CN110981754A - Diphenylethane diisocyanate and preparation method thereof - Google Patents
Diphenylethane diisocyanate and preparation method thereof Download PDFInfo
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- CN110981754A CN110981754A CN201911314315.2A CN201911314315A CN110981754A CN 110981754 A CN110981754 A CN 110981754A CN 201911314315 A CN201911314315 A CN 201911314315A CN 110981754 A CN110981754 A CN 110981754A
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- Prior art keywords
- diaminodiphenylethane
- substituent
- dinitrodiphenylethane
- dimethyl
- polyurethane
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
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Images
Classifications
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polyurethanes Or Polyureas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses diphenylethane diisocyanate and a preparation method thereof, relating to the technical field of preparation of high polymer material monomers; diphenylethane diisocyanate has the structure shown below:
r is H or alkyl, and 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; the EDI is used as a polyurethane monomer in polyurethane materials, and comprises synthetic materials such as polyurethane foam, polyurethane adhesives, polyurethane synthetic leather, polyurethane fabric coatings, polyurethane resin coatings, polyurethane elastomers and the like.
Description
Technical Field
The invention discloses diphenylethane diisocyanate and a preparation method thereof, and relates to the technical field of preparation of high polymer material monomers.
Background
The polyurethane monomer 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, and 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. 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.
However, various polyurethane materials prepared from the existing MDI and other monomers still face the problem that the indexes such as tensile property, tearing strength and the like of the elastomer can not meet higher requirements in practical application, and the existing isocyanate preparation has fussy points and is not beneficial to industrial production.
Disclosure of Invention
The invention provides a Diphenylethane diisocyanate and a preparation method thereof aiming at the problems of the prior art, wherein Diphenylethane diisocyanate (EDI) has more excellent performance, better elongation, tensile strength and tearing strength, can realize the usability of wider polyurethane materials, and has wide application prospect.
The specific scheme provided by the invention is as follows:
a diphenylethane diisocyanate having the structure shown below:
wherein the substituent R is H or alkyl, and 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.
Preferred substituents R are H or methyl or ethyl or n-propyl.
A preparation method of an intermediate of diphenylethane diisocyanate comprises the following steps: reacting dinitrodiphenylethane with hydrogen under the protection of Raney Ni catalyst and nitrogen to prepare diaminodiphenylethane, wherein the structural formula is as follows:
wherein the substituent R is H or alkyl, and the substituent R is positioned at the 2(2 ') position or the 3 (3') position; substituent-NH2At the 4(4 ') bit, 5(5 ') bit or 6(6 ') bit. Preferred substituents R are H or methyl or ethyl or n-propyl.
The reaction formula for the preparation of the diphenylethane diisocyanate intermediate is 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; substituent-NO2At the 4(4 ') or 5(5 ') or 6(6 '); substituent-NH2At the 4(4 ') bit, 5(5 ') bit or 6(6 ') bit.
A preparation method of diphenylethane diisocyanate comprises the following steps: dissolving diaminodiphenylethane obtained in the preparation method of the intermediate of diphenylethane diisocyanate in a solvent, introducing nitrogen for protection, introducing phosgene at low temperature, reacting at-20-200 ℃ for 0.1-72h, and separating and purifying to obtain the EDI compound.
The reaction formula for preparing diphenylethane diisocyanate is 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; substituent-NH2At the 4(4 ') or 5(5 ') or 6(6 '); the substituent-NCO is located at the 4(4 ') position, or the 5(5 ') position, or the 6(6 ') position.
The starting reactant dinitrodiphenylethane in the preparation method includes, but is not limited to, 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. Preferably selected from 6,6' -diaminodiphenylethane, 5' -diaminodiphenylethane, 4' -diaminodiphenylethane, 2' -dimethyl-6, 6' -diaminodiphenylethane, 2' -dimethyl-5, 5' -diaminodiphenylethane, 2,2 '-dimethyl-4, 4' -diaminodiphenylethane, 3 '-dimethyl-5, 5' -diaminodiphenylethane, 3 '-dimethyl-4, 4' -diaminodiphenylethane, 3 '-diethyl-5, 5' -diaminodiphenylethane, 3 '-diethyl-4, 4' -diaminodiphenylethane.
The solvent in the preparation method is selected from inert solvents, preferably one or more of normal alkane, cyclohexane, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, trichlorobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-xylene, m-xylene, p-xylene, hemimellitene, mesitylene, ethylbenzene, propylbenzene and the like.
In the preparation method, the dosage of the solvent is that every kilogram of diaminodiphenylethane is dissolved in 1L-100L of solvent, preferably 2L-10L.
In the preparation method, the molar ratio of the diaminodiphenylethane to the phosgene is 1:1 (1.0-3.0), and preferably 1:1 (1.1-1.5).
The preferable reaction temperature in the preparation method is 25-120 ℃.
The separation and purification method in the preparation method is selected from 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 diphenylethane diisocyanate obtained by the preparation method.
The invention also provides 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 diphenylethane diisocyanate and a preparation method thereof, the diphenylethane diisocyanate compound prepared by the method has more excellent performance on indexes such as tensile strength, elongation, tearing strength and the like due to the chemical structure of the diphenylethane diisocyanate compound having the structural characteristic of diphenylethane, and can meet the higher requirements in the existing production application.
Drawings
FIG. 1 is a schematic diagram of the chemical structure of EDI in 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.
Preparation work: the chemistry can be applied according to the synthesis [ J ] of 4,4' -dinitrodiphenylethane (ene) such as lujunri, wanya, linvon yan, 2000, 17 (6): 651-653. the process mentioned therein produces dinitrodiphenylethane.
Reagents are procured or configured.
Dinitrodiphenylethane preparation Process 1: adding 13.71kg of p-nitrotoluene and 120L of tert-butyl alcohol into a reaction kettle, heating to 45 ℃ under stirring, adding the sodium alkoxide solution, adding 2.5kg of flaky metal sodium into 30L of tert-butyl alcohol, fully reacting and uniformly stirring to obtain the sodium alkoxide solution, reacting for 15min, 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 hot suction filtration, fully washing the filter cake with hot water above 90 ℃ to neutrality, performing suction filtration, drying at 80-90 ℃ to constant weight to obtain light yellow 4,4'12.27kg of dinitrodiphenylethane, the purity detected by an HPLC normalization method is 96.24 percent, the yield is 90.2 percent,13C NMR(100MHz,CDCl3) δ 148.35, 148.35, 145.12, 145.12, 129.43, 129.43, 129.43, 129.43, 123.82, 123.82, 123.82, 123.82, 37.41, 37.41; FAB-HRMS: m/e (272.2548), formula: c14H12N2O4。
Dinitrodiphenylethane preparation Process 2: adding 15.12kg of 4-nitro-o-xylene and 150L of tert-butyl alcohol into a reaction 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 ℃, obtaining light yellow 2,2 '-dimethyl-4, 4' -dinitrodiphenylethane 12.81k g, detecting the purity of 95.64% by an HPLC normalization method, and obtaining the 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。
Dinitrodiphenylethane preparation Process 3: adding 15.12k g 3-nitro-o-xylene and 150L of tert-butyl alcohol into a reaction 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 with hot water above 90 ℃ to neutrality, performing suction filtration, drying at 80-90 ℃ to constant weight to obtain 2-light yellow, 2' -dimethyl6,6' -dinitrodiphenylethane 12.28k g, purity 95.11% by HPLC normalization method, yield 81.7%,13C NMR(100MHz,CDCl3) δ 147.91, 147.91, 136.64, 136.64, 135.41, 135.41, 128.92, 128.92, 126.73, 126.73, 121.81, 121.81, 29.65, 29.65, 18.14, 18.14; FAB-HRMS: m/e (300.3075), formula: c16H16N2O4。
Dinitrodiphenylethane, dimethyl-dinitrodiphenylethane, diethyl-dinitrodiphenylethane, di-n-propyl-dinitrodiphenylethane, etc. can be produced by a method similar to the process 1 to the process 3, using an appropriate starting material.
Example 1
Weighing 2.72kg of 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 4 hours at the stirring speed of 1000r/min, the reaction temperature of 60 ℃ and the reaction pressure of 3.0MPa, and carrying out HPLC (high performance liquid chromatography) under the chromatographic conditions: the chromatographic column is Agilent ZorbaxSB-C18(4.6mm × 150mm,5um), the mobile phase is acetonitrile-water (90: 10), and the flow rate is 1.0 mL/min-1Detecting the total reaction of 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 obtain 1.90kg of white crystal product, detecting the product purity to be 98.9 percent by using an HPLC normalization method,13CNMR(100MHz,CDCl3) δ 145.63, 145.63, 132.22, 132.322, 128.54, 128.54, 128.54, 128.54, 115.23, 115.23, 115.23, 115.23, 37.45, 37.45; FAB-HRMS: m/e (212.2890), formula: c14H16N2Namely 4,4' -diaminodiphenylethane.
Example 2
Weighing 2.72kg of 6,6' -dinitrodiphenylethane, 300.0g of Raney Ni catalyst, 8.0L 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 4 hours at the stirring speed of 1000r/min, the reaction temperature of 80 ℃ and the reaction pressure of 2.0MPa, and carrying out HPLC (high performance liquid chromatography) under the chromatographic conditions: the chromatographic column is Agilent ZorbaxSB-C18(4.6mm × 150mm,5 u)m), the mobile phase is acetonitrile-water (90: 10), and the flow rate is 1.0 mL/min-1Detecting the total reaction of 6,6' -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 obtain 1.82kg of white crystal product, detecting the product purity to be 98.0 percent by using an HPLC normalization method,13CNMR(100MHz,CDCl3) δ 145.12, 145.12, 126.73, 126.73, 125.64, 125.64, 125.31, 125.31, 122.56, 122.56, 122.04, 122.04, 32.35, 32.35; FAB-HRMS: m/e (212.2892), formula: c14H16N2Namely 6,6' -diaminodiphenylethane.
Example 3
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, introducing hydrogen, reacting for 4 hours at the stirring rotation speed of 1000r/min, the reaction temperature of 60 ℃, the reaction pressure of 3.0MPa, and the chromatographic conditions of HPLC: the chromatographic column is Agilent Zorbax SB-C18(4.6mm × 150mm,5um), the mobile phase is acetonitrile-water (90: 10), and the flow rate is 1.0 mL/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 using an HPLC normalization method,13C NMR(100MHz,CDCl3) δ 145.55, 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.
Example 4
Weighing 3.00kg of 2,2 '-dimethyl-5, 5' -dinitrodiphenylethane, 300.0g of Raney Ni catalyst, 8.0L of absolute ethyl alcohol, adding the absolute ethyl alcohol into a reaction kettle with a stirrer, introducing nitrogen to replace air, introducing hydrogen, reacting for 5 hours at the stirring rotation speed of 1000r/min, the reaction temperature of 80 ℃ and the reaction pressure of 5.0MPa, and the chromatographic conditions of HPLC: the chromatographic column is AgilentZorbax SB-C18(4.6mm × 150mm,5um), acetonitrile-water (90: 10) as mobile phase, and flow rate of 1.0 mL/min-1Detecting the complete reaction of the 2,2 '-dimethyl-5, 5' -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 2.26kg of white crystal product, detecting the product purity to be 98.7 percent by using an HPLC normalization method,13C NMR(100MHz,CDCl3) δ 144.84, 144.84, 141.63, 141.63, 138.12, 138.12, 128.63, 128.63, 124.01, 124.01, 121.65, 121.65, 36.51, 36.51, 19.75, 19.75; FAB-HRMS: m/e (240.3425), formula: c16H20N2Namely 2,2 '-dimethyl-5, 5' -diaminodiphenylethane.
Example 5
Weighing 3.00kg of 2,2 '-dimethyl-6, 6' -dinitrodiphenylethane, 300.0g of Raney Ni catalyst, 8.0L of absolute ethyl alcohol, adding the absolute ethyl alcohol into a reaction kettle with a stirrer, introducing nitrogen to replace air, introducing hydrogen, reacting for 4 hours at the stirring rotation speed of 1000r/min, the reaction temperature of 80 ℃, the reaction pressure of 2.0MPa, and the chromatographic conditions of HPLC: the chromatographic column is AgilentZorbax SB-C18(4.6mm × 150mm,5um), the mobile phase is acetonitrile-water (90: 10), and the flow rate is 1.0 mL/min-1Detecting the complete reaction of the 2,2 '-dimethyl-6, 6' -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 2.30kg of white crystal product, detecting the product purity to be 98.6 percent by using an HPLC normalization method,13C NMR(100MHz,CDCl3) δ 143.65, 143.65, 136.33, 136.33, 126.64, 126.64, 125.42, 125.42, 120.31, 120.31, 113.22, 113.22, 30.13, 30.13, 19.12, 19.12; FAB-HRMS: m/e (240.3422), formula: c16H20N2Namely 2,2 '-dimethyl-6, 6' -diaminodiphenylethane.
Example 6
Weighing 3.00kg of 2,2 '-dimethyl-4, 6' -dinitrodiphenylethane, 300.0g of Raney Ni catalyst, 5.0L of n-propanol, adding into a reaction kettle with a stirrer, introducing nitrogen to replace air, then introducing hydrogen, and stirring at the rotation speed of 1000r/min, the reaction temperature of 60 ℃ and the reaction pressure of 10.0MPa for 4h, chromatographic conditions of HPLC: the chromatographic column is AgilentZorbax SB-C18(4.6mm × 150mm,5um), the mobile phase is acetonitrile-water (90: 10), and the flow rate is 1.0 mL/min-1Detecting the complete reaction of 2,2 '-dimethyl-4, 6' -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 2.25kg of white crystal product, detecting the product purity to be 99.2 percent by using an HPLC normalization method,13C NMR(100MHz,CDCl3) δ 145.55, 143.64, 137.24, 136.33, 126.62, 125.43, 124.82, 120.35, 115.91, 113.32, 113.21, 112.13, 36.10, 30.15, 19.12, 19.10; FAB-HRMS: m/e (240.3419), formula: c16H20N2Namely 2,2 '-dimethyl-4, 6' -diaminodiphenylethane.
2,2 '-dimethyl-4, 5' -diaminodiphenylethane and 2,2 '-dimethyl-5, 6' -diaminodiphenylethane can be prepared respectively by a method similar to that of example 3 to example 6, using appropriate starting materials, 2 '-dimethyl-4, 5' -dinitrodiphenylethane and 2,2 '-dimethyl-5, 6' -dinitrodiphenylethane.
Example 7
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 obtain 2.22kg of white crystal product, and comparing the white crystal product with the product of example 1 and the product of example 2 by an HPLC method to obtain the product of dimethyl diaminodiphenylethane, wherein the product is 60.1 percent of 2,2 '-dimethyl-4, 4' -diaminodiphenylethane and 39.9 percent of 2,2 '-dimethyl-6, 6' -diaminodiphenylethane.
A mixture of dimethyldiaminodiphenylethanes can be prepared in a manner analogous to that described in example 7, using a suitable starting material, a mixture of dimethyldinitrodiphenylethanes.
The solvent and the catalyst can be repeatedly used in the reaction processes of the embodiments 3 to 7, and the whole process is safe and environment-friendly, low in cost, low in energy consumption and high in yield.
Examples 1-7 highlight the preparation of the intermediate diaminodiphenylethane.
Example 8
Adding 4.0L of cyclohexane into a reaction kettle, adding 2.12kg of 4,4' -diaminodiphenylethane, stirring and dissolving, cooling to 0.0 ℃, introducing nitrogen to replace air, dissolving 1.5kg of phosgene at 0.0 ℃ in 3.0L of cyclohexane, adding the phosgene, keeping the temperature at 0.0-10.0 ℃ for reaction for 1h, heating to 50.0 ℃, continuing to add the rest 2/3 parts of phosgene, keeping the temperature at 50.0 ℃, stirring and reacting for 1h, heating to 80.0 ℃, and continuing to react under the vacuum degree of-10 kPa,
petroleum ether-ethyl acetate (1:1) as developing agent, 5% phosphomolybdic acid ethanol solution as developer, TLC detecting 4,4' -diaminodiphenylethane, removing solvent to obtain white powder product 2.30kg, HPLC normalization method detecting product purity 96.3%,13C NMR(100MHz,CDCl3) δ 139.35, 139.35, 130.83, 130.83, 130.31, 130.31, 130.31, 130.31, 127.74, 127.74, 125.13, 125.13, 125.13, 125.13, 37.42, 34.42; FAB-HRMS: m/e (264.2766), 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 8, using the appropriate starting materials, 5 '-diaminodiphenylethane and 6,6' -diaminodiphenylethane, respectively.
Example 9
Adding 4.0L of toluene into a reaction kettle, adding 2.4kg of 2,2 '-dimethyl-4, 4' -diaminodiphenylethane, stirring and dissolving, cooling to 0.0 ℃, introducing nitrogen to replace air, dissolving 1.5kg of phosgene at 0.0 ℃ into 3.0L of toluene, adding the phosgene, keeping the temperature at 0.0-10.0 ℃ for reaction for 1h, heating to 60.0 ℃, continuously adding the rest 2/3 parts of phosgene, keeping the temperature at 60.0 ℃ for stirring and reacting for 1h, heating to 110.0 ℃, and continuously reacting at the vacuum degree of-10 kPa,
a developing agent of petroleum ether-ethyl acetate (1:1), a color developing agent of 5 percent phosphomolybdic acid ethanol solution, TLC detection of the complete reaction of 2,2 '-dimethyl-4, 4' -diaminodiphenylethane, removal of the solvent to prepare 2.45kg of white powder products, HPLC normalization method detection of product purity of 95.5 percent,13C NMR(100MHz,CDCl3) δ 136.76, 136.76, 134.43, 134.43, 130.72, 130.72, 130.15, 130.15, 127.73, 127.73, 126.52, 126.52, 122.04, 122.04, 35.41, 35.41, 19.12, 19.12; FAB-HRMS: m/e (292.3301), formula: c18H16O2N2Namely, 2 '-dimethyl-diphenylethane-4, 4' -diisocyanate (EDI-b 1).
Example 10
Adding 8.0L of dimethylbenzene into a reaction kettle, adding 2.40kg of 2,2 '-dimethyl-5, 5' -diaminodiphenylethane, stirring and heating to 10.0 ℃, introducing nitrogen to replace air, dissolving 1.5kg of phosgene at 5.0 ℃ into 2.0L of dimethylbenzene, adding the phosgene, keeping the temperature and reacting for 1h at 5.0-10.0 ℃ after the phosgene is added, heating to 110.0 ℃, adding 2/3 parts of residual phosgene, keeping the temperature and stirring and reacting for 1h at 50.0 ℃, heating to 130.0 ℃, and continuously reacting under the vacuum degree of-10 kPa,
petroleum ether-ethyl acetate (1:1) as developing agent, 5% phosphomolybdic acid ethanol solution as developer, TLC detecting 2,2 '-dimethyl-5, 5' -diaminodiphenylethane, removing solvent to obtain white powder product 2.40kg, HPLC normalization method detecting product purity 96.0%,13C NMR(100MHz,CDCl3) δ 138.33, 138.33, 132.74, 132.74, 130.50, 130.50, 128.85, 128.85, 127.43, 127.43, 125.32, 125.32, 122.24, 122.24, 36.41, 36.41, 19.11, 19.11; FAB-HRMS: m/e (292.3299), formula: c18H16O2N2Namely, 2 '-dimethyl-diphenylethane-5, 5' -diisocyanate (EDI-b 2).
Example 11
Adding 2.0L of dimethylbenzene into a reaction kettle, adding 2.40kg of 2,2 '-dimethyl-6, 6' -diaminodiphenylethane, stirring and heating to 30.0 ℃, introducing nitrogen to replace air, dissolving 2.2kg of phosgene in 2.0L of dimethylbenzene at 20.0 ℃, adding the phosgene, carrying out heat preservation reaction for 1h at 20.0-30.0 ℃, heating to 80.0 ℃, adding 2/3 parts of the residual phosgene, carrying out heat preservation and stirring reaction for 1h at 60.0 ℃, heating to 140.0 ℃, and continuously reacting at the vacuum degree of-90 kPa,
a developing agent of petroleum ether-ethyl acetate (1:1), a color developing agent of 5 percent phosphomolybdic acid ethanol solution, TLC detection of the complete reaction of 2,2 '-dimethyl-6, 6' -diaminodiphenylethane, evaporation of most of solvent to about 1L, cooling to room temperature, standing for 4-6h, filtration, vacuum drying of solid to obtain 2.25kg of white powder product, HPLC normalization method detection of product purity of 96.2 percent,13CNMR(100MHz,CDCl3) δ 136.55, 136.55, 130.16, 130.16, 130.10, 130.10, 127.75, 127.75, 127.53, 127.53, 126.92, 126.92, 120.74, 120.74, 30.22, 30.22, 19.13, 19.13; FAB-HRMS: m/e (292.3302), formula: c18H16O2N2Namely, 2 '-dimethyl-diphenylethane-6, 6' -diisocyanate (EDI-b 3).
Example 12
Adding 5.0L of chlorobenzene into a reaction kettle, adding 2.40kg of 2,2 '-dimethyl-4, 6' -diaminodiphenylethane, stirring and heating to 30.0 ℃, introducing nitrogen to replace air, dissolving 2.2kg of phosgene in 2.0L of chlorobenzene at 20.0 ℃, adding the phosgene, carrying out heat preservation reaction for 1h at 20.0-30.0 ℃, adding 2/3 parts of the residual phosgene at 60.0 ℃, carrying out heat preservation and stirring reaction for 1h at 60.0 ℃, heating to 130.0 ℃, and continuously reacting at the vacuum degree of-10 kPa,
petroleum ether-ethyl acetate (1:1) as developing agent, 5% phosphomolybdic acid ethanol solution as developer, TLC detecting 2,2 '-dimethyl-4, 6' -diaminodiphenylethane, removing solvent to obtain white powder product 2.25kg, HPLC normalization method detecting product purity 95.4%,13C NMR(100MHz,CDCl3)δ136.65，136.62，134.23，130.76，130.17，130.15，130.23，127.85，127.85，127.50，126.93，126.51，122.02，120.74，36.43，30.32，19.22, 19.22; FAB-HRMS: m/e (292.3299), 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 9 through 12, using the appropriate starting materials 2,2 '-dimethyl-4, 5' -diaminodiphenylethane and 2,2 '-dimethyl-5, 6' -diaminodiphenylethane, respectively.
Example 13
Adding 5.0L of chlorobenzene and 2.40kg of dimethyl diaminodiphenylethane (60.1 percent of 2,2 '-dimethyl-4, 4' -diaminodiphenylethane and 39.9 percent of 2,2 '-dimethyl-6, 6' -diaminodiphenylethane) into a reaction kettle, stirring and dissolving at room temperature, introducing nitrogen to replace air, dissolving 2.0kg of phosgene at 20.0 ℃ in 2.0L of chlorobenzene, adding the phosgene, carrying out heat preservation reaction at 20-30 ℃ for 1h, heating to 50.0 ℃, adding 2/3 parts of the residual phosgene, carrying out heat preservation stirring reaction at 60.0 ℃ for 1h, heating to 180.0 ℃, and continuing the reaction at the vacuum degree of-10 kPa,
the developing agent is petroleum ether-ethyl acetate (1:1), the developer is 5% phosphomolybdic acid ethanol solution, all reactions of dimethyl diaminodiphenylethane are detected by TLC, 2.24kg of white powder products are prepared after the solvent is removed, the purity of the products is 95.5% by HPLC normalization method, and the products are dimethyl diphenylethane diisocyanate (2,2 '-dimethyl-diphenylethane-4, 4' -diisocyanate 60.1%, 2 '-dimethyl-diphenylethane-6, 6' -diisocyanate 39.9%) by HPLC method compared with EDI-b1 products and EDI-b3 products (EDI-b 1-60).
A mixture of dimethyldiphenylethane diisocyanates can be prepared in a manner similar to that of example 13, using the appropriate starting materials, dimethyldiaminodiphenylethane mixtures.
Example 14
Adding 4.0L of cyclohexane into a reaction kettle, adding 2.65kg of 2,2 '-ethyl-4, 4' -diaminodiphenylethane, stirring and dissolving, cooling to 0.0 ℃, introducing nitrogen to replace air, dissolving 1.5kg of phosgene at 0.0 ℃ into 3.0L of cyclohexane, adding the phosgene, keeping the temperature at 0.0-10.0 ℃ for reaction for 1h, heating to 50.0 ℃, continuously adding 2/3 parts of the residual phosgene, keeping the temperature at 50.0 ℃ for stirring and reacting for 1h, heating to 80.0 ℃, and continuously reacting under the vacuum degree of-10 kPa,
petroleum ether-ethyl acetate (1:1) as developing agent, 5% phosphomolybdic acid ethanol solution as developer, TLC detecting 2,2 '-diethyl-4, 4' -diaminodiphenylethane, removing solvent to obtain white powder product 2.72kg, HPLC normalization method detecting product purity 95.6%,13C NMR(100MHz,CDCl3) δ 137.06, 137.06, 133.12, 133.12, 130.74, 130.74, 130.11, 130.11, 127.74, 127.74, 125.23, 125.23, 122.24, 122.24, 36.71, 36.71, 26.00, 26.00, 14.82, 14.82; FAB-HRMS: m/e (320.3824), formula: c20H20O2N2Namely, 2 '-diethyl-diphenylethane-4, 4' -diisocyanate (EDI-c 1).
The corresponding diethyldiphenylethane diisocyanate can be prepared in a similar manner to example 14, using the appropriate starting material, diethyldiaminodiphenylethane.
Example 15
Adding 4.0L of cyclohexane into a reaction kettle, adding 2.88kg of 2,2 '-di-n-propyl-4, 4' -diaminodiphenylethane, stirring and dissolving, cooling to 0.0 ℃, introducing nitrogen to replace air, dissolving 1.5kg of phosgene at 0.0 ℃ into 3.0L of cyclohexane, adding the phosgene, keeping the temperature at 0.0-10.0 ℃ for reaction for 1h, heating to 50.0 ℃, continuously adding 2/3 parts of the rest phosgene, keeping the temperature at 50.0 ℃, stirring and reacting for 1h, heating to 80.0 ℃, and continuously reacting under the vacuum degree of-10 kPa,
a developing agent of petroleum ether-ethyl acetate (1:1), a color developing agent of 5 percent phosphomolybdic acid ethanol solution, 3.05kg of white powdery product is prepared after TLC detection of the complete reaction of 2,2 '-di-n-propyl-4, 4' -diaminodiphenylethane and solvent removal, the purity of the product is 94.8 percent by HPLC normalization method,13C NMR(100MHz,CDCl3)δ135.76，135.76，133.51，133.51，131.12，131.12，130.34，130.34，127.75，127.75，125.63，125.63，122.21，122.21，36.72，36.72，35.03，35.03，24.40，24.40，13.72，13.72；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 15, using the appropriate starting material di-n-propyldiaminodiphenylethane.
Example 16
Adding 8.0L of dimethylbenzene into a reaction kettle, adding 2.40kg of 3,3 '-dimethyl-6, 6' -diaminodiphenylethane, stirring and heating to 10.0 ℃, introducing nitrogen to replace air, dissolving 1.5kg of phosgene at 5.0 ℃ into 2.0L of dimethylbenzene, adding the phosgene, keeping the temperature and reacting for 1h at 10.0-20.0 ℃ after the phosgene is added, heating to 50.0 ℃, adding 2/3 parts of the residual phosgene, keeping the temperature and stirring and reacting for 1h at 60.0 ℃, heating to 140.0 ℃, and continuously reacting at the vacuum degree of-10 kPa,
a developing agent of petroleum ether-ethyl acetate (1:1), a color developing agent of 5 percent phosphomolybdic acid ethanol solution, TLC detection of the complete reaction of 3,3 '-dimethyl-6, 6' -diaminodiphenylethane, removal of the solvent to prepare 2.21kg of white powder products, HPLC normalization method detection of the product purity of 95.35 percent,13C NMR(100MHz,CDCl3) δ 136.53, 136.53, 135.54, 135.54, 130.70, 130.70, 127.85, 127.85, 127.43, 127.43, 127.22, 127.22, 124.84, 124.84, 32.83, 32.83, 21.61, 21.61; FAB-HRMS: m/e (292.3295), formula: c18H16O2N2Namely 3,3 '-dimethyl-diphenylethane-6, 6' -diisocyanate (EDI-e 1).
Diethyl diphenylethane diisocyanate and di-n-propyl diphenylethane diisocyanate can be prepared by a method similar to example 16 by using appropriate starting materials diethyl diaminodiphenylethane and di-n-propyl diaminodiphenylethane.
EDI polyurethane elastomer performance test:
the preparation of a sample comprises the steps of dehydrating polyester polyol (hydroxyl value 56, Shandong Dada company) at 110 ℃ in vacuum until the moisture is less than 0.05 percent, cooling to 80 ℃, adding metered diisocyanate respectively with the numbers of EDI-a1, EDI-b1, EDI-b2, EDI-b3, EDI-b4, EDI-b5, EDI-b6, EDI-b1-60, EDI-c1, EDI-d1 and TDI-80, stirring uniformly, pouring into a mold after vacuum degassing, curing and molding at 100 ℃ 110, completely vulcanizing, and standing at room temperature for 7 days to prepare a polyurethane elastomer sample.
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
Isocyanate index 1.03
As can be seen from the experimental results, the hardness of the EDI samples, including sample 1, sample 2, sample 3, sample 4, sample 5, sample 6, sample 7, sample 8, sample 9, sample 10, sample 11, sample 12 and sample 13, is equivalent to TDI-80 (sample 14) and MDI-50 (sample 15); EDI samples, including sample 1, sample 2, sample 3, sample 4, sample 5, sample 6, sample 7, sample 8, sample 9, sample 10, sample 11, sample 12, sample 13, have significantly higher elongation than TDI-80 (sample 14) and MDI-50 (sample 15); the tensile strength and tear strength of EDI samples, including sample 1, sample 2, sample 3, sample 4, sample 5, sample 6, sample 7, sample 8, sample 9, sample 10, sample 11, sample 12, and sample 13, were also improved over TDI-80 (sample 14) and MDI-50 (sample 15).
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 diphenylethane diisocyanate characterized by the structure:
wherein the substituent R is H or hydrocarbyl, and 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.
2. A diphenylethane diisocyanate according to claim 1 wherein the substituent R is H or methyl or ethyl or n-propyl.
3. A preparation method of an intermediate of diphenylethane diisocyanate is characterized in that dinitrodiphenylethane reacts with hydrogen under the protection of Raney Ni catalyst and nitrogen to prepare diaminodiphenylethane, and the structural formula is as follows:
wherein the substituent R is H or alkyl, and the substituent R is positioned at the 2(2 ') position or the 3 (3') position; substituent-NH2At the 4(4 ') bit, 5(5 ') bit or 6(6 ') bit.
4. The process according to claim 3, wherein the substituent R is H or methyl or ethyl or n-propyl.
5. A process for preparing diphenylethane diisocyanate, which comprises dissolving diaminodiphenylethane obtained by the process of claim 3 or 4 in solvent, introducing nitrogen for protection, introducing phosgene at low temperature, reacting at-20-200 deg.C for 0.1-72 hr, separating and purifying to obtain EDI compound.
6. The process according to claim 5, wherein the solvent is selected from inert solvents, preferably from one or more of n-alkanes, cyclohexane, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, trichlorobenzene, s-trichlorobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-xylene, m-xylene, p-xylene, hemimellitene, mesitylene, ethylbenzene, propylbenzene, etc.
7. The process according to claim 5 or 6, wherein the solvent is used in an amount of 1L to 100L, preferably 2L to 10L, of diaminodiphenylethane per kg of diaminodiphenylethane.
8. The process according to claim 7, wherein the molar ratio of diaminodiphenylethane to phosgene is 1: 1.0-3.0, preferably 1: 1.1-1.5.
9. A diphenylethane diisocyanate characterized by being obtained by the production method as described in claims 5 to 8.
10. Use of a diphenylethane diisocyanate according to claim 1, 2 or 9 in the preparation of chemically synthesized materials.
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