CN101397258B - Process for preparation of 3,3-diamino-4,4-dihydroxybiphenyl - Google Patents
Process for preparation of 3,3-diamino-4,4-dihydroxybiphenyl Download PDFInfo
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- CN101397258B CN101397258B CN2008100413437A CN200810041343A CN101397258B CN 101397258 B CN101397258 B CN 101397258B CN 2008100413437 A CN2008100413437 A CN 2008100413437A CN 200810041343 A CN200810041343 A CN 200810041343A CN 101397258 B CN101397258 B CN 101397258B
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- dihydroxybiphenyl
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Abstract
The invention relates to a preparation method of 3, 3'-diamino-4, 4'-dihydroxy biphenyl, which comprises the steps: 3, 3'-dinitro-4, 4'-dihydroxy biphenyl is reacted for 1 to 5 hours in a system with palladium/carbon, hydrazine hydrate solution and an organic solvent within the temperature range of 70 DEG C to 150 DEG C, the filtration is carried out, mother liquor is cooled, products are precipitated, filtered and vacuum dried, thereby obtaining the 3, 3'-diamino-4, 4'-dihydroxy biphenyl. The preparation method has simple operation, no follow-up refining and purification processes, less timeconsumption, high product yield and high purity of more than 99 percent, thereby being applicable to industrial production.
Description
Technical field
The invention belongs to the preparation field of phenolic hydroxy group aromatic dicarboxylic primary amine, particularly relate to a kind of 3,3 '-diamino-4, the preparation method of 4 '-dihydroxybiphenyl.
Background technology
The heteroaromatic polymkeric substance has outstanding thermostability, anti-nuclear radiation, flame retardant resistance, organic solvent resistance and good high cryogenic mechanics performance and electric property, has obtained widespread use in space flight and aviation, electronics microelectronics, automobile boats and ships, electric contour performance field.
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, high strength heat-resisting, low-k and low-dielectric loss etc. as the needs height.Therefore, polyimide material enjoys favor in the FCCL field.
3,3 '-diamino-4,4 '-dihydroxybiphenyl are one of important source material of synthetic hydroxyl polyimide resin, and therefore, it not only can be applicable to the FCCL field, but also can be applicable to the photo-sensistive polyimide material.In addition, 3,3 '-diamino-4,4 '-dihydroxybiphenyl also are the important raw and processed materials of synthetic polybenzoxazole resin.
3,3 '-diamino-4,4 '-dihydroxybiphenyl are one of a kind of important aromatic dicarboxylic primary amine.The preparation method of aromatic dicarboxylic primary amine has many patents, bibliographical information:
Chinese patent CN1485315A, disclose a kind of 3,4 '-preparation method of diaminodiphenyl oxide;
Chinese patent CN1425644A, disclose a kind of 2, the preparation method of two [4-(4-amino-benzene oxygen) phenyl] propane of 2-;
Japanese Patent JP63-126848, disclose a kind of 4,4 '-two (3-amino-benzene oxygen)-3,3 ', 5,5 '-preparation method of tetramethyl biphenyl;
Japanese Patent JP62-248635, disclose a kind of 4,4 '-preparation method of two (3-amino-benzene oxygen) biphenyl;
U.S. Pat 4377525, disclose a kind of 1, the preparation method of two (3-amino-benzene oxygen) benzene of 3-;
U.S. Pat 4064107, disclose a kind of 4,4 '-preparation method of two (4-amino-benzene oxygen) phenyl ether;
Chinese patent CN1919829A discloses a kind of preparation method of alkyl substituent aromatic diamine;
Chinese patent CN101134730A, disclose a kind of 4,4 '-diamino-4 "-preparation method of hydroxy benzophenone alkane;
Chinese patent CN101157623A, disclose a kind of 1, the preparation method of two (4-amino-benzene oxygen) benzene of 4-;
Chinese patent CN101117324A, disclose a kind of 2, the preparation method of two (4-amino-benzene oxygen) cyanobenzenes of 6-;
Chinese patent CN101100446A, disclose a kind of 2, the preparation method of two [3-amino-4-(4-cyano-benzene oxygen) phenyl] propane of 2-;
Chinese patent CN101130502A, disclose a kind of 2, two [3-amino-4-(4-nitrophenoxy) phenyl]-1,1,1,3,3 of 2-, the preparation method of 3-HFC-236fa;
Chinese patent CN101186579A, disclose a kind of 4,4 '-two (4-amino-benzene oxygen)-3,3 ', 5,5 '-preparation method of tetramethyl biphenyl;
It is a kind of 1 that people such as Yu Xinhai [insulating material communication, 1999,32 (5): 1-4] disclose, the preparation method of two (3-amino-benzene oxygen) benzene of 3-, simultaneously, the also synthetic series of heat plastic polyimide that obtained.
That people such as Yu Xinhai [insulating material, 2001,34 (4): 13-16] disclose is a kind of 3,3 '-preparation method of diaminodiphenyl oxide;
It is a kind of 2 that people such as Yu Xinhai [insulating material, 2001,34 (6): 3-6] disclose, the preparation method of two [4-(3-amino-benzene oxygen) phenyl] propane of 2-;
It is a kind of 2 that people such as Yu Xinhai [insulating material, 2002,35 (4): 3-7] disclose, the preparation method of two [4-(4-amino-benzene oxygen) phenyl] propane of 2-;
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;
That people such as Yu Xinhai [insulating material, 2006,39 (5): 1-3,6] disclose is a kind of 4,4 '-preparation method of two (3-amino-benzene oxygen) benzophenone;
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-;
It is a kind of 2 that people such as Yu Xinhai [insulating material, 2007,40 (4): 1-5,8] disclose, two (the 3-amino-4-hydroxy phenyl)-1,1,1,3,3 of 2-, the preparation method of 3-HFC-236fa;
That people such as Yu Xinhai [insulating material, 2008,41 (2): 10-14] disclose is a kind of 4,4 '-preparation method of two (4-amino-benzene oxygen) biphenyl.
But 3,3 '-diamino-4, the simple and yield of the technology of 4 '-dihydroxybiphenyl, the preparation method that purity is high also do not have report.
Summary of the invention
The purpose of this invention is to provide a kind of 3,3 '-diamino-4, the preparation method of 4 '-dihydroxybiphenyl, this method technology is simple, need not follow-up refining purifying technique, consuming time few, the three wastes are few, the purity of product and yield height, are applicable to suitability for industrialized production.
Chemical equation of the present invention is as follows:
Of the present invention a kind of 3,3 '-diamino-4, the preparation method of 4 '-dihydroxybiphenyl comprises the following steps:
3,3 '-dinitrobenzene-4,4 '-dihydroxybiphenyl, in palladium/charcoal, hydrazine hydrate solution and organic solvent system in 70 ℃～150 ℃ temperature range internal reactions after 1～5 hour, filtered while hot, the cooling mother liquor is separated out the white crystal product, filters, dry, obtain 3 of white, 3 '-diamino-4,4 '-dihydroxybiphenyl crystal.
Described palladium/charcoal is that the palladium mass percent is palladium/charcoal of 1%～15%.
Described hydrazine hydrate solution is that mass percent concentration is 60%～85% hydrazine hydrate solution.
Described organic solvent is methyl alcohol, ethanol, Virahol, n-propyl alcohol, propyl carbinol, isopropylcarbinol, ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-dioxane, 2-methyl cellosolve, cellosolvo, 2-methyl cellosolve, 3-methoxypropanol, 2-oxyethyl group propyl alcohol, 3-oxyethyl group propyl alcohol, N-ethyl-2-pyrrolidone, N-N-methyl-2-2-pyrrolidone N-, dimethyl sulfoxide (DMSO), N, one or more mixtures in dinethylformamide, the N,N-dimethylacetamide.
Described 3,3 '-dinitrobenzene-4, the weight ratio of 4 '-dihydroxybiphenyl and palladium/charcoal is 100: 1～20.
Described 3,3 '-dinitrobenzene-4, the mol ratio of 4 '-dihydroxybiphenyl and hydrazine hydrate is 1: 10～30.
Described 3,3 '-dinitrobenzene-4, the weightmeasurement ratio of 4 '-dihydroxybiphenyl and organic solvent are 1 gram: 15 milliliters～100 milliliters.
Beneficial effect of the present invention:
(1) the present invention is preparation 3,3 '-diamino-4, the commercial run of 4 '-dihydroxybiphenyl;
(2) three wastes are few, and are environmentally friendly;
(3) consuming time few, obviously energy-saving and cost-reducing;
(4) industrial chemicals convenient sources simple to operate, related, kind is few;
(5) product yield and purity are all very high, and purity reaches more than 99%.
Description of drawings
Fig. 1 is 3,3 '-diamino-4, the molecular structure of 4 '-dihydroxybiphenyl;
Fig. 2 is 3,3 '-diamino-4, the differential scanning calorimeter of 4 '-dihydroxybiphenyl crystallized product (DSC) scanning spectra.
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.
With 27.6 gram (0.1 moles) 3,3 '-dinitrobenzene-4,4 '-dihydroxybiphenyl, 0.3 gram palladium mass percent are that 15% palladium/charcoal and 480ml ethylene glycol add in the reaction flask, stir, heat temperature raising to 60 ℃, begin to drip mass concentration and be 60% hydrazine hydrate solution, totally 160.0 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃-150 ℃ temperature range, continued stirring reaction 1 hour, cold slightly, filtered while hot, cooling mother liquor, separate out the white crystals product, filter, vacuum-drying obtains 3 of 19.5 gram whites, 3 '-diamino-4,4 '-dihydroxybiphenyl crystal, fusing point are 334.4 ℃ (seeing accompanying drawing 2), and purity is 99.8%, according to 3 of reality acquisition, 3 '-diamino-4, the amount of 4 '-dihydroxybiphenyl and theoretical amount (21.6 gram) calculate 3,3 '-diamino-4, the yield of 4 '-dihydroxybiphenyl are 90.2%.
With 27.6 gram (0.1 moles) 3,3 '-dinitrobenzene-4,4 '-dihydroxybiphenyl, 5.5 gram palladium mass percents are that 1% palladium/charcoal, 2500ml ethylene glycol and 260ml ethanol add in the reaction flask, stir, heat temperature raising to 60 ℃, begin to drip mass concentration and be 85% hydrazine hydrate solution, totally 95.0 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃-150 ℃ temperature range, continued stirring reaction 5 hours, cold slightly, filtered while hot, cooling mother liquor, separate out the white crystals product, filter, vacuum-drying obtains 3 of 18.3 gram whites, 3 '-diamino-4,4 '-dihydroxybiphenyl crystal, fusing point are 335.9 ℃, and purity is 99.9%, according to 3 of reality acquisition, 3 '-diamino-4, the amount of 4 '-dihydroxybiphenyl and theoretical amount (21.6 gram) calculate 3,3 '-diamino-4, the yield of 4 '-dihydroxybiphenyl are 84.5%.
Embodiment 3
With 27.6 gram (0.1 moles) 3,3 '-dinitrobenzene-4,4 '-dihydroxybiphenyl, 4.0 gram palladium mass percents are that 5% palladium/charcoal, 500ml ethylene glycol and 500ml 2-methyl cellosolve add in the reaction flask, stir, heat temperature raising to 60 ℃, begin to drip mass concentration and be 80% hydrazine hydrate solution, totally 90.6 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃-150 ℃ temperature range, continued stirring reaction 4 hours, cold slightly, filtered while hot, the cooling mother liquor is separated out the white crystals product, filter, vacuum-drying obtains 3 of 20.0 gram whites, 3 '-diamino-4,4 '-dihydroxybiphenyl crystal, purity is 99.7%, according to 3 of reality acquisition, 3 '-diamino-4, the amount of 4 '-dihydroxybiphenyl and theoretical amount (21.6 gram), calculate 3,3 '-diamino-4, the yield of 4 '-dihydroxybiphenyl are 92.5%.
With 27.6 gram (0.1 moles) 3,3 '-dinitrobenzene-4,4 '-dihydroxybiphenyl, 3.0 gram palladium mass percents are 10% palladium/charcoal, 200ml N, N-N,N-DIMETHYLACETAMIDE and 1000ml 1, the 2-propylene glycol adds in the reaction flask, stirs heat temperature raising to 60 ℃, begin to drip mass concentration and be 80% hydrazine hydrate solution, totally 185.0 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃-150 ℃ temperature range, continued stirring reaction 1 hour, cold slightly, filtered while hot, the cooling mother liquor is separated out the white crystals product, filter, vacuum-drying obtains 3 of 19.7 gram whites, 3 '-diamino-4,4 '-dihydroxybiphenyl crystal, purity is 99.8%, according to 3 of reality acquisition, 3 '-diamino-4, the amount of 4 '-dihydroxybiphenyl and theoretical amount (21.6 gram), calculate 3,3 '-diamino-4, the yield of 4 '-dihydroxybiphenyl are 91.0%.
Embodiment 5
With 27.6 gram (0.1 moles) 3,3 '-dinitrobenzene-4,4 '-dihydroxybiphenyl, 3.5 gram palladium mass percents are that 10% palladium/charcoal, 600ml dimethyl sulfoxide (DMSO), 20ml methyl alcohol and 1200ml cellosolvo add in the reaction flask, stir, heat temperature raising to 60 ℃, begin to drip mass concentration and be 85% hydrazine hydrate solution, totally 80.6 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃-150 ℃ temperature range, continued stirring reaction 2 hours, cold slightly, filtered while hot, the cooling mother liquor is separated out the white crystals product, filter, vacuum-drying obtains 3 of 17.8 gram whites, 3 '-diamino-4,4 '-dihydroxybiphenyl crystal, purity is 99.8%, according to 3 of reality acquisition, 3 '-diamino-4, the amount of 4 '-dihydroxybiphenyl and theoretical amount (21.6 gram), calculate 3,3 '-diamino-4, the yield of 4 '-dihydroxybiphenyl are 82.5%.
With 27.6 gram (0.1 moles) 3,3 '-dinitrobenzene-4,4 '-dihydroxybiphenyl, 1.6 gram palladium mass percents are 15% palladium/charcoal, 200ml ethanol, 1200ml cellosolvo and 800ml 1, ammediol adds in the reaction flask, stir, heat temperature raising to 60 ℃ begins to drip mass concentration and is 60% hydrazine hydrate solution, totally 90.0 grams (solution weight).After hydrazine hydrate is added dropwise to complete, in 70 ℃-150 ℃ temperature range, continued stirring reaction 5 hours, cold slightly, filtered while hot, the cooling mother liquor is separated out the white crystals product, filter, vacuum-drying obtains 3 of 14.1 gram whites, 3 '-diamino-4,4 '-dihydroxybiphenyl crystal, purity is 99.5%, according to 3 of reality acquisition, 3 '-diamino-4, the amount of 4 '-dihydroxybiphenyl and theoretical amount (21.6 gram), calculate 3,3 '-diamino-4, the yield of 4 '-dihydroxybiphenyl are 65.4%.
Claims (6)
1. one kind 3,3 '-diamino-4, the preparation method of 4 '-dihydroxybiphenyl comprises the following steps:
3,3 '-dinitrobenzene-4,4 '-dihydroxybiphenyl, in palladium/charcoal, hydrazine hydrate solution and organic solvent system in 70 ℃～150 ℃ temperature range internal reactions after 1～5 hour, filter, the cooling mother liquor is separated out product, filters, drying gets 3,3 '-diamino-4,4 '-dihydroxybiphenyl; Described organic solvent is methyl alcohol, ethanol, Virahol, n-propyl alcohol, propyl carbinol, isopropylcarbinol, ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-dioxane, 2-methyl cellosolve, cellosolvo, 2-methyl cellosolve, 3-methoxypropanol, 2-oxyethyl group propyl alcohol, 3-oxyethyl group propyl alcohol, N-ethyl-2-pyrrolidone, dimethyl sulfoxide (DMSO), N, one or more mixtures in dinethylformamide, the N,N-dimethylacetamide.
2. according to claim 13,3 '-diamino-4, the preparation method of 4 '-dihydroxybiphenyl is characterized in that: described palladium/charcoal is that the palladium mass percent is palladium/charcoal of 1%～15%.
3. according to claim 13,3 '-diamino-4, the preparation method of 4 '-dihydroxybiphenyl is characterized in that: described hydrazine hydrate solution is that mass percent concentration is 60%～85% hydrazine hydrate solution.
4. according to claim 1 and 23,3 '-diamino-4, the preparation method of 4 '-dihydroxybiphenyl is characterized in that: described 3,3 '-dinitrobenzene-4, the weight ratio of 4 '-dihydroxybiphenyl and palladium/charcoal is 100: 1～20.
5. according to claim 1 or 3 described 3,3 '-diamino-4, the preparation method of 4 '-dihydroxybiphenyl is characterized in that: described 3,3 '-dinitrobenzene-4, the mol ratio of 4 '-dihydroxybiphenyl and hydrazine hydrate is 1: 10～30.
6. according to claim 1 or 4 described 3,3 '-diamino-4, the preparation method of 4 '-dihydroxybiphenyl is characterized in that: described 3,3 '-dinitrobenzene-4, the weightmeasurement ratio of 4 '-dihydroxybiphenyl and organic solvent are 1 gram: 15 milliliters～100 milliliters.
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