CN101225059A - Method for preparing 3,3'-diamino-4,4'-di(4-cyano-benzene oxygen) biphenyl - Google Patents
Method for preparing 3,3'-diamino-4,4'-di(4-cyano-benzene oxygen) biphenyl Download PDFInfo
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- CN101225059A CN101225059A CNA2008100329117A CN200810032911A CN101225059A CN 101225059 A CN101225059 A CN 101225059A CN A2008100329117 A CNA2008100329117 A CN A2008100329117A CN 200810032911 A CN200810032911 A CN 200810032911A CN 101225059 A CN101225059 A CN 101225059A
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Abstract
The invention relates to a preparation method for 3,3'-diamino-4,4'-bi (4-cyanophenoxy) biphenyl, which comprises the steps as follows: (1) making 3,3'-diamino-4,4'-4,4'-dihydroxybiphenyl and 4-halogenated benzonitrile in the molar ratio of 1:2.0 to 2.4 react together, in a nitrogen protection, for 10 to 30 hours, at 120 DEG C to 200 DEG C, in salt forming agents, azeotrope former, and aprotic polar solvent; (2) filtering while hot, removing filter residue, concentrating the mother liquor under a reduced pressure, cooling, crystallizing, filtering, and drying, to get 3,3'-diamino-4,4'-bi (4-cyanophenoxy) biphenyl. The preparation method of 3,3'-diamino-4,4'-bi (4-cyanophenoxy) biphenyl has the advantages of sample preparation technique, easy recovery of the reaction solvent, being recycled, less wastes, good working environment, higher product purity and yield, being suitable for industrialized production.
Description
Technical field
The invention belongs to the preparation method of the aromatic dicarboxylic primary amine that contains fragrant cyano group, be specifically related to a kind of 3,3 '-diamino-4,4 '-preparation method of two (4-cyano-benzene oxygen) biphenyl.
Background technology
The aromatic dicarboxylic primary amine that contains fragrant cyano group in the molecular structure is the important raw and processed materials that preparation fire resistant polyimide resin, liquid crystal aligning are arranged agent, carbon fiber enhancing advanced composite material matrix resin, high impact-resistant epoxy curing agent, polyurethane chain extender, super large-scale integration passivating coating and alpha-particle blocking layer coating material and printed electronics board substrate matrix resin or tackiness agent.
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.
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 in the molecular structure.Existing a lot of patents and document disclose the preparation method of various aromatic dicarboxylic primary amine both at home and abroad.Disclose as Chinese patent CN03132010.4 a kind of 2, the preparation method of two [4-(4-amino-benzene oxygen) phenyl] propane of 2-; That Japanese Patent JP63-126848 discloses is a kind of 4,4 '-two (3-amino-benzene oxygens)-3,3 ', 5,5 '-preparation method of tetramethyl biphenyl; U.S. Pat 4377525, disclose a kind of 1, the preparation method of two (3-amino-benzene oxygen) benzene of 3-; It is a kind of 2 that Yu Xinhai [New Chemical Materials, 2003,31 (10): 24-27] discloses, two [4-(4-amino-benzene oxygen) phenyl]-1,1,1,3,3 of 2-, the preparation method of 3-HFC-236fa; It is a kind of 1 that people such as Yu Xinhai [insulating material, 2006,39 (3): 1-4,8] disclose, the preparation method of two (4-amino-benzene oxygen) benzene of 3-.
But 3,3 '-diamino-4,4 '-preparation method of two (4-cyano-benzene oxygen) biphenyl, not seeing as yet so far has disclosed document or patent report.
Summary of the invention
That technical problem solved by the invention provides is a kind of 3,3 '-diamino-4,4 '-preparation method of two (4-cyano-benzene oxygen) biphenyl, preparation technology is simple for this method, and Working environment is good, and product purity, yield height are fit to suitability for industrialized production.
Provided by the invention 3,3 '-diamino-4,4 '-preparation method's of two (4-cyano-benzene oxygen) biphenyl chemical equation is as follows:
Wherein, X is fluorine, chlorine, bromine etc.
Of the present invention 3,3 '-diamino-4,4 '-preparation method of two (4-cyano-benzene oxygen) biphenyl, specifically comprise the following steps:
(1) mol ratio be 1: 2.0～2.4 3,3 '-diamino-4,4 '-dihydroxybiphenyl and 4-halogeno-benzene formonitrile HCN, under nitrogen protection, in salt forming agent, entrainer, aprotic polar solvent, reacted 10～30 hours down in 120 ℃～200 ℃, wherein, salt forming agent and 3,3 '-diamino-4,4 '-mol ratio of dihydroxybiphenyl is 1.2～3.2: 1, and the volume ratio of entrainer and aprotic polar solvent is 1: 0.6～3.0, and the proportioning of 4-halogeno-benzene formonitrile HCN and entrainer is 1 mole: 350 milliliters～700 milliliters;
(2) filtered while hot is removed filter residue, the mother liquor concentrating under reduced pressure, cooling, crystallization is filtered, oven dry, obtain 3,3 of higher degree '-diamino-4,4 '-two (4-cyano-benzene oxygen) biphenyl.
Described 4-halogeno-benzene formonitrile HCN is selected from one or more in 4-fluorobenzonitrile, 4-chlorobenzonitrile, the 4-bromobenzylcyanide.
Salt forming agent in the described step (1) is selected from one or more in salt of wormwood, yellow soda ash, saleratus, sodium bicarbonate, sodium hydroxide, the potassium hydroxide, preferred salt of wormwood, potassium hydroxide or sodium bicarbonate, most preferably salt of wormwood.
Entrainer in the described step (1) is selected from one or more in benzene,toluene,xylene, mono chloro benzene, the orthodichlorobenzene, preferred toluene or orthodichlorobenzene, most preferably toluene.
Aprotic polar solvent in the described step (1) is selected from N, one or more in dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, the dimethyl sulfoxide (DMSO), preferred N, dinethylformamide or N-Methyl pyrrolidone, N most preferably, dinethylformamide.
Beneficial effect of the present invention:
(1) the present invention is a kind of commercial run, and its preparation process operation steps is simple, can finish in same reactor
(2) reaction solvent reclaims easily, reusable edible, and the three wastes are few, and Working environment is good;
(2) can make with crystallization process highly purified 3,3 '-diamino-4,4 '-two (4-cyano-benzene oxygen) biphenyl (purity reaches more than 99%), and yield is higher.
Description of drawings
Figure is 3,3 '-diamino-4,4 '-molecular structure of two (4-cyano-benzene oxygen) biphenyl.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
With 21.6 gram (0.1 moles) 3,3 '-diamino-4,4 '-dihydroxybiphenyl, 33.0 gram (0.24 mole) 4-chlorobenzonitrile, 44.2 gram (0.32 mole) salt of wormwood, 252 milliliters of N, dinethylformamide (DMF) and 84 milliliters of toluene join the band thermometer, nitrogen tube, water-and-oil separator, in the round-bottomed flask of reflux condensing tube and mechanical stirrer, logical nitrogen stirred after 0.5 hour under the room temperature, heat temperature raising to 120 ℃ reaction is after 3 hours, improve temperature of reaction gradually, rise to 150 ℃ at last, last 1 hour, and, be cooled to 80 ℃ keeping reaction under 150 ℃ after 26 hours, filtered while hot, remove filter residue, the mother liquor concentrating under reduced pressure, cooling, crystallization, filter, oven dry obtains 3,3 '-diamino-4,4 '-two (4-cyano-benzene oxygen) biphenyl, according to 3,3 '-diamino-4,4 '-charging capacity and the product flow measurement of dihydroxybiphenyl, yield 96.3% (purity 99.2%).
Embodiment 2
With 21.6 gram (0.1 moles) 3,3 '-diamino-4,4 '-dihydroxybiphenyl, 0.12 moles of hydrogen potassium oxide, 100 milliliters of N-Methyl pyrrolidone (NMP) and 100 milliliters of dimethylbenzene join the band thermometer, nitrogen tube, water-and-oil separator, in the round-bottomed flask of reflux condensing tube and mechanical stirrer, logical nitrogen stirred after 0.5 hour under the room temperature, heat temperature raising refluxes, and goes out cooling reaction system to 90 ℃ until anhydrous assay, add 27.5 gram (0.20 mole) 4-chlorobenzonitriles, heated and stirred, 120 ℃ of reactions improve temperature of reaction after 3 hours gradually, rise to 150 ℃ at last, last 1 hour, and, be cooled to 80 ℃ keeping reaction under 150 ℃ after 18 hours, filtered while hot, remove filter residue, the mother liquor concentrating under reduced pressure, cooling, crystallization, filter, oven dry obtains 3,3 '-diamino-4,4 '-two (4-cyano-benzene oxygen) biphenyl, according to 3,3 '-diamino-4,4 '-charging capacity and the product flow measurement of dihydroxybiphenyl, yield 67.2%.
Embodiment 3
With 21.6 gram (0.1 moles) 3,3 '-diamino-4,4 '-dihydroxybiphenyl, 0.22 mole 4-chlorobenzonitrile, 0.2 mole salt of wormwood, 120 milliliters of N, dinethylformamide (DMF) and 200 milliliters of toluene join the band thermometer, nitrogen tube, water-and-oil separator, in the round-bottomed flask of reflux condensing tube and mechanical stirrer, logical nitrogen stirred after 0.5 hour under the room temperature, and heat temperature raising to 120 ℃ reaction improves temperature of reaction after 3 hours gradually, rise to 150 ℃ at last, last 1 hour, and, be cooled to 80 ℃ keeping reaction under 150 ℃ after 26 hours, filtered while hot, remove filter residue, the mother liquor concentrating under reduced pressure, cooling, crystallization, filter, oven dry obtains 3,3 '-diamino-4,4 '-two (4-cyano-benzene oxygen) biphenyl, according to 3,3 '-diamino-4,4 '-charging capacity and the product flow measurement of dihydroxybiphenyl, yield 79.2%.
Embodiment 4
Use instead 26.9 gram (0.32 mole) sodium bicarbonates except that 44.2 gram (0.32 mole) salt of wormwood that add, other processing step, inventory and reaction parameter are all with embodiment 1.The result obtains 3,3 '-diamino-4,4 '-two (4-cyano-benzene oxygen) biphenyl, yield 81.1%.
Embodiment 5
Remove 200 milliliters of N that add, dinethylformamide (DMF) and 70 milliliters of toluene are used 100 milliliters of N-Methyl pyrrolidone (NMP) and 100 milliliters of orthodichlorobenzenes instead, maximum temperature is that other processing step, inventory and reaction parameter are all with embodiment 1 outside 200 ℃ (keeping 10 hours).The result obtains 3,3 '-diamino-4,4 '-two (4-cyano-benzene oxygen) biphenyl, yield 85.6%.
Embodiment 6
Use instead 0.24 mole the 4-fluorobenzonitrile except that 33.0 of adding restrains (0.24 mole) 4-chlorobenzonitriles, other processing step, inventory and reaction parameter are all with embodiment 1.The result obtains 3,3 '-diamino-4,4 '-two (4-cyano-benzene oxygen) biphenyl, yield 82.3%.
Embodiment 7
Use instead 0.20 mole the 4-fluorobenzonitrile except that 33.0 of adding restrains (0.24 mole) 4-chlorobenzonitriles, other processing step, inventory and reaction parameter are all with embodiment 1.The result obtains 3,3 '-diamino-4,4 '-two (4-cyano-benzene oxygen) biphenyl, yield 77.3%.
Embodiment 8
Use instead 0.24 mole the 4-bromobenzylcyanide except that 33.0 of adding restrains (0.24 mole) 4-chlorobenzonitriles, other processing step, inventory and reaction parameter are all with embodiment 1.The result obtains 3,3 '-diamino-4,4 '-two (4-cyano-benzene oxygen) biphenyl, yield 72.7%.
Claims (11)
1. one kind 3,3 '-diamino-4,4 '-preparation method of two (4-cyano-benzene oxygen) biphenyl, comprise the following steps:
(1) mol ratio be 1: 2.0～2.4 3,3 '-diamino-4,4 '-dihydroxybiphenyl and 4-halogeno-benzene formonitrile HCN, under nitrogen protection, in salt forming agent, entrainer, aprotic polar solvent, 120 ℃～200 ℃ down reactions 10～30 hours;
(2) filtered while hot is removed filter residue, the mother liquor concentrating under reduced pressure, cooling, crystallization is filtered, oven dry, 3,3 '-diamino-4,4 '-two (4-cyano-benzene oxygen) biphenyl.
2. according to claim 13,3 '-diamino-4,4 '-preparation method of two (4-cyano-benzene oxygen) biphenyl, it is characterized in that: described 4-halogeno-benzene formonitrile HCN is selected from one or more in 4-fluorobenzonitrile, 4-chlorobenzonitrile, the 4-bromobenzylcyanide.
3. according to claim 13,3 '-diamino-4,4 '-preparation method of two (4-cyano-benzene oxygen) biphenyl, it is characterized in that: the salt forming agent in the described step (1) is selected from one or more in salt of wormwood, yellow soda ash, saleratus, sodium bicarbonate, sodium hydroxide, the potassium hydroxide, salt forming agent and 3,3 '-diamino-4,4 '-mol ratio of dihydroxybiphenyl is 1.2～3.2: 1.
4. according to claim 33,3 '-diamino-4,4 '-preparation method of two (4-cyano-benzene oxygen) biphenyl, it is characterized in that: the salt forming agent in the described step (1) is salt of wormwood, potassium hydroxide or sodium bicarbonate.
5. according to claim 43,3 '-diamino-4,4 '-preparation method of two (4-cyano-benzene oxygen) biphenyl, it is characterized in that: the salt forming agent in the described step (1) is a salt of wormwood.
6. according to claim 13,3 '-diamino-4,4 '-preparation method of two (4-cyano-benzene oxygen) biphenyl, it is characterized in that: the entrainer in the described step (1) is selected from one or more in benzene,toluene,xylene, mono chloro benzene, the orthodichlorobenzene, and the proportioning of entrainer and 4-halogeno-benzene formonitrile HCN is 350 milliliters～700 milliliters: 1 mole.
7. according to claim 63,3 '-diamino-4,4 '-preparation method of two (4-cyano-benzene oxygen) biphenyl, it is characterized in that: the entrainer in the described step (1) is toluene or orthodichlorobenzene.
8. according to claim 73,3 '-diamino-4,4 '-preparation method of two (4-cyano-benzene oxygen) biphenyl, it is characterized in that: the entrainer in the described step (1) is a toluene.
9. according to claim 13,3 '-diamino-4,4 '-preparation method of two (4-cyano-benzene oxygen) biphenyl, it is characterized in that: the aprotic polar solvent in the described step (1) is selected from N, dinethylformamide, N, in N-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, the dimethyl sulfoxide (DMSO) one or more, the volume ratio of aprotic polar solvent and entrainer are 0.6～3.0: 1.
10. according to claim 93,3 '-diamino-4,4 '-preparation method of two (4-cyano-benzene oxygen) biphenyl, it is characterized in that: the aprotic polar solvent in the described step (1) is N, dinethylformamide or N-Methyl pyrrolidone.
11. according to claim 10 3,3 '-diamino-4,4 '-preparation method of two (4-cyano-benzene oxygen) biphenyl, it is characterized in that: the aprotic polar solvent in the described step (1) is N, dinethylformamide.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110256290A (en) * | 2019-08-06 | 2019-09-20 | 宜春学院 | A kind of preparation method of -4 '-cyano-phenyl ether of 4- cyano benzyloxy |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110256290A (en) * | 2019-08-06 | 2019-09-20 | 宜春学院 | A kind of preparation method of -4 '-cyano-phenyl ether of 4- cyano benzyloxy |
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