CN101602677A - Three (3-trifluoromethyl-4-amino-benzene) amine and preparation method thereof - Google Patents
Three (3-trifluoromethyl-4-amino-benzene) amine and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to organic compound and preparing technical field thereof, be specifically related to a kind of three (3-trifluoromethyl-4-amino-benzene) amine of preparing super-branched polyimide and preparation method thereof that can be used for.It is with 3-trifluoromethyl-4-N-methyl-p-nitroaniline and 2-trifluoromethyl-4-chloronitrobenzene (or 2-trifluoromethyl-4-fluoronitrobenzene, 2-trifluoromethyl-4-bromo nitrobenzene) reacts, generate three (3-trifluoromethyl-4 oil of mirbane) amine, then this trinitro-monomer reduction is obtained three (3-trifluoromethyl-4-amino-benzene) amine.Synthetic route of the present invention is simpler, as long as just can obtain three amine monomers through two-step reaction, has reduced cost.Introducing that it should be noted that fluorine atom can reduce the loss of light at 1.3 microns and 1.5 microns places, trifluoromethyl is at the ortho position of amido simultaneously, carry out helping after the polymerization dispersion of electric charge, help the stable of polymkeric substance, therefore will use to some extent in the field of superbranched light wave conductive material.
Description
Technical field
The invention belongs to organic compound and preparing technical field thereof, be specifically related to a kind of three (3-trifluoromethyl-4-amino-benzene) amine of preparing super-branched polyimide and preparation method thereof that can be used for.
Background technology
The globalization of Internet and multimedia communication is popularized at a high speed and has been quickened the optical communication networks development, and opticfiber communication or high speed optical fiber communication more and more are subject to people's attention, and has become the heat subject of people's research as the optical communication material of optical-fibre communications carrier.Because organic polymer material self has that specific inductivity is little, electric light is big with thermo-optical coeffecient, loss is little, be easy to processing and advantage such as can be vertical integrated, make organic polymer optical waveguide become the focus of Recent study, the application prospect with very attractive is arranged aspect optical communication widely.
In the optical communication wave band polymer optical wave guide material of current research, polyimide (PI) has shown some outstanding characteristics.Because its second-order transition temperature height, characteristics such as specific inductivity is low, and the coefficient of expansion is low are applied to aerospace, electron trade very early as resistant to elevated temperatures insulating material, lubricant etc.Because the aromaticity polyimide has outstanding heat, machinery, light and dielectric properties, it is widely used in electronics industry.The applied research of fluorinated polyimide (FPI) in the optical waveguides field began in recent years.Fluorine atom is incorporated in the skeleton of polymkeric substance, can strengthens thermostability, hydrophobicity, oil repellency and the chemical resistance of polymkeric substance, and reduce the internal cohesive energy of material, thereby be subjected to extensive attention.The FPI material not only has high thermostability, low rate of moisture absorption, and good characteristics such as solvability, and show extremely low absorption at infrared band (particularly two communication windows of 1310nm and 1550nm), shown potentiality in organic waveguide material application facet.Than linear polyimide, it is good that super-branched polyimide has solvability, and melt viscosity is low, the many and modifiable characteristics of capping group number, and isotropic character of dissaving structure can reduce the double refraction of material significantly simultaneously.
At the characteristics of above introduction, the present invention has synthesized a kind of novel fluorine-containing three amine monomers, contains trifluoromethyl, if make it be used to prepare super-branched polyimide, will make polymkeric substance have lower refractive index, lower double refraction, solvability preferably, and have a plurality of end groups of modifying.
Summary of the invention
The object of the invention provides a kind of three amine monomers of brand new---three (3-trifluoromethyl-4-amino-benzene) amine and provide the preparation this monomer methods, this monomeric structure is as follows:
The preparation of three (3-trifluoromethyl-4-amino-benzene) amine is with 3-trifluoromethyl-4-N-methyl-p-nitroaniline and 2-trifluoromethyl-4-chloronitrobenzene (or 2-trifluoromethyl-4-fluoronitrobenzene, 2-trifluoromethyl-4-bromo nitrobenzene) reacts, generate three (3-trifluoromethyl-4 oil of mirbane) amine, then this trinitro-monomer reduction is obtained three (3-trifluoromethyl-4-amino-benzene) amine, concrete preparation process is as follows:
The first step reaction, with 3-trifluoromethyl-4-N-methyl-p-nitroaniline, 2-trifluoromethyl-4-chloronitrobenzene (or 2-trifluoromethyl-4-fluoronitrobenzene, 2-trifluoromethyl-4-bromo nitrobenzene) and salt of wormwood put into mechanical stirring be housed, water-taker, in the there-necked flask of thermometer, with N, dinethylformamide (or N, the N-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO)) is solvent, 3-trifluoromethyl-4-N-methyl-p-nitroaniline, 2-trifluoromethyl-4-chloronitrobenzene and salt of wormwood three's mol ratio is 1: 2～3: 1～1.5, and the solid content of system is 20～50%, add toluene (solvent volume be 10～40%), logical nitrogen slowly is warmed up to 130～140 ℃, band water reaction 2～10 hours, emit toluene, reacted 2～20 hours under 140～155 ℃ of conditions then, be cooled to 20～120 ℃, discharging is in deionized water; Then product is washed repeatedly with deionized water, washed with ethanol again, suction filtration, vacuum drying gets yellow powder, i.e. three (3-trifluoromethyl-4-oil of mirbane) amine;
The reaction of second step, three (3-trifluoromethyl-4-oil of mirbane) amine and reduced iron powder put into churned mechanically there-necked flask is housed, solvent is the mixed solvent of acetone, ethanol, water, be heated to backflow under nitrogen protection, slow then dripping hydrochloric acid was reacted 2～6 hours again, dropping sodium solution then, react filtered while hot after 10～80 minutes after dropwising again, filtrate is fallen in deionized water, gets i.e. three (3-trifluoromethyl-4-amino-benzene) amine of pressed powder; Wash with deionized water repeatedly, suction filtration places vacuum drying oven with pressed powder again, dry three (3-trifluoromethyl-4-amino-benzene) amine powder; Wherein, the mol ratio of three (3-trifluoromethyl-4-oil of mirbane) amine, reduced iron powder, hydrochloric acid, sodium hydroxide is 1: 15～20: 3～5: 0.6～1.2; Acetone, water, alcoholic acid mol ratio are 1: 1～5: 1～8.
Further in the preferred implementation, the mol ratio of the 3-trifluoromethyl-4-N-methyl-p-nitroaniline of above-mentioned steps, 2-trifluoromethyl-4-chloronitrobenzene, salt of wormwood is 1: 2～2.5: 1～1.3, the toluene band water reaction times is 4～8 hours, reacts 4～16 hours under 149～154 ℃ of conditions after emitting toluene; The mol ratio of three (3-trifluoromethyl-4-oil of mirbane) amine, reduced iron powder, hydrochloric acid, sodium hydroxide is 1: 18～19: 3～4: 0.8～1.0, and acetone, water, alcoholic acid mol ratio are 1: 2～4: 2～5; Be heated to backflow under nitrogen protection, slow then dripping hydrochloric acid was reacted 2～4 hours again, and dropping sodium solution reacts filtered while hot after 10～50 minutes again after dropwising then;
Be the building-up reactions formula of three (3-trifluoromethyl-4-amino-benzene) amine monomers below:
In the building-up reactions: DMF is N, dinethylformamide.
Compare with background technology, three (3-trifluoromethyl-4-amino-benzene) of the present invention amine is to adopt the brand-new compound of diverse synthetic route synthetic.Synthetic route of the present invention is simpler, as long as just can obtain three amine monomers through two-step reaction, has reduced cost.Introducing that it should be noted that fluorine atom can reduce the loss of light at 1.3 microns and 1.5 microns places, trifluoromethyl is at the ortho position of amido simultaneously, carry out helping after the polymerization dispersion of electric charge, help the stable of polymkeric substance, therefore will use to some extent in the field of superbranched light wave conductive material.
Description of drawings
Fig. 1: the mass spectrum of three (3-trifluoromethyl-4-amino-benzene) amine of the embodiment of the invention 3;
Fig. 2: the nucleus magnetic hydrogen spectrum figure of three (3-trifluoromethyl-4-amino-benzene) amine of the embodiment of the invention 3;
Fig. 3: the infrared spectrum of three (3-trifluoromethyl-4-amino-benzene) amine of the embodiment of the invention 3.
The molecular weight of three (3-trifluoromethyl-4-aminobenzene) amine is 494 as seen from Figure 1, with soft with chemistry The molecular weight 494.36 that part ChemDraw calculates is in full accord. Prove that we had got this Triamine monomer;
Each hydrogen of three (3-trifluoromethyl-4-aminobenzene) amine has had good ownership as seen from Figure 2, Proved that further we have synthesized this Triamine monomer;
From the infrared spectrum of Fig. 3, can see that three (3-trifluoromethyl-4-aminobenzene) amine is at 3241cm-1、
3336cm
-1、3407cm
-1And 3470cm-1Produce a quadruple honeybee, this is the amino of multiamino compound The INFRARED ABSORPTION characteristics, proved further that again we have synthesized Triamine monomer.
Embodiment
Embodiment 1: the process of synthetic three (3-trifluoromethyl-4-oil of mirbane) amine
Is being furnished with thermometer, the nitrogen port, mechanical stirring, water-taker in the 500ml there-necked flask of spherical condensating tube, adds 47.36 gram (0.21mol) 2-trifluoromethyl-4-chloronitrobenzenes, 20.6 gram (0.1mol) 3-trifluoromethyl-4-N-methyl-p-nitroaniline, 17.94 gram (0.13mol) salt of wormwood, 240ml N, dinethylformamide (solid content is 22.5%), 60ml toluene, logical nitrogen slowly heats up, and 134 ℃ of toluene band water reacted 6 hours, emit toluene then, be warming up to again 150 ℃ the reaction 5 hours, be cooled to 110 ℃ after, discharging is in deionized water; Wash 5 times with deionized water repeatedly, wash 3 times with ethanol again, suction filtration, vacuum-drying gets yellow powder, i.e. three (3-trifluoromethyl-4-oil of mirbane) amine, 22.5 grams.
Embodiment 2:
Method is with embodiment 1, changes the amount of 2-trifluoromethyl-4-chloronitrobenzene into 76.2 grams (0.33mol), and the amount of 3-trifluoromethyl-4-N-methyl-p-nitroaniline changes 30.9 grams (0.15mol) into, and the consumption of salt of wormwood is 27 grams (0.20mol).These two kinds of monomers are packed into be furnished with thermometer, nitrogen port, mechanical stirring, water-taker in the 1000ml there-necked flask of spherical condensating tube, adds 400ml N again, dinethylformamide and 80ml toluene, logical nitrogen, band water heats up, the band water temp is 138 ℃, and the band water time is 8 hours, emits toluene then, heat up 152 ℃, reacted 12 hours again, and cooled to 60 ℃ then, discharging is in deionized water.Wash 5 times with deionized water repeatedly, wash 4 times with ethanol again, get yellow powder three (3-trifluoromethyl-4-oil of mirbane) amine after the same drying, 29 grams.
Embodiment 3: the process of synthetic three (3-trifluoromethyl-4-amino-benzene) amine
Be furnished with the nitrogen port, dropping funnel, mechanical stirring in the there-necked flask of spherical condensating tube, adds 7.6 gram (0.013mol) three (3-trifluoromethyl-4-oil of mirbane) amine, 13.1 gram (0.233mol) reduced iron powders, 40ml ethanol, 20ml deionized water, 10ml acetone.In dropping funnel, add 10ml water, 10ml ethanol, 0.69ml concentrated hydrochloric acid (0.039mol).Heating, the hydrochloric acid soln when beginning to reflux in the addition funnel dripped off in 2 hours, reacted 3.5 hours again.(0.3276 restrains dropping sodium solution then, 0.0082mol sodium hydroxide is dissolved in 10ml water and the 10ml alcoholic acid mixing solutions), dripped off in 15 minutes, reacted again 20 minutes, filtered while hot, filtrate is fallen in deionized water, with massive laundering 5 times, suction filtration places dry field gray powder three (3-trifluoromethyl-4-amino-benzene) amine that gets of vacuum drying oven, 4.7 grams.
Embodiment 4:
Method is with embodiment 3, changes the amount of three (3-trifluoromethyl-4-oil of mirbane) amine into 25.68 grams (0.044mol), and the amount of reduced iron powder changes 44.35 grams into.Add 100ml ethanol, 60ml deionized water, 60ml acetone in the there-necked flask, add 15ml water in the titration funnel, 15ml ethanol and 2.33ml (0.132mol) concentrated hydrochloric acid is heated to backflow, hydrochloric acid soln in the beginning addition funnel dripped off in 1.5 hours, reacted 2.5 hours again.Dropping sodium solution (1.11 gram be that 0.028mol sodium hydroxide is dissolved in 15ml water and the 15ml alcoholic acid mixing solutions) then, dripped off in 20 minutes, reacted again 30 minutes, filtered while hot, filtrate is fallen in deionized water, uses massive laundering 6 times, suction filtration, place the vacuum drying oven drying to obtain field gray powder three (3-trifluoromethyl-4-amino-benzene) amine equally, 15.6 grams.
Claims (7)
1, three (3-trifluoromethyl-4-amino-benzene) amine, its structural formula is as follows:
2, the preparation method of three (3-trifluoromethyl-4-amino-benzene) amine, its step is as follows:
The first step reaction, with 3-trifluoromethyl-4-N-methyl-p-nitroaniline, 2-trifluoromethyl-4-chloronitrobenzene, 2-trifluoromethyl-4-fluoronitrobenzene or 2-trifluoromethyl-4-bromo nitrobenzene, salt of wormwood is put into mechanical stirring is housed, water-taker, in the there-necked flask of thermometer, three's mol ratio is 1: 2～3: 1～1.5, with N, dinethylformamide, N, the N-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone or dimethyl sulfoxide (DMSO) are solvent, the solid content of system is 20～50%, adds the toluene of solvent volume 10～40%, logical nitrogen, slowly be warmed up to 130～140 ℃, toluene is emitted in band water reaction 2～10 hours, reacts 2～20 hours under 140～155 ℃ of conditions then, be cooled to 20～120 ℃, discharging is in deionized water; Then product is washed repeatedly with deionized water, washed with ethanol again, suction filtration, vacuum drying gets yellow powder, i.e. three (3-trifluoromethyl-4-oil of mirbane) amine;
The reaction of second step, three (3-trifluoromethyl-4-oil of mirbane) amine and reduced iron powder put into churned mechanically there-necked flask is housed, solvent is the mixed solvent of acetone, ethanol, water, is heated to backflow under nitrogen protection, slow then dripping hydrochloric acid, reacted again 2～6 hours, dropping sodium solution reacts filtered while hot after 10～80 minutes again after dropwising then, and filtrate is fallen in deionized water, get pressed powder, i.e. three (3-trifluoromethyl-4-amino-benzene) amine; Wash with deionized water repeatedly, suction filtration places vacuum drying oven with pressed powder again, dry three (3-trifluoromethyl-4-amino-benzene) amine powder; Wherein, the mol ratio of three (3-trifluoromethyl-4-oil of mirbane) amine, reduced iron powder, hydrochloric acid, sodium hydroxide is 1: 15～20: 3～5: 0.6～1.2; Acetone, water, alcoholic acid mol ratio are 1: 1～5: 1～8.
3, the preparation method of three (3-trifluoromethyl-4-amino-benzene) as claimed in claim 2 amine, it is characterized in that: 3-trifluoromethyl-4-N-methyl-p-nitroaniline, 2-trifluoromethyl-4-chloronitrobenzene, 2-trifluoromethyl-4-fluoronitrobenzene or 2-trifluoromethyl-4-bromo nitrobenzene, salt of wormwood three's mol ratio is 1: 2～2.5: 1～1.3.
4, the preparation method of three (3-trifluoromethyl-4-amino-benzene) as claimed in claim 2 amine, it is characterized in that: the toluene band water reaction times is 4～8 hours, reacts 4～16 hours under 149～154 ℃ of conditions after emitting toluene.
5, the preparation method of three (3-trifluoromethyl-4-amino-benzene) as claimed in claim 2 amine, it is characterized in that: the mol ratio of three (3-trifluoromethyl-4-oil of mirbane) amine, reduced iron powder, hydrochloric acid, sodium hydroxide is 1: 18～19: 3～4: 0.8～1.0.
6, the preparation method of three (3-trifluoromethyl-4-amino-benzene) as claimed in claim 2 amine, it is characterized in that: acetone, water, alcoholic acid mol ratio are 1: 2～4: 2～5.
7, the preparation method of three (3-trifluoromethyl-4-amino-benzene) as claimed in claim 2 amine; it is characterized in that: under nitrogen protection, be heated to backflow; slow then dripping hydrochloric acid; reacted again 2～4 hours; dropping sodium solution reacts filtered while hot after 10～50 minutes again after dropwising then.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102267940A (en) * | 2011-05-31 | 2011-12-07 | 湖北大学 | Synthesis of triamine containing symmetrical triaryl pyridine structure and hyperbranched polyimide thereof |
| CN105566127A (en) * | 2016-03-02 | 2016-05-11 | 吉林大学 | Triamine monomer and preparation method and application thereof |
| CN106674520A (en) * | 2017-02-09 | 2017-05-17 | 吉林大学 | Preparation and application for hyperbranched polyimide containing unequal activity triamine monomer |
| CN108976133A (en) * | 2018-07-31 | 2018-12-11 | 湖南工业大学 | A kind of Triamine monomer of the structure containing phenanthrene ring and its preparation method and application |
-
2009
- 2009-07-09 CN CNA2009100672578A patent/CN101602677A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102267940A (en) * | 2011-05-31 | 2011-12-07 | 湖北大学 | Synthesis of triamine containing symmetrical triaryl pyridine structure and hyperbranched polyimide thereof |
| CN105566127A (en) * | 2016-03-02 | 2016-05-11 | 吉林大学 | Triamine monomer and preparation method and application thereof |
| CN106674520A (en) * | 2017-02-09 | 2017-05-17 | 吉林大学 | Preparation and application for hyperbranched polyimide containing unequal activity triamine monomer |
| CN106674520B (en) * | 2017-02-09 | 2019-03-26 | 吉林大学 | The preparation and application of super-branched polyimide containing non-isoreactivity Triamine monomer |
| CN108976133A (en) * | 2018-07-31 | 2018-12-11 | 湖南工业大学 | A kind of Triamine monomer of the structure containing phenanthrene ring and its preparation method and application |
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Application publication date: 20091216 |