylethane-6, 6' -diisocyanate, 2' -ethylmethyldiphenylethane-5, 5' -diisocyanate, 2' -diethyldiphenylethane-4, 4' -diisocyanate, 2' -diethyldiphenylethane-4, 5' -diisocyanate, 2' -diethyldiphenylethane-4, 6' -diisocyanate, 2' -diethyldiphenylethane-5, 6' -diisocyanate, 2' -di-n-propyldiphenylethane-6, 6' -diisocyanate, 2' -di-n-propyldiphenylethane-5, 5' -diisocyanate, 2' -di-n-propyldiphenylethane-4, 4' -diisocyanate, 2' -di-n-propyldiphenylethane-4, 5' -diisocyanate, 2' -di-n-propyldiphenylethane-4, 6' -diisocyanate, 2' -di-n-propyldiphenylethane-5, 6' -diisocyanate, 3' -dimethyldiphenylethane-6, 6' -diisocyanate, 3' -dimethyldiphenylethane-5, 5' -diisocyanate, 3' -dimethyldiphenylethane-4, 4' -diisocyanate, 3' -diethyldiphenylethane-6, 6' -diisocyanate, 3' -diethyldiphenylethane-5, 5' -diisocyanate, 3,3 '-diethyldiphenylethane-4, 4' -diisocyanate, 3 '-di-n-propyldiphenylethane-6, 6' -diisocyanate, 3 '-di-n-propyldiphenylethane-5, 5' -diisocyanate, 3 '-di-n-propyldiphenylethane-4, 4' -diisocyanate.
Further EDI is preferably selected from diphenylethane-6, 6' -diisocyanate, diphenylethane-5, 5' -diisocyanate, diphenylethane-4, 4' -diisocyanate, 2' -dimethyldiphenylethane-6, 6' -diisocyanate, 2' -dimethyldiphenylethane-5, 5' -diisocyanate, 2' -dimethyldiphenylethane-4, 4' -diisocyanate, 3' -dimethyldiphenylethane-5, 5' -diisocyanate, 3' -dimethyldiphenylethane-4, 4' -diisocyanate, 3' -diethyldiphenylethane-5, 5' -diisocyanate, mixtures thereof, and mixtures thereof, 3,3 '-diethyldiphenylethane-4, 4' -diisocyanate.
The application of the diphenylethane diisocyanate in preparing chemical synthetic materials. Particularly in synthesizing polyurethane, including polyurethane foam, polyurethane adhesive, polyurethane synthetic leather, polyurethane fabric coating, polyurethane resin coating, polyurethane elastomer and other synthetic materials.
The invention has the advantages that:
the invention provides a preparation method of dimethyl carbonate of diphenylethane diisocyanate and application thereof, which adopts the dimethyl carbonate method to prepare EDI, wherein the dimethyl carbonate has the characteristics of safe and convenient use, little pollution, convenient metering and the like, and has the advantages of low toxicity, environmental protection, convenient use and the like. The dimethyl carbonate method not only improves the working condition, but also improves the quality and the yield of the EDI product. In addition, the EDI compound prepared by the invention can be used for preparing polyurethane, and has more excellent properties, such as better elongation, tensile strength and tearing strength of the elastomer compared with MDI, and can meet the application of higher requirements of polyurethane materials.
Drawings
FIG. 1 is a schematic process flow diagram of the process of the present invention.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred embodiments and materials described herein are intended to be exemplary only.
Dinitrodiphenylethane is purchased as a raw material, and partially produced, and the production method is carried out according to the literature (synthesis of 4,4 '-dinitrodiphenylethane (alkene), such as lujunri, wanya, linvon yan [ J ], applied chemistry, 2000, 17 (6): 651-653.), and 4,4' -dinitrodiphenylethane, dimethyl-dinitrodiphenylethane, diethyl-dinitrodiphenylethane, and di-n-propyl-dinitrodiphenylethane can be produced.
Reagents are procured or configured.
The preparation process of the dinitrodiphenylethane comprises the following steps: in the reverse directionAdding 15.12k g 4-nitro-o-xylene and 150L of tert-butyl alcohol into a kettle, heating to 50 ℃ under stirring, adding sodium alkoxide solution, adding 2.5kg of flaky metallic sodium into 30L of tert-butyl alcohol, fully reacting and uniformly stirring to obtain the sodium alkoxide solution, reacting for 30min, dropwise adding 20kg of 30% hydrogen peroxide into the sodium alkoxide solution within 2h at the same temperature, continuing to react for 2h, filtering while hot, washing a filter cake with a proper amount of tert-butyl alcohol, recovering filtrate, placing the filter cake into 50L of deionized water, heating to 90-100 ℃ under stirring, preserving heat for 10min, performing suction filtration while hot, fully washing the filter cake to neutrality with hot water above 90 ℃, performing suction filtration, drying to constant weight at 80-90 ℃ to obtain pale yellow 2,2 '-dimethyl-4, 4' -dinitrodiphenylethane 12.81k g, 95.64% (HPLC, normalization method), and obtaining yield of 85.3%,13C NMR(100MHz,CDCl3) δ 145.05, 145.05, 143.34, 143.34, 136.41, 136.41, 129.22, 129.22, 125.35, 125.35, 120.84, 120.84, 36.45, 36.45, 18.12, 18.12; FAB-HRMS: m/e (300.3077), formula: c16H16N2O4。
According to the above process, dinitrodiphenylethane such as dinitrodiphenylethane, dimethyl-dinitrodiphenylethane, diethyl-dinitrodiphenylethane, di-n-propyl-dinitrodiphenylethane and the like can be produced by using an appropriate starting material.
Diaminodiphenylethane preparation procedure 1:
weighing 3.00kg of 2,2 '-dimethyl-4, 4' -dinitrodiphenylethane, 300.0g of Raney Ni catalyst, 10.0L of absolute ethyl alcohol, adding the absolute ethyl alcohol into a reaction kettle with a stirrer, introducing nitrogen to replace air, then introducing hydrogen, reacting for 4h at the stirring speed of 1000r/min, the reaction temperature of 60 ℃ and the reaction pressure of 3.0MPa, and performing HPLC (chromatographic conditions: Agilent Zorbax SB-C18(4.6mm multiplied by 150mm,5um), acetonitrile-water (90: 10) as a mobile phase, and the flow rate of 1.0mL min-1Detecting the complete reaction of the 2,2 '-dimethyl-4, 4' -dinitrodiphenylethane at the detection wavelength of 265nm and the column temperature of 35 ℃), filtering and recovering Raney Ni catalyst, recovering ethanol solvent from filtrate to prepare 2.32kg of white crystal product, detecting the product purity to be 98.5 percent by an HPLC normalization method,13C NMR(100MHz,CDCl3)δ145.55，145.55，136.34，136.34, 127.22, 127.22, 124.82, 124.82, 115.93, 115.93, 112.11, 112.11, 36.43, 36.43, 19.13, 19.13; FAB-HRMS: m/e (240.3424), formula: c16H20N2Namely 2,2 '-dimethyl-4, 4' -diaminodiphenylethane.
Diaminodiphenylethane such as diaminodiphenylethane, dimethyl-diaminodiphenylethane, diethyl-diaminodiphenylethane, di-n-propyl-diaminodiphenylethane, etc. can be prepared by selecting appropriate starting materials according to the above-described preparation process.
Diaminodiphenylethane preparation procedure 2:
weighing 3.00kg of dimethyl dinitrodiphenylethane (60.0 percent of 2,2 '-dimethyl-4, 4' -dinitrodiphenylethane and 40.0 percent of 2,2 '-dimethyl-6, 6' -dinitrodiphenylethane), 300.0g of Raney Ni catalyst, 6.0L of n-propanol, adding the n-propanol into a reaction kettle with a stirrer, introducing nitrogen to replace air, then introducing hydrogen, reacting for 4 hours at the stirring speed of 1000r/min, the reaction temperature of 50 ℃ and the reaction pressure of 3.0MPa, and performing HPLC (chromatographic conditions, namely an Agilent Zorbax SB-C18(4.6mm multiplied by 150mm,5um) column, acetonitrile-water (90: 10) as a mobile phase and the flow rate of 1.0 mL/min-1Detecting the total reaction of the dimethyl dinitrodiphenylethane at the detection wavelength of 265nm and the column temperature of 35 ℃), filtering and recovering Raney Ni catalyst, recovering n-propanol solvent from filtrate to prepare 2.22kg of white crystal product, comparing the product with the product in the process 2 by an HPLC method, and detecting the product to be the dimethyl diaminodiphenylethane (60.1 percent of the 2,2 '-dimethyl-4, 4' -diaminodiphenylethane and 39.9 percent of the 2,2 '-dimethyl-6, 6' -diaminodiphenylethane) by an HPLC normalization method.
According to the preparation process, the dimethyl diamino diphenyl ethane mixture can be respectively prepared by selecting a proper starting material dimethyl dinitrodiphenyl ethane mixture.
The solvent and the catalyst can be repeatedly used in the reaction process, and the whole process is safe and environment-friendly, low in cost, low in energy consumption and high in yield.
Example 1
Adding 20.0L dimethyl carbonate into a reaction kettle, adding 2.12kg of 4,4' -diaminodiphenylethane, stirring for dissolving, adding 0.7kg of anhydrous zinc acetate, reacting at room temperature for 0.5h, heating at about 90 ℃ for reflux reaction for 2-12h,
petroleum ether-ethyl acetate (1:1) as developing agent, 5% phosphomolybdic acid ethanol solution as color developing agent, TLC detecting 4,4' -diaminodiphenylethane to completely react, removing solvent to obtain 3.20kg of white powdery intermediate product, dissolving 3.20kg of intermediate product in 15.0L of toluene, heating and refluxing at about 110 ℃ for 0.5-2h,
petroleum ether-ethyl acetate (1:1) as a developing agent, 5% phosphomolybdic acid ethanol solution as a color developing agent, performing TLC detection on all the intermediate reactions, cooling to room temperature after the reaction is finished, filtering, and evaporating the solvent under reduced pressure to obtain 2.51kg of a white powdery product. The purity of the product is 97.6 percent by HPLC normalization method,13C NMR(100MHz,CDCl3) δ 139.33, 139.33, 130.81, 130.81, 130.29, 130.29, 130.29, 130.29, 127.72, 127.72, 125.11, 125.11, 125.11, 125.11, 37.40, 34.40; FAB-HRMS: m/e (264.2764), formula: c16H12O2N2Namely diphenylethane-4, 4' -diisocyanate (EDI-a 1).
Diphenylethane-5, 5 '-diisocyanate (EDI-a2) and diphenylethane-6, 6' -diisocyanate (EDI-a3) were prepared in a similar manner to example 1, using appropriate starting materials, 5 '-diaminodiphenylethane and 6,6' -diaminodiphenylethane, respectively.
Example 2
Adding 25.0L of dimethyl carbonate into a reaction kettle, adding 2.40kg of 2,2 '-dimethyl-4, 4' -diaminodiphenylethane, stirring for dissolving, adding 0.8kg of anhydrous zinc acetate, reacting at room temperature for 0.5h, heating to 100 ℃, refluxing and reacting for 2-12h, developing agents of petroleum ether-ethyl acetate (1:1), color developing agents of 5% phosphomolybdic acid ethanol solution, detecting by TLC (thin layer chromatography) to completely react with the 2,2 '-dimethyl-4, 4' -diaminodiphenylethane, and removing the solvent to obtain 3.45kg of a white powdery intermediate product. Dissolving 3.45kg of intermediate product in 25.0L of chlorobenzene, heating to 110 ℃ for reaction for 0.5-2h,
petroleum ether-ethyl acetate (1:1) as developing agent, 5% phosphomolybdic acid ethanol solution as developer, TLC detecting all the reactions of intermediate, and after the reaction is finishedCooling to room temperature, filtering, and distilling off the solvent under reduced pressure to obtain 2.65kg of white powdery product. The purity of the product is 96.6 percent by HPLC normalization method,13C NMR(100MHz,CDCl3) δ 136.75, 136.75, 134.42, 134.42, 130.71, 130.71, 130.14, 130.14, 127.72, 127.72, 126.51, 126.51, 122.03, 122.03, 35.40, 35.40, 19.11, 19.11; FAB-HRMS: m/e (292.3301), formula: c18H16O2N2Namely, 2 '-dimethyl-diphenylethane-4, 4' -diisocyanate (EDI-b 1).
Example 3
Adding 20.0L of dimethyl carbonate into a reaction kettle, adding 2.40kg of 2,2 '-dimethyl-5, 5' -diaminodiphenylethane, stirring for dissolving, adding 0.4kg of nano zinc oxide, reacting at room temperature for 0.5h, heating to 50 ℃ for 2-12h, completely reacting a developing agent, namely petroleum ether-ethyl acetate (1:1), a color developing agent, namely 5% phosphomolybdic acid ethanol solution, detecting by TLC (thin layer chromatography), and removing the solvent to obtain 3.42kg of a white powdery intermediate product. Dissolving 3.42kg of intermediate product in 20.0L of chlorobenzene, heating to 120 ℃ for reaction for 0.5-2h,
petroleum ether-ethyl acetate (1:1) as a developing agent, 5% phosphomolybdic acid ethanol solution as a color developing agent, performing TLC detection on all the intermediate reactions, cooling to room temperature after the reaction is finished, filtering, and evaporating the solvent under reduced pressure to obtain 2.55kg of a white powdery product. The purity of the product is 97.4 percent by HPLC normalization method,13C NMR(100MHz,CDCl3) δ 138.31, 138.31, 132.72, 132.72, 130.48, 130.48, 128.83, 128.83, 127.41, 127.41, 125.30, 125.30, 122.22, 122.22, 36.40, 36.40, 19.09, 19.09; FAB-HRMS: m/e (292.3299), formula: c18H16O2N2Namely, 2 '-dimethyl-diphenylethane-5, 5' -diisocyanate (EDI-b 2).
Example 4
Adding 15.0L of dimethyl carbonate into a reaction kettle, adding 2.40kg of 2,2 '-dimethyl-6, 6' -diaminodiphenylethane, stirring for dissolving, adding 0.3kg of nano zinc oxide, reacting at room temperature for 0.5h, heating at about 90 ℃ for reflux reaction for 2-12h, developing agents, namely petroleum ether-ethyl acetate (1:1), developing agents, namely 5% phosphomolybdic acid ethanol solution, detecting by TLC (thin layer chromatography), completely reacting the 2,2 '-dimethyl-6, 6' -diaminodiphenylethane, and removing the solvent to obtain 3.35kg of a white powdery intermediate product. Dissolving 3.35kg of intermediate product in 15.0L of chlorobenzene, heating and refluxing at about 132 ℃ for 0.5-2h,
petroleum ether-ethyl acetate (1:1) as developing agent, 5% phosphomolybdic acid ethanol solution as color developing agent, TLC detecting all reactions of intermediate, cooling to room temperature after reaction, filtering, distilling off solvent under reduced pressure to obtain white product, vacuum drying to obtain white powder product 2.35kg, HPLC normalization method detecting product purity of 97.2%,13C NMR(100MHz,CDCl3) δ 136.54, 136.54, 130.15, 130.15, 130.09, 130.09, 127.74, 127.74, 127.52, 127.52, 126.91, 126.91, 120.73, 120.73, 30.22, 30.22, 19.12, 19.12; FAB-HRMS: m/e (292.3300), formula: c18H16O2N2Namely, 2 '-dimethyl-diphenylethane-6, 6' -diisocyanate (EDI-b 3).
Example 5
Adding 25.0L of dimethyl carbonate into a reaction kettle, adding 2.40kg of 2,2 '-dimethyl-4, 6' -diaminodiphenylethane, stirring for dissolving, adding 0.2kg of nano zinc oxide, reacting at room temperature for 0.5h, heating at about 90 ℃ for reflux reaction for 2-12h, developing agents, namely petroleum ether-ethyl acetate (1:1), developing agents, namely 5% phosphomolybdic acid ethanol solution, detecting by TLC (thin layer chromatography), completely reacting the 2,2 '-dimethyl-4, 6' -diaminodiphenylethane, and removing the solvent to obtain 3.30kg of a white powdery intermediate product. Dissolving 3.30kg of intermediate product in 30.0L of chlorobenzene, heating and refluxing at about 132 ℃ for 0.5-2h,
petroleum ether-ethyl acetate (1:1) as developing agent, 5% phosphomolybdic acid ethanol solution as color developing agent, TLC detecting the intermediate to completely react, cooling to room temperature after the reaction is finished, filtering, distilling off solvent under reduced pressure to obtain white product, vacuum drying to obtain 2.40kg white powder product with purity of 96.5% as detected by HPLC normalization method,13C NMR(100MHz,CDCl3)δ136.66，136.63，134.24，130.77，130.18，130.16，130.24，127.86，127.86，127.51，126.94，126.52，122.03，120.75，36.44，30.33，19.23, 19.23; FAB-HRMS: m/e (292.3298), formula: c18H16O2N2Namely, 2 '-dimethyl-diphenylethane-4, 6' -diisocyanate (EDI-b 4).
2,2 '-dimethyl-diphenylethane-4, 5' -diisocyanate (EDI-b5) and 2,2 '-dimethyl-diphenylethane-5, 6' -diisocyanate (EDI-b6) were prepared in a similar manner to examples 2 through 5, using the appropriate starting materials 2,2 '-dimethyl-4, 5' -diaminodiphenylethane and 2,2 '-dimethyl-5, 6' -diaminodiphenylethane, respectively.
Example 6
Adding 12.0L of dimethyl carbonate into a reaction kettle, adding 2.40kg of dimethyl diaminodiphenylethane (60.0 percent of 2,2 '-dimethyl-4, 4' -diaminodiphenylethane and 40.0 percent of 2,2 '-dimethyl-6, 6' -diaminodiphenylethane), stirring and dissolving, adding 0.8kg of zinc phenylacetate, reacting at room temperature for 0.5h, heating to 150 ℃ and reacting for 2-12h, detecting all reactions of dimethyl diaminodiphenylethane by TLC (thin layer chromatography), and removing the solvent to obtain 3.10kg of a white powdery intermediate product. Dissolving 3.10kg of intermediate product in 15.0L of chlorobenzene, heating to 200 ℃ for reaction for 0.5-2h,
petroleum ether-ethyl acetate (1:1) as a developing agent, 5% phosphomolybdic acid ethanol solution as a color developing agent, performing TLC detection on all intermediates for reaction, cooling to room temperature after the reaction is finished, filtering, evaporating the solvent under reduced pressure, and drying in vacuum to obtain 2.25kg of a white powdery product, wherein the purity of the product is 96.5% by HPLC (high performance liquid chromatography) normalization method, and the product is dimethyldiphenylethane diisocyanate (60.0% of 2,2 '-dimethyl-diphenylethane-4, 4' -diisocyanate, 40.0% of 2,2 '-dimethyl-diphenylethane-6, 6' -diisocyanate) by comparison with EDI-b1 product and EDI-b3 product, and the EDI-b 1-60%).
A mixture of dimethyldiphenylethane diisocyanates can be prepared in a manner similar to that of example 6, using the appropriate starting materials, dimethyldiaminodiphenylethane mixtures.
Example 7
Adding 22.0L of dimethyl carbonate into a reaction kettle, adding 2.65kg of 2,2 '-diethyl-4, 4' -diaminodiphenylethane, stirring for dissolving, adding 0.2kg of nano zinc oxide, reacting at room temperature for 0.5h, heating to 120 ℃, refluxing and reacting for 2-12h, developing agents of petroleum ether-ethyl acetate (1:1), color developing agents of 5% phosphomolybdic acid ethanol solution, detecting by TLC (thin layer chromatography) that 2,2 '-diethyl-4, 4' -diaminodiphenylethane completely reacts, and removing the solvent to obtain 3.55kg of a white powdery intermediate product. Dissolving 3.55kg of intermediate product in 25.0L of chlorobenzene, heating to 160 ℃ for reaction for 0.5-2h,
petroleum ether-ethyl acetate (1:1) as developing agent, 5% phosphomolybdic acid ethanol solution as color developing agent, TLC detecting all reactions of intermediate, cooling to room temperature after reaction, filtering, distilling off solvent under reduced pressure to obtain white product, vacuum drying to obtain white powder product 2.84kg, HPLC normalization method detecting product purity of 96.5%,13C NMR(100MHz,CDCl3) δ 137.05, 137.05, 133.11, 133.11, 130.73, 130.73, 130.10, 130.10, 127.73, 127.70, 125.22, 125.22, 122.23, 122.23, 36.70, 36.70, 25.99, 25.99, 14.81, 14.81; FAB-HRMS: m/e (320.3822), formula: c20H20O2N2Namely, 2 '-diethyl-diphenylethane-4, 4' -diisocyanate (EDI-c 1).
The corresponding diethyldiphenylethane diisocyanate was prepared in a similar manner to example 7, using the appropriate starting material, diethyldiaminodiphenylethane.
Example 8
Adding 22.0L dimethyl carbonate into a reaction kettle, adding 2.88kg of 2,2 '-di-n-propyl-4, 4' -diaminodiphenylethane, stirring for dissolving, adding 0.6kg of nano zinc oxide, reacting at room temperature for 0.5h, heating to 60 ℃ for 2-12h,
the developing agent is petroleum ether-ethyl acetate (1:1), the color developing agent is 5% phosphomolybdic acid ethanol solution, the TLC detects that the 2,2 '-di-n-propyl-4, 4' -diaminodiphenylethane completely reacts, and 3.90kg of white powdery intermediate product is prepared after the solvent is removed. Dissolving 3.90kg of intermediate product in 30.0L of chlorobenzene, heating to 100 ℃ for reaction for 0.5-2h,
developing agent petroleum ether-ethyl acetate (1:1) for developing color5 percent phosphomolybdic acid ethanol solution, TLC detection of the intermediate for complete reaction, cooling to room temperature after the reaction is finished, filtering, evaporating the solvent under reduced pressure to obtain a white product, vacuum drying to obtain 3.10kg of a white powder product, detecting the product purity to be 96.5 percent by an HPLC normalization method,13C NMR(100MHz,CDCl3) δ 135.76, 135.76, 133.51, 133.51, 131.12, 131.12, 130.34, 130.34, 127.75, 127.75, 125.63, 125.63, 122.21, 122.21, 36.72, 36.72, 35.03, 35.03, 24.40, 24.40, 13.72, 13.72; FAB-HRMS: m/e (348.4369), formula: c22H24O2N2Namely, 2 '-di-n-propyl-diphenylethane-4, 4' -diisocyanate (EDI-d 1).
Corresponding di-n-propyldiphenylethane diisocyanate can be prepared in a similar manner to example 8, using the appropriate starting material di-n-propyldiaminodiphenylethane.
Example 9
Adding 25.0L of dimethyl carbonate into a reaction kettle, adding 2.40kg of 3,3 '-dimethyl-4, 4' -diaminodiphenylethane, stirring for dissolving, adding 0.8kg of zinc fumarate, reacting at room temperature for 1h, heating to 80 ℃ for reacting for 2-12h, completely reacting a developing agent petroleum ether-ethyl acetate (1:1), a color developing agent 5% phosphomolybdic acid ethanol solution, detecting by TLC (thin layer chromatography), and removing the solvent to obtain 3.30kg of a white powdery intermediate product. Dissolving 3.30kg of intermediate product in 25.0L of chlorobenzene, heating to 100 ℃ for reaction for 0.5-2h,
petroleum ether-ethyl acetate (1:1) as a developing agent, 5% phosphomolybdic acid ethanol solution as a color developing agent, performing TLC detection on all the intermediate reactions, cooling to room temperature after the reaction is finished, filtering, and evaporating the solvent under reduced pressure to obtain 2.55kg of a white powdery product. The purity of the product is 96.40 percent by HPLC normalization method,13C NMR(100MHz,CDCl3) δ 136.50, 136.50, 135.51, 135.51, 130.67, 130.67, 127.82, 127.82, 127.40, 127.40, 127.19, 127.19, 124.81, 124.81, 32.80, 32.80, 21.58, 21.58; FAB-HRMS: m/e (292.3293), formula: c18H16O2N2I.e. 3,3' -dimethyl-diphenylethane-66' -diisocyanate (EDI-e 1).
The corresponding diethyl diphenylethane diisocyanate, di-n-propyl diphenylethane diisocyanate can be prepared by a method similar to examples 7 and 8, using appropriate starting materials diethyl diaminodiphenylethane, di-n-propyl diaminodiphenylethane.
Examples 1 to 9, dimethyl carbonate was used as both solvent and reactant, and the recovered dimethyl carbonate was reused.
EDI polyurethane elastomer performance test:
the preparation of the sample comprises the steps of dehydrating polyester polyol (hydroxyl value 56, Shandong Dada company) in vacuum at 110 ℃ until the moisture is less than 0.05 percent, cooling to 80 ℃, respectively adding metered diisocyanate (EDI-a1, EDI-b1, EDI-b2, EDI-b3, EDI-b4, EDI-b5, EDI-b6, EDI-b1-60, EDI-c1, EDI-d1, TDI-80 import and MDI-50 Wanhua), uniformly stirring, vacuum degassing, pouring into a mold, curing and molding at 100-.
The performance test tests various performances according to the national standard: the test is carried out by testing hardness GB531-92, tensile strength GB528-98, elongation GB528-98 and tear strength GB 592-99. The results are summarized in Table 1.
TABLE 1
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. A process for preparing diphenyl ethane diisocyanate by dimethyl carbonate method includes such steps as introducing nitrogen gas to protect dinitro diphenyl ethane, adding catalyst, introducing hydrogen gas, reacting to obtain diamino diphenyl ethane,
dissolving diaminodiphenylethane in dimethyl carbonate, performing amidation reaction at 0-150 ℃ under the action of a catalyst, performing pyrolysis reaction at 80-200 ℃ to the end point after reacting for a certain time, and separating and purifying to obtain the diphenylethane diisocyanate compound.
2. The process of claim 1, wherein the amidation reaction is according to the formula:
wherein R is H or a hydrocarbyl group; the substituent R is positioned at the 2(2 ') position or the 3 (3') position; -NH2The substituent is positioned at the 4(4 ') position, the 5(5 ') position or the 6(6 ') position; -NHCOOCH3The substituent is located at the 4(4 ') position, or the 5(5 ') position, or the 6(6 ') position.
3. The process of claim 2, wherein the pyrolysis reaction is according to the formula:
wherein R is H or a hydrocarbyl group; the substituent R is positioned at the 2(2 ') position or the 3 (3') position; -NHCOOCH3The substituent is positioned at the 4(4 ') position, the 5(5 ') position or the 6(6 ') position; the-NCO substituent is located at the 4(4 ') position or the 5(5 ') position or the 6(6 ') position.
4. The process for the preparation of diphenylethane diisocyanate according to claim 2 or 3, wherein the substituent R is H or methyl or ethyl or n-propyl.
5. The process for preparing diphenylethane diisocyanate according to claim 1 or 4, wherein the amount of dimethyl carbonate is 1L to 100L of dimethyl carbonate per kg of diaminodiphenylethane.
6. The dimethyl carbonate method for preparing diphenylethane diisocyanate according to claim 5, wherein the ratio of diaminodiphenylethane to dimethyl carbonate is 1 kg: 2.0L-50.0L.
7. The preparation of diphenylethane diisocyanate by dimethyl carbonate method according to claim 1 or 6, wherein the catalyst for amidation reaction includes but is not limited to one or more of organic zinc, nano zinc oxide, and zinc organic complex.
8. The method for preparing diphenylethane diisocyanate according to claim 1 or 7, wherein the separation and purification method comprises one or more of filtration, resin treatment, water washing, distillation, crystallization, extraction, activated carbon treatment, molecular sieve treatment and chromatography.
9. A diphenylethane diisocyanate characterized by being obtained by the process for preparing diphenylethane diisocyanate according to the dimethyl carbonate process of any one of claims 1 to 8.
10. Use of a diphenylethane diisocyanate according to claim 9 in the preparation of chemically synthesized materials.
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