CN101117324B - Method for preparing 2,6-di(4-amino-benzene oxygen) cyanobenzene - Google Patents
Method for preparing 2,6-di(4-amino-benzene oxygen) cyanobenzene Download PDFInfo
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- CN101117324B CN101117324B CN200710044319A CN200710044319A CN101117324B CN 101117324 B CN101117324 B CN 101117324B CN 200710044319 A CN200710044319 A CN 200710044319A CN 200710044319 A CN200710044319 A CN 200710044319A CN 101117324 B CN101117324 B CN 101117324B
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Abstract
The invention relates to a preparation process for 2, 6-bis(4-diaminophenoxy) benzonitrile. The invention comprises the following procedures: the p-aminophenol with mole ratios of 1.0:0.1 to 2.5 and the halogen agent are made a refluence reaction for 0.5 to 5 hours in organic solvent system under inertia atmosphere, and 2, 6-dihalogenated benzonitrile is added to react together for 3 to 12 hours at 170 to 200 DEG C, then the mixing solution are filtered and cleaned as well as dried in vacuum to obtain the brown 2, 6-bis(4-diaminophenoxy) benzonitrile solid product. The preparation process of the invention has simple process, low cost, environment-friendly feature, less energy consumption work hours, high yields and purity, and is suitable for industrialized production.
Description
Technical field
The invention belongs to the preparation field of organic compound, particularly relate to a kind of 2, the preparation method of two (4-amino-benzene oxygen) cyanobenzenes of 6-.
Background technology
2, two (4-amino-benzene oxygen) cyanobenzenes of 6-belong to the aromatic dicarboxylic primary amine class of ether-containing key in the molecular structure.As everyone knows, the aromatic dicarboxylic primary amine is one of important source material of synthesis of polyimides material, and the aromatic dicarboxylic primary amine of ether-containing key is the important source material of synthetic thermoplastic polyimide.
Aromatic polyimide has outstanding thermostability, anti-nuclear radiation, excellent mechanical property, electric property and organic solvent resistance, has obtained widespread use in space flight and aviation, electronics microelectronics, field such as electric.
Along with the information electronic product towards high performance, lightweight, slimming, the development that becomes more meticulous, the insulating material of flexible copper-clad plate (FCCL) is had higher requirement, low-dielectric loss heat-resisting, high strength etc. as the needs height.Therefore, polyimide material enjoys favor in the FCCL field, and particularly the thermoplastic polyimide material of using in two stratotype FCCL is of greatest concern.Therefore synthetic its raw material 2, the method for two (4-amino-benzene oxygen) cyanobenzenes of 6-becomes an important topic of this area contriver research.
Journal of Applied Polymer Science; 2002; 85:1317-1327 discloses a kind of 2; the preparation method of two (4-amino-benzene oxygen) cyanobenzenes of 6-is primarily characterized in that 2; the 6-dichlorobenzonitrile; the 4-amino-phenol; anhydrous sodium carbonate is in DMAC and toluene mixed solvent system; under the argon shield, 120 ℃ of back flow reaction were told toluene after 4 hours; rising temperature of reaction to 140 ℃ reaction 30 hours; be cooled to 50 ℃ subsequently, reactant poured into separated out product in the frozen water, cold aqueous sodium hydroxide solution (5%) washing; use acetone solution; add elutriation again and go out product, filter; drying, the mixed solvent of spent glycol monomethyl ether and water (volume ratio 2: 1) recrystallization; obtain amber 2; two (4-amino-benzene oxygen) the cyanobenzene solid products of 6-, 210 ℃～212 ℃ of fusing points, productive rate 70%.
Polymer International, 2005,54:544-552 discloses a kind of 2, the preparation method of two (4-amino-benzene oxygen) cyanobenzenes of 6-is primarily characterized in that the 4-amino-phenol, Anhydrous potassium carbonate, NMP and toluene, in nitrogen atmosphere, with 140 ℃～150 ℃ reactions, keep reaction after divide water to finish, tell toluene, cooling reaction system to 130 ℃ subsequently, add 2 in batches, the 6-dichlorobenzonitrile, in 195 ℃～200 ℃ the reaction 4 hours after, cooling reaction system, and pour in the big water gaging with the precipitating product, filter, vacuum-drying, and with toluene/ethanol mixed solvent (volume ratio 1: 1) recrystallization, obtain brown 2, two (4-amino-benzene oxygen) the cyanobenzene solid products of 6-, 212 ℃～213 ℃ of fusing points, productive rate 65%.
Above preparation method needs to improve from the control of environmental protection, production cost, and the productive rate of target product and fusing point are all lower, so can not satisfy the demand of suitability for industrialized production.
Summary of the invention
Technical problem to be solved by this invention provides 2, the preparation method of two (4-amino-benzene oxygen) cyanobenzenes of 6-.
Chemical equation of the present invention is as follows:
S: salt forming agent;
A: organic solvent;
X: fluorine (F), chlorine (Cl), bromine (Br).
Of the present invention 2, the preparation method of two (4-amino-benzene oxygen) cyanobenzenes of 6-comprises the steps:
4-amino-phenol and salt forming agent are under inert atmosphere conditions, back flow reaction is after 0.5～5 hour in organic solvent system, add 2,6-phenyl-dihalide formonitrile HCN, in 170 ℃～200 ℃ reactions 3～12 hours,, obtain 2 of brown through the filtration washing drying, two (4-amino-benzene oxygen) the cyanobenzene solid products of 6-, the mole proportioning of reactant is the 4-amino-phenol: salt forming agent=1.0: 0.1～2.5.
Described salt forming agent is selected from one or more mixtures in lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate, the saleratus.A kind of in the preferred yellow soda ash of the present invention, salt of wormwood, sodium hydroxide or the saleratus.
Described inert atmosphere is nitrogen atmosphere or argon gas atmosphere.
Described organic solvent is the mixture that anhydrous strong aprotic, polar is transmitted organic solvent or strong aprotic, polar transmission organic solvent and water-insoluble organic solvent.
Described anhydrous strong aprotic, polar is transmitted organic solvent and is selected from anhydrous N, dinethylformamide, anhydrous N,N-dimethylacetamide, anhydrous N-N-methyl-2-2-pyrrolidone N-, one or more mixtures in the anhydrous dimethyl sulphoxide.
Described anhydrous strong aprotic, polar is transmitted organic solvent and is selected from anhydrous N, dinethylformamide, anhydrous N,N-dimethylacetamide, anhydrous N-N-methyl-2-2-pyrrolidone N-, one or more mixtures in the anhydrous dimethyl sulphoxide.
Described strong aprotic, polar is transmitted the organic solvent agent and is selected from N, one or more mixtures in dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, the dimethyl sulfoxide (DMSO).
Described water-insoluble organic solvent is selected from one or more mixtures in benzene,toluene,xylene, monochloro-benzene, the dichlorobenzene.
The envelope-bulk to weight ratio that described anhydrous strong aprotic, polar is transmitted organic solvent and 4-amino-phenol is 40 milliliters～100 milliliters: 10 grams;
The envelope-bulk to weight ratio that described strong aprotic, polar is transmitted organic solvent and 4-amino-phenol is 10 milliliters～200 milliliters: 10 grams;
It is 1: 0.5～50 that described water-insoluble transmission organic solvent transmits the volume of organic solvent ratio with strong aprotic, polar;
Described 2,6-phenyl-dihalide formonitrile HCN restriction 2,6-dichlorobenzene formonitrile HCN, 2,6-dibromo-benzene formonitrile HCN, 2, the mixture of one or more in the 6-phenyl-difluoride formonitrile HCN.
Described 2, the mol ratio of 6-phenyl-dihalide formonitrile HCN and 4-amino-phenol is 1.0: 1.9～2.2.
Preparation method of the present invention has following beneficial effect:
(1) the present invention produces 2, the commercial run of two (4-amino-benzene oxygen) cyanobenzenes of 6-;
(2) preparation method's simple possible of the present invention, good work environment;
(3) product need not the operation of recrystallization purification, and this not only can reduce cost, and can reduce the generation of the three wastes simultaneously;
(4) production cost of products is cheap, helps it and further applies;
(5) yield and the purity of the product of the present invention's preparation are all higher.
Description of drawings
Fig. 1 is embodiment 1 a product DSC fusing point scanning curve.
Fig. 2 is embodiment 1 a product F TIR infrared spectrogram.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.These embodiment only are used to the present invention is described and are not used in and limit the scope of the invention.
4-amino-phenol (4AP) with 21.8 grams (0.2 mole), 27.6 gram (0.2 mole) salt of wormwood, 200 milliliters of N-N-methyl-2-2-pyrrolidone N-s (NMP) and 200 milliliters of dimethylbenzene add in the reaction flask, logical nitrogen, the reflux water-dividing reaction is after 2 hours, cooling reaction solution to 80 ℃, add 17.2 gram (0.1 moles) 2,6-dichlorobenzene formonitrile HCN (26DCBN), heat temperature raising back flow reaction, limit are told part to whole dimethylbenzene, to improve temperature of reaction, in 170 ℃～200 ℃ temperature range internal reactions 12 hours, cooling reaction solution to 80 ℃, filtered while hot is removed inorganic salt, leave and take mother liquor, be cooled to room temperature, drip water, the precipitating product, filter and (collect mother liquor, to reclaim organic solvent), washing leaching cake, vacuum-drying obtains 2 of 28.9 gram brown, two (4-amino-benzene oxygen) cyanobenzene (26B4APBN) solid products of 6-, according to theoretical yield (31.7 gram) and real income amount, calculating productive rate is 91.2%; Recording its fusing point by DSC is 214.1 ℃ (as shown in Figure 1), and test condition is: nitrogen atmosphere, 10 ℃/min of temperature rise rate; The FTIR infrared spectrogram presents tangible fragrant cyano group absorption peak (2214.30cm as shown in Figure 2
-1) and aryl primary amine absorption peak (3456.53cm
-1, 3411.58cm
-1, 3358.46cm
-1, 3329.85cm
-1).
Embodiment 2
4-amino-phenol (4AP) with 21.8 grams (0.2 mole), 2.76 gram (0.02 mole) salt of wormwood, 90 milliliters of anhydrous N-N-methyl-2-2-pyrrolidone N-s (NMP) add in the reaction flask, logical argon gas, after the back flow reaction 0.5 hour, cooling reaction solution to 80 ℃, add 26.1 gram (0.1 moles) 2,6-dibromo-benzene formonitrile HCN (26DBBN), heat temperature raising, in 170 ℃～200 ℃ temperature range internal reactions 3 hours, cooling reaction solution to 80 ℃, filtered while hot is removed inorganic salt, leave and take mother liquor, be cooled to room temperature, drip water, the precipitating product, filter and (collect mother liquor, to reclaim organic solvent), washing leaching cake, vacuum-drying obtains 2 of 12.1 gram brown, two (4-amino-benzene oxygen) cyanobenzene (26B4APBN) solid products of 6-, according to theoretical yield (31.7 gram) and real income amount, calculating productive rate is 38.2%.
Embodiment 3
4-amino-phenol (4AP) with 24.0 grams (0.22 mole), 26.5 gram (0.25 mole) yellow soda ash, 200 milliliters of anhydrous N-N-methyl-2-2-pyrrolidone N-s (NMP) and 40 milliliters of anhydrous N, N-N,N-DIMETHYLACETAMIDE (DMAc) adds in the reaction flask, logical nitrogen, after the back flow reaction 5 hours, cooling reaction solution to 80 ℃, add 13.9 gram (0.1 moles) 2,6-phenyl-difluoride formonitrile HCN (26DFBN), heat temperature raising, in 170 ℃～200 ℃ temperature range internal reactions 7 hours, cooling reaction solution to 80 ℃, filtered while hot, remove inorganic salt, leave and take mother liquor, be cooled to room temperature, drip water, the precipitating product filters (collecting mother liquor, to reclaim organic solvent), washing leaching cake, vacuum-drying, obtain 2 of 25.9 gram brown, two (4-amino-benzene oxygen) cyanobenzene (26B4APBN) solid products of 6-, according to theoretical yield (31.7 gram) and real income amount, calculating productive rate is 81.6%.
Embodiment 4
4-amino-phenol (4AP) with 20.7 grams (0.19 mole), 4.0 gram (0.1 mole) sodium hydroxide, 100 milliliters of toluene add in the reaction flask, logical nitrogen, the reflux water-dividing reaction is after 5 hours, cooling reaction solution to 80 ℃, add 100 milliliters of N-N-methyl-2-2-pyrrolidone N-s (NMP) and 17.2 gram (0.1 moles) 2,6-dichlorobenzene formonitrile HCN (26DCBN), heat temperature raising back flow reaction, limit are told part to whole toluene, to improve temperature of reaction, in 170 ℃～200 ℃ temperature range internal reactions 10 hours, cooling reaction solution to 80 ℃, filtered while hot is removed inorganic salt, leave and take mother liquor, be cooled to room temperature, drip water, the precipitating product, filter and (collect mother liquor, to reclaim organic solvent), washing leaching cake, vacuum-drying obtains 2 of 21.8 gram brown, two (4-amino-benzene oxygen) cyanobenzene (26B4APBN) solid products of 6-, according to theoretical yield (30.1 gram) and real income amount, calculating productive rate is 72.4%.
Embodiment 5
4-amino-phenol (4AP) with 24.0 grams (0.22 mole), 25.0 gram (0.25 mole) saleratus, 100 milliliters of N-N-methyl-2-2-pyrrolidone N-s (NMP) and 100 milliliters of orthodichlorobenzenes (ODCB) add in the reaction flask, logical nitrogen, the reflux water-dividing reaction is after 0.5 hour, cooling reaction solution to 80 ℃, add 17.2 gram (0.1 moles) 2,6-dichlorobenzene formonitrile HCN (26DCBN), heat temperature raising, in 170 ℃～200 ℃ temperature range internal reactions 5 hours, cooling reaction solution to 80 ℃, filtered while hot is removed inorganic salt, leave and take mother liquor, be cooled to room temperature, drip water, the precipitating product, filter and (collect mother liquor, to reclaim organic solvent), washing leaching cake, vacuum-drying obtains 2 of 28.1 gram brown, two (4-amino-benzene oxygen) cyanobenzene (26B4APBN) solid products of 6-, according to theoretical yield (31.7 gram) and real income amount, calculating productive rate is 88.6%.
Embodiment 6
4-amino-phenol (4AP) with 24.0 grams (0.22 mole), 27.6 gram (0.2 mole) salt of wormwood, 24 milliliters of N-N-methyl-2-2-pyrrolidone N-s (NMP) and 1200 milliliters of orthodichlorobenzenes (ODCB) add in the reaction flask, logical nitrogen, the reflux water-dividing reaction is after 0.5 hour, cooling reaction solution to 80 ℃, add 17.2 gram (0.1 moles) 2,6-dichlorobenzene formonitrile HCN (26DCBN), heat temperature raising, in 170 ℃～200 ℃ temperature range internal reactions 10 hours, cooling reaction solution to 80 ℃, filtered while hot is removed inorganic salt, leave and take mother liquor, be cooled to room temperature, drip water, the precipitating product, filter and (collect mother liquor, to reclaim organic solvent), washing leaching cake, vacuum-drying obtains 2 of 17.6 gram brown, two (4-amino-benzene oxygen) cyanobenzene (26B4APBN) solid products of 6-, according to theoretical yield (31.7 gram) and real income amount, calculating productive rate is 55.4%.
Claims (3)
1. one kind 2, the preparation method of two (4-amino-benzene oxygen) cyanobenzenes of 6-is characterized in that:
4-amino-phenol with 0.2 mole, 0.2 mole salt of wormwood, 200 milliliters of N-N-methyl-2-2-pyrrolidone N-s and 200 milliliters of dimethylbenzene add in the reaction flask, logical nitrogen, after the reflux water-dividing reaction 2 hours, cooling reaction solution to 80 ℃ adds 0.1 mole 2,6-dichlorobenzene formonitrile HCN, the heat temperature raising back flow reaction is told part to whole dimethylbenzene, to improve temperature of reaction, in 170 ℃～200 ℃ temperature range internal reactions 12 hours, cooling reaction solution to 80 ℃, filtered while hot is removed inorganic salt, leave and take mother liquor, be cooled to room temperature, drip water, the precipitating product, filter, collect mother liquor, to reclaim organic solvent, washing leaching cake, vacuum-drying, obtain 2 of 28.9 gram brown, two (4-amino-benzene oxygen) the cyanobenzene solid products of 6-.
2. one kind 2, the preparation method of two (4-amino-benzene oxygen) cyanobenzenes of 6-is characterized in that:
4-amino-phenol with 0.19 mole, 0.1 molar sodium hydroxide, 100 milliliters of toluene add in the reaction flask, logical nitrogen, after the reflux water-dividing reaction 5 hours, cooling reaction solution to 80 ℃ adds 100 milliliters of N-N-methyl-2-2-pyrrolidone N-s and 0.1 mole 2,6-dichlorobenzene formonitrile HCN, the heat temperature raising back flow reaction is told part to whole toluene, to improve temperature of reaction, in 170 ℃～200 ℃ temperature range internal reactions 10 hours, cooling reaction solution to 80 ℃, filtered while hot is removed inorganic salt, leave and take mother liquor, be cooled to room temperature, drip water, the precipitating product, filter, collect mother liquor, to reclaim organic solvent, washing leaching cake, vacuum-drying, obtain 2 of 21.8 gram brown, two (4-amino-benzene oxygen) the cyanobenzene solid products of 6-.
3. one kind 2, the preparation method of two (4-amino-benzene oxygen) cyanobenzenes of 6-is characterized in that:
4-amino-phenol with 0.22 mole, 0.25 mole saleratus, 100 milliliters of N-N-methyl-2-2-pyrrolidone N-s and 100 milliliters of orthodichlorobenzenes add in the reaction flask, logical nitrogen, and the reflux water-dividing reaction is after 0.5 hour, cooling reaction solution to 80 ℃, add 0.1 mole 2,6-dichlorobenzene formonitrile HCN, heat temperature raising, in 170 ℃～200 ℃ temperature range internal reactions 5 hours, cooling reaction solution to 80 ℃, filtered while hot is removed inorganic salt, leave and take mother liquor, be cooled to room temperature, drip water, the precipitating product, filter, collect mother liquor, to reclaim organic solvent, washing leaching cake, vacuum-drying, obtain 2 of 28.1 gram brown, two (4-amino-benzene oxygen) the cyanobenzene solid products of 6-.
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Non-Patent Citations (2)
| Title |
|---|
| Akanksha Saxena,et al.Synthesis and characterization ofpolyamidesandpoly(amide-imide)sderivedfrom2,6-bis(3-aminophenoxy)benzonitrileor2,6-bis(4-aminophenoxy)benzonitrile.Polymer International54.2004,54544-552. * |
| QIANG FANG,et al.Syntheses of an Aromatic Nitrile Ether DiamineandtheBismaleimide Bearing the Diamine and thePropertiesofTheir Copolymerswith4,4＇-Bismaleimidodiphenylmethane(BMDPM).Journal of Applied Polymer Science85.2002,851317-1327. * |
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