CN101186579A - Method for preparing 4,4'-di(4-aminophenoxy)-3,3',5,5'-tetramethylbiphenyl - Google Patents
Method for preparing 4,4'-di(4-aminophenoxy)-3,3',5,5'-tetramethylbiphenyl Download PDFInfo
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Abstract
The invention relates to a preparation method of 4, 4'-dia(4-aminophenoxy)-3, 3', 5, 5'-tetramethylbenzene, which comprises that heating, refluxing, dividing and reaction of 3, 3', 5, 5'-tetramethyl-4', 4'-biphenyl diphenol and 4-halogenated nitrobenzene, in salt forming agents, strongly polar protonic or water insoluble organic solvent system, concentrating, cooling, and adding water, precipitating product, filtering, washing and drying to obtain 4, 4'-dia(4-aminophenoxy)-3, 3', 5, 5'-tetramethylbenzene and the 4, 4'-dia(4-aminophenoxy)-3, 3', 5, 5'-tetramethylbenzene in the reduction system of ferric chloride/20-85% hydrazine hydrate to be reacted and reduced via the cooperation of alcohol solvent and active carbon to obtain final product. The invention has simple and environment-friend operation, which can be used for industrialization production, while the product can reach more than 99% of purity and the solvent can be reclaimed.
Description
Technical field
The invention belongs to the preparation field of aromatic dicarboxylic primary amine, particularly relate to a kind of 4,4 '-two (4-amino-benzene oxygen)-3,3 ', 5, the preparation method of 5 '-tetramethyl biphenyl.
Background technology
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 blue or green hiding 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.
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 oxygens)-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;
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 1 that people such as Yu Xinhai [insulating material, 2007,40 (3): 11-14] disclose, the preparation method of two (4-amino-benzene oxygen) benzene of 4-.
People [Journal of Polymer Research such as Sheng-Huei Hsiao, 1995,2 (1): 1-12] disclose a kind of 4,4 '-two (4-amino-benzene oxygens)-3,3 ', 5, the preparation method of 5 '-tetramethyl biphenyl, be primarily characterized in that, with reference to the preparation method of 4,4 '-two (4-amino-benzene oxygen) biphenyl: the first step: 4,4 '-'-biphenyl diphenol, the 4-chloronitrobenzene, the mixture of Anhydrous potassium carbonate and DMF is in 160 ℃ of back flow reaction after 10 hours, cooling, pour into subsequently in the mixed solution of first alcohol and water (volume is 1: 1) and separate out solid product, filter, use the DMF recrystallization, obtain 4,4 '-two (4-nitrophenoxy) biphenyl; Second step: 4,4 '-two (4-nitrophenoxy) biphenyl closes at the 10%Pd/C-alcohol-water and carries out reduction reaction in the hydrazine system, after reaction finishes, filter, remove Pd/C, 4 of white is separated out in cooling, 4 '-two (4-amino based phenoxy group) biphenyl solid product, filter, wash drying with water, obtain 4,4 '-two (4-amino-benzene oxygen) biphenyl.With 3,3 ', 5,5 '-tetramethyl--4,4 '-'-biphenyl diphenol replaces 4, and 4 '-'-biphenyl diphenol has made 4,4 '-two (4-nitrophenoxy)-3,3 ', 5,5 '-tetramethyl biphenyl (fusing point is 249-250 ℃, yield 74%) and 4,4 '-two (4-amino-benzene oxygens)-3,3 ', 5,5 '-tetramethyl biphenyl (fusing point is 227-228 ℃, yield 72%).
This preparation method's shortcoming is: (1) organic solvent in whole process of preparation reclaims difficulty, is unfavorable for environment protection; (2) in synthetic 4,4 '-two (4-nitrophenoxy)-3,3 ', 5, in the process of 5 '-tetramethyl biphenyl, reaction mixture is directly poured in the mixed solution of first alcohol and water and is separated out product, causes waste water serious, and the processing costs height is unfavorable for environment protection; (3) organic solvent reclaims difficulty; (4) synthetic 4,4 '-two (4-nitrophenoxy)-3 that obtain, 3 ', 5,5 '-tetramethyl biphenyl also need pass through the DMF recrystallization, and this has not only increased cost, but also has additionally produced the three wastes; (5) use 10%Pd/C in the reduction reaction, cause product cost to raise, be unfavorable for commercially producing; (6) 4,4 '-two (4-amino-benzene oxygen)-3,3 ', 5 of reduction reaction acquisition, 5 '-tetramethyl biphenyl also need wash with water, and this has not only increased cost, and has produced the three wastes again; (7) the first step and the yield in second step are on the low side, cause total recovery lower, have only 74%*72%=53.28%.
Japanese Patent JP H03-101644 discloses a kind of 4,4 '-two (4-amino-benzene oxygen)-3,3 ', 5, the preparation method of 5 '-tetramethyl biphenyl is primarily characterized in that, 3,3 ', 5,5 '-tetramethyl--4,4 '-'-biphenyl diphenol, parachloronitrobenzene, potassium hydroxide, dimethyl sulfoxide (DMSO) are mixed, and reaction is 1-10 hour under 50-150 ℃ of temperature, obtain 4,4 '-two (4-nitrophenoxy)-3,3 ', 5,5 '-tetramethyl biphenyl, yield 78%; With 4,4 '-two (4-nitrophenoxy)-3,3 ', 5,5 '-tetramethyl biphenyl and 5%Pd/C-H
2-ethanol system is in 20-200 ℃ (temperature), normal pressure-50kg/cm
2Under (pressure) condition, reduction obtains 4,4 '-two (4-amino-benzene oxygen)-3,3 ', 5,5 '-tetramethyl biphenyl, fusing point 203-205 ℃, yield 89%.
This preparation method's shortcoming is: (1) 4,4 '-two (4-nitrophenoxy)-3, and 3 ', 5, the yield of 5 '-tetramethyl biphenyl has only 78%, and is on the low side; (2) reduction reaction needs to carry out under high temperature, the condition of high voltage, to the requirement height of equipment, and has certain danger; (3) use noble metal catalyst, product cost is raise, be unfavorable for commercially producing; (4) reduction reaction is used hydrogen, exists certain security risk; (5) 4,4 '-two (4-amino-benzene oxygen)-3,3 ', 5, the fusing point of 5 '-tetramethyl biphenyl product (203-205 ℃) is on the low side, illustrates that purity is on the low side.
Summary of the invention
The purpose of this invention is to provide a kind of 4,4 '-two (4-amino-benzene oxygen)-3,3 ', 5, the preparation method of 5 '-tetramethyl biphenyl, this method technology is simple, cost is low, environmental friendliness, purity and yield height.
Chemical equation of the present invention is as follows:
Wherein, X is a halogen atom, i.e. fluorine (F), chlorine (Cl), bromine (Br), iodine (I).
4,4 '-two (4-amino-benzene oxygen)-3,3 ', 5 of the present invention, the preparation method of 5 '-tetramethyl biphenyl comprises the steps:
(1) mol ratio be 1.00: 2.00～2.20 3,3 ', 5,5 '-tetramethyl--4,4 '-'-biphenyl diphenol and 4-halogenated nitrobenzene, in salt forming agent, strong aprotic, polar or water-insoluble organic solvent system, reflux divides the water reaction after 2～18 hours, concentration of reaction solution, the cooling reactant system adds water, separate out the tawny solid product, filter drip washing, drying obtains 4,4 '-two (4-nitrophenoxy)-3,3 ', 5,5 '-tetramethyl biphenyl;
(2) 4,4 '-two (4-nitrophenoxy)-3,3 ', 5,5 '-tetramethyl biphenyl, under the acting in conjunction of the reduction system of iron trichloride/20%～85% hydrazine hydrate, alcoholic solvent, gac, 50 ℃-90 ℃, reacted 8～20 hours, reduction obtains 4,4 '-two (4-amino-benzene oxygen)-3,3 ' of white, 5,5 '-tetramethyl biphenyl crystalline product.
4-halogenated nitrobenzene described in the step (1) is selected from one or more mixtures in 4-fluoro oil of mirbane, 4-chloronitrobenzene, 4-bromo nitryl benzene, the 4-iodo oil of mirbane.
Salt forming agent described in the step (1) is selected from one or more mixtures in Quilonum Retard, yellow soda ash, salt of wormwood, lithium bicarbonate, sodium bicarbonate, saleratus, Calcium hydrogen carbonate, Magnesium hydrogen carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, the calcium hydroxide.
Salt forming agent and 3 described in the step (1), 3 ', 5,5 '-tetramethyl--4, the ratio of the mole number of 4 '-'-biphenyl diphenol is 0.10～8.00: 1.00.
Organic solvent and 3 described in the step (1), 3 ', 5, the envelope-bulk to weight ratio of 5 '-tetramethyl biphenyl diphenol is 5 milliliters～80 milliliters: 1 gram.
Strong polar non-proton organic solvent described in the step (1) is selected from N, one or more mixtures in dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, the dimethyl sulfoxide (DMSO).
Water-insoluble organic solvent described in the step (1) is selected from one or more mixtures in benzene,toluene,xylene, monochloro-benzene, dichlorobenzene, trichloro-benzene, ethylbenzene, diethylbenzene, a chlorotoluene, the dichloro-toluene.
Water-insoluble organic solvent described in the step (1) is 1: 0.05～10 with the volume ratio of strong polar non-proton organic solvent.
Described in the step (2) 4,4 '-two (4-nitrophenoxy)-3,3 ', 5,5 '-tetramethyl biphenyl is 1: 5～30 with the ratio of the mole number of hydrazine hydrate.
Iron trichloride and 4 described in the step (2), 4 '-two (4-nitrophenoxy)-3,3 ', 5, the ratio of the weight of 5 '-tetramethyl biphenyl is 1: 2～50.
Gac and 4 described in the step (2), 4 '-two (4-nitrophenoxy)-3,3 ', 5, the ratio of the weight of 5 '-tetramethyl biphenyl is 1: 0.5～50.
Alcoholic solvent described in the step (2) is selected from methyl alcohol, ethanol, Virahol, n-propyl alcohol, propyl carbinol, isopropylcarbinol, ethylene glycol, 1,2-propylene glycol, 1, ammediol, one or more mixtures in 2-methyl cellosolve, cellosolvo, 2-methyl cellosolve, 3-methoxypropanol, 2-oxyethyl group propyl alcohol, the 3-oxyethyl group propyl alcohol.
Alcoholic solvent and 4 described in the step (2), 4 '-two (4-nitrophenoxy)-3,3 ', 5, the envelope-bulk to weight ratio of 5 '-tetramethyl biphenyl is 1 milliliter～100 milliliters: 1 gram.
Beneficial effect of the present invention:
(1) the present invention is preparation 4,4 '-two (a 4-amino-benzene oxygen)-3,3 ', 5, the commercial run of 5 '-tetramethyl biphenyl;
(2) environmentally friendly, the three wastes are few;
(3) simple to operate, reaction process is carried out under normal pressure, does not relate to also not producing corrosives, equipment is not had particular requirement, less investment;
(4) kind of used organic solvent is few;
(5) organic solvent reclaims conveniently, and Recycling repeatedly;
(6) product yield and purity are all very high;
(7) raw materials used convenient sources, cost is lower, does not relate to the use noble metal catalyst;
(8) production cost of products is cheap, helps it and further applies.
Description of drawings
Fig. 1 is 4,4 '-two (4-nitrophenoxy)-3,3 ', 5, the molecular structural formula of 5 '-tetramethyl biphenyl (3355TMBNPOBP);
Fig. 2 is 4,4 '-two (4-amino-benzene oxygen)-3,3 ', 5, the molecular structural formula of 5 '-tetramethyl biphenyl (3355TMBAPOBP);
Fig. 3 is 4,4 '-two (4-nitrophenoxy)-3,3 ', 5, the infrared spectrogram of 5 '-tetramethyl biphenyl (3355TMBNPOBP);
Fig. 4 is 4,4 '-two (4-nitrophenoxy)-3,3 ', 5, the differential scanning DSC collection of illustrative plates of 5 '-tetramethyl biphenyl (3355TMBNPOBP);
Fig. 5 is 4,4 '-two (4-amino-benzene oxygen)-3,3 ', 5, the infrared spectrogram of 5 '-tetramethyl biphenyl (3355TMBAPOBP);
Fig. 6 is 4,4 '-two (4-amino-benzene oxygen)-3,3 ', 5, the differential scanning DSC collection of illustrative plates of 5 '-tetramethyl biphenyl (3355TMBAPOBP).
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 24.2 gram (0.10 moles) 3,3 ', 5,5 '-tetramethyl--4,4 '-'-biphenyl diphenol, 34.6 gram (0.22 mole) 4-chloronitrobenzene, 110.4 gram (0.80 mole) salt of wormwood, 700 milliliters of N, dinethylformamide and 180 milliliters of toluene are put into reactor, stir, reflux divides the water reaction after 18 hours, concentration of reaction solution, reclaim solvent to recycle, the cooling reactant system adds water, separate out the tawny solid product, drying obtains 45.1 grams, 4,4 '-two (4-nitrophenoxy)-3,3 ', 5,5 '-tetramethyl biphenyl, fusing point are 251.5 ℃, purity is 99.5%, obtain 1 according to reality, amount of two (4-nitrophenoxy) benzene of 4-and theoretical amount (48.4 gram) calculate 4,4 '-two (4-nitrophenoxy)-3,3 ', 5, the yield of 5 '-tetramethyl biphenyl is 93.2%.4,4 '-two (4-nitrophenoxy)-3,3 ', 5, the fourier transform infrared spectrometry of 5 '-tetramethyl biphenyl (FTIR) figure sees accompanying drawing 3, differential scanning calorimeter scanning spectra (DSC) is seen accompanying drawing 4.
With 24.2 gram (0.10 moles) 3,3 ', 5,5 '-tetramethyl--4,4 '-'-biphenyl diphenol, 44.5 gram (0.22 mole) 4-bromo nitryl benzene, 55.2 gram (0.40 mole) salt of wormwood, 150 milliliters of N,N-dimethylacetamide and 15 milliliters of dimethylbenzene are put into reactor, stir, reflux divides the water reaction after 2 hours, concentration of reaction solution, reclaim solvent to recycle, the cooling reactant system adds water, separate out the tawny solid product, purifying, drying obtains 31.7 grams 4,4 '-two (4-nitrophenoxy)-3,3 ', 5,5 '-tetramethyl biphenyl, fusing point is 251.3 ℃, purity is 99.5%, obtains 4,4 '-two (4-nitrophenoxy)-3 according to reality, 3 ', 5, the amount of 5 '-tetramethyl biphenyl and theoretical amount (48.4 gram) calculate 4,4 '-two (4-nitrophenoxy)-3,3 ', 5, the yield of 5 '-tetramethyl biphenyl is 65.5%.
With 24.2 gram (0.10 moles) 3,3 ', 5,5 '-tetramethyl--4,4 '-'-biphenyl diphenol, 28.4 gram (0.18 mole) 4-chloronitrobenzene, 10.6 gram (0.10 mole) yellow soda ash, 40 milliliters of N-N-methyl-2-2-pyrrolidone N-s and 15 milliliters of dichlorobenzenes are put into reactor, stir, reflux divides the water reaction after 10 hours, and concentration of reaction solution reclaims solvent to recycle, the cooling reactant system, add water, separate out the tawny solid product, purifying, dry, obtain 40.1 grams, 4,4 '-two (4-nitrophenoxy)-3,3 ', 5,5 '-tetramethyl biphenyl, fusing point are 250.5 ℃, and purity is 99.0%, obtain 4 according to reality, 4 '-two (4-nitrophenoxy)-3,3 ', 5, the amount of 5 '-tetramethyl biphenyl and theoretical amount (43.5 gram), calculate 4,4 '-two (4-nitrophenoxy)-3,3 ', 5, the yield of 5 '-tetramethyl biphenyl is 92.5%.
With 24.2 gram (0.10 moles) 3,3 ', 5,5 '-tetramethyl--4,4 '-'-biphenyl diphenol, 31.1 gram (0.22 mole) 4-fluoro oil of mirbane, 11.8 gram (0.21 mole) potassium hydroxide, 20 milliliters of N, dinethylformamide and 400 milliliters of dichlorobenzenes are put into reactor, stir, reflux divides the water reaction after 15 hours, concentration of reaction solution, reclaim solvent to recycle, the cooling reactant system adds water, separates out the tawny solid product, dry, obtain 45.8 grams, 4,4 '-two (4-nitrophenoxy)-3,3 ', 5,5 '-tetramethyl biphenyl, fusing point are 251.8 ℃, and purity is 99.6%, obtain 4 according to reality, 4 '-two (4-nitrophenoxy)-3,3 ', 5, the amount of 5 '-tetramethyl biphenyl and theoretical amount (48.4 gram), calculate 4,4 '-two (4-nitrophenoxy)-3,3 ', 5, the yield of 5 '-tetramethyl biphenyl is 94.6%.
With 24.2 gram (0.10 moles) 3,3 ', 5,5 '-tetramethyl--4,4 '-'-biphenyl diphenol, 34.6 gram (0.22 mole) 4-chloronitrobenzene, 80.0 gram (0.80 mole) saleratus, 300 milliliters of dimethyl sulfoxide (DMSO) and 100 milliliters of dimethylbenzene are put into reactor, stir, reflux divides the water reaction after 18 hours, and concentration of reaction solution reclaims solvent to recycle, the cooling reactant system adds water, separates out the tawny solid product, drying obtains 44.1 grams, 4,4 '-two (4-nitrophenoxy)-3,3 ', 5,5 '-tetramethyl biphenyl, fusing point is 251.1 ℃, purity is 99.2%, obtains 4,4 '-two (4-nitrophenoxy)-3 according to reality, 3 ', 5, the amount of 5 '-tetramethyl biphenyl and theoretical amount (48.4 gram) calculate 4,4 '-two (4-nitrophenoxy)-3,3 ', 5, the yield of 5 '-tetramethyl biphenyl is 91.1%.
With 48.4 gram (0.10 mole) 4,4 '-two (4-nitrophenoxy)-3,3 ', 5,5 '-tetramethyl biphenyl, 17.6 the gram iron trichloride, 3520 milliliters of ethanol and 70.4 gram gacs are put into reactor together, stir, heat temperature raising to 50 ℃ begins to drip concentration and is 20% hydrazine hydrate, totally 750.0 grams (3.00 moles) last 3 hours, after hydrazine hydrate is added dropwise to complete, heat temperature raising to 77 ℃ was kept reaction after 17 hours, the cooling reaction solution, heat filtering is removed gac, the cooling mother liquor, separate out white solid product, filter, drying obtains 4 of 36.6 gram whites, 4 '-two (4-amino-benzene oxygens)-3,3 ', 5,5 '-tetramethyl biphenyl crystal, fusing point is 229.0 ℃, purity is 99.6%, obtains 4,4 '-two (4-amino-benzene oxygens)-3 according to reality, 3 ', 5, the amount of 5 '-tetramethyl biphenyl and theoretical amount (42.4 gram), calculating yield is 86.5%.4,4 '-two (4-amino-benzene oxygen)-3,3 ', 5, the fourier transform infrared spectrometry of 5 '-tetramethyl biphenyl (FTIR) figure sees accompanying drawing 5, differential scanning calorimeter scanning spectra (DSC) is seen accompanying drawing 6.
Embodiment 7
With 48.4 gram (0.10 mole) 4,4 '-two (4-nitrophenoxy)-3,3 ', 5,5 '-tetramethyl biphenyl, 0.7 the gram iron trichloride, 40 milliliters of ethylene glycol and 0.7 gram gac are put into reactor together, stir, heat temperature raising to 50 ℃ begins to drip concentration and is 90% hydrazine hydrate, totally 28.0 grams (0.50 mole) last 1 hour, after hydrazine hydrate is added dropwise to complete, heat temperature raising to 75 ℃ was kept reaction after 19 hours, the cooling reaction solution, heat filtering is removed gac, the cooling mother liquor, separate out white solid product, filter drying, obtain 10.8 grams, 4,4 '-two (4-amino-benzene oxygen)-3,3 ', 5,5 '-tetramethyl biphenyl crystal obtains 4,4 '-two (4-amino-benzene oxygens)-3 according to reality, 3 ', 5, the amount of 5 '-tetramethyl biphenyl and theoretical amount (42.4 gram), calculating yield is 25.4%.
Embodiment 8
With 48.4 gram (0.10 mole) 4,4 '-two (4-nitrophenoxy)-3,3 ', 5,5 '-tetramethyl biphenyl, 8.2 the gram iron trichloride, 300 milliliters of 2-methyl cellosolves and 50.0 gram gacs are put into reactor together, stir, heat temperature raising to 50 ℃ begins to drip concentration and is 80% hydrazine hydrate, totally 125.0 grams (2.00 moles) last 1 hour, after hydrazine hydrate is added dropwise to complete, heat temperature raising to 70 ℃ was kept reaction after 20 hours, the cooling reaction solution, heat filtering is removed gac, the cooling mother liquor, separate out white solid product, filter drying, obtain 28.2 grams, 4,4 '-two (4-amino-benzene oxygen)-3,3 ', 5,5 '-tetramethyl biphenyl crystal obtains 4,4 '-two (4-amino-benzene oxygens)-3 according to reality, 3 ', 5, the amount of 5 '-tetramethyl biphenyl and theoretical amount (42.4 gram), calculating yield is 66.5%.
With 48.4 gram (0.10 mole) 4,4 '-two (4-nitrophenoxy)-3,3 ', 5,5 '-tetramethyl biphenyl, 10.0 the gram iron trichloride, 400 milliliter 1, ammediol and 30.0 gram gacs are put into reactor together, stir heat temperature raising to 50 ℃, begin to drip concentration and be 90% hydrazine hydrate, totally 166.7 grams (3.00 moles) last 0.5 hour, after hydrazine hydrate was added dropwise to complete, heat temperature raising to 82 ℃ was kept reaction after 8 hours, the cooling reaction solution, heat filtering is removed gac, the cooling mother liquor is separated out white solid product, filters, drying obtains 15.4 grams, 4,4 '-two (4-amino-benzene oxygens)-3,3 ', 5,5 '-tetramethyl biphenyl crystal, obtain 4 according to reality, 4 '-two (4-amino-benzene oxygen)-3,3 ', 5, the amount of 5 '-tetramethyl biphenyl and theoretical amount (42.4 gram), calculating yield is 36.3%.
With 48.4 gram (0.10 mole) 4,4 '-two (4-nitrophenoxy)-3,3 ', 5,5 '-tetramethyl biphenyl, 5.4 the gram iron trichloride, 600 milliliters of ethanol and 26.8 gram gacs are put into reactor together, stir, heat temperature raising to 50 ℃ begins to drip concentration and is 85% hydrazine hydrate, totally 58.8 grams (1.00 moles) last 1.5 hours, after hydrazine hydrate is added dropwise to complete, heat temperature raising to 90 ℃ was kept reaction after 15 hours, the cooling reaction solution, heat filtering is removed gac, the cooling mother liquor, separate out white solid product, filter drying, obtain 30.7 grams, 4,4 '-two (4-amino-benzene oxygen)-3,3 ', 5,5 '-tetramethyl biphenyl crystal obtains 4,4 '-two (4-amino-benzene oxygens)-3 according to reality, 3 ', 5, the amount of 5 '-tetramethyl biphenyl and theoretical amount (42.2 gram), calculating yield is 72.8%.
Claims (13)
1.4,4 '-two (4-amino-benzene oxygen)-3,3 ', 5, the preparation method of 5 '-tetramethyl biphenyl comprises step:
(1) mol ratio be 1.00: 2.00～2.20 3,3 ', 5,5 '-tetramethyl--4,4 '-'-biphenyl diphenol and 4-halogenated nitrobenzene, in salt forming agent, strong aprotic, polar or water-insoluble organic solvent system, reflux divides the water reaction after 2～18 hours, concentration of reaction solution, the cooling reactant system adds water, separate out the tawny solid product, filter drip washing, drying obtains 4,4 '-two (4-nitrophenoxy)-3,3 ', 5,5 '-tetramethyl biphenyl;
(2) 4,4 '-two (4-nitrophenoxy)-3,3 ', 5,5 '-tetramethyl biphenyl, under the acting in conjunction of the reduction system of iron trichloride/20%～85% hydrazine hydrate, alcoholic solvent, gac, 50 ℃-90 ℃, reacted 8～20 hours, reduction obtains 4,4 '-two (4-amino-benzene oxygen)-3,3 ' of white, 5,5 '-tetramethyl biphenyl crystalline product.
2. according to claim 14,4 '-two (4-amino-benzene oxygens)-3,3 ', 5, the preparation method of 5 '-tetramethyl biphenyl, it is characterized in that the 4-halogenated nitrobenzene described in the step (1) is selected from one or more mixtures in 4-fluoro oil of mirbane, 4-chloronitrobenzene, 4-bromo nitryl benzene, the 4-iodo oil of mirbane.
3. according to claim 14,4 '-two (4-amino-benzene oxygens)-3,3 ', 5, the preparation method of 5 '-tetramethyl biphenyl, it is characterized in that the salt forming agent described in the step (1) is selected from one or more mixtures in Quilonum Retard, yellow soda ash, salt of wormwood, lithium bicarbonate, sodium bicarbonate, saleratus, Calcium hydrogen carbonate, Magnesium hydrogen carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, the calcium hydroxide.
4. according to claim 1 or 3 described 4,4 '-two (4-amino-benzene oxygens)-3,3 ', 5, the preparation method of 5 '-tetramethyl biphenyl, it is characterized in that, salt forming agent and 3 described in the step (1), 3 ', 5,5 '-tetramethyl--4, the ratio of the mole number of 4 '-'-biphenyl diphenol is 0.10～8.00: 1.00.
5. according to claim 14,4 '-two (4-amino-benzene oxygens)-3,3 ', 5, the preparation method of 5 '-tetramethyl biphenyl, it is characterized in that, organic solvent and 3 described in the step (1), 3 ', 5,5 '-tetramethyl--4, the envelope-bulk to weight ratio of 4 '-'-biphenyl diphenol are 5 milliliters～80 milliliters: 1 gram.
6. according to claim 14,4 '-two (4-amino-benzene oxygens)-3,3 ', 5, the preparation method of 5 '-tetramethyl biphenyl is characterized in that, the strong polar non-proton organic solvent described in the step (1) is selected from N, one or more mixtures in dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, the dimethyl sulfoxide (DMSO).
7. according to claim 14,4 '-two (4-amino-benzene oxygens)-3,3 ', 5, the preparation method of 5 '-tetramethyl biphenyl, it is characterized in that the water-insoluble organic solvent described in the step (1) is selected from one or more mixtures in benzene,toluene,xylene, monochloro-benzene, dichlorobenzene, trichloro-benzene, ethylbenzene, diethylbenzene, a chlorotoluene, the dichloro-toluene.
8. according to claim 1,6 or 7 described 4,4 '-two (4-amino-benzene oxygens)-3,3 ', 5, the preparation method of 5 '-tetramethyl biphenyl is characterized in that, the water-insoluble organic solvent described in the step (1) is 1: 0.05～10 with the volume ratio of strong polar non-proton organic solvent.
9. according to claim 14,4 '-two (4-amino-benzene oxygens)-3,3 ', 5, the preparation method of 5 '-tetramethyl biphenyl, it is characterized in that, described in the step (2) 4,4 '-two (4-nitrophenoxy)-3,3 ', 5,5 '-tetramethyl biphenyl is 1: 5～30 with the ratio of the mole number of hydrazine hydrate.
10. according to claim 14,4 '-two (4-amino-benzene oxygen)-3,3 ', 5, the preparation method of 5 '-tetramethyl biphenyl, it is characterized in that, it is characterized in that, the iron trichloride and 4 described in the step (2), 4 '-two (4-nitrophenoxy)-3,3 ', 5, the ratio of the weight of 5 '-tetramethyl biphenyl is 1: 2～50.
11. according to claim 14,4 '-two (4-amino-benzene oxygens)-3,3 ', 5, the preparation method of 5 '-tetramethyl biphenyl, it is characterized in that, gac and 4 described in the step (2), 4 '-two (4-nitrophenoxy)-3,3 ', 5, the ratio of the weight of 5 '-tetramethyl biphenyl is 1: 0.5～50.
12. according to claim 14,4 '-two (4-amino-benzene oxygens)-3,3 ', 5, the preparation method of 5 '-tetramethyl biphenyl is characterized in that, alcoholic solvent described in the step (2) is selected from methyl alcohol, ethanol, Virahol, n-propyl alcohol, propyl carbinol, isopropylcarbinol, ethylene glycol, 1,2-propylene glycol, 1, ammediol, one or more mixtures in 2-methyl cellosolve, cellosolvo, 2-methyl cellosolve, 3-methoxypropanol, 2-oxyethyl group propyl alcohol, the 3-oxyethyl group propyl alcohol.
13. according to claim 1 or 12 described 4,4 '-two (4-amino-benzene oxygens)-3,3 ', 5, the preparation method of 5 '-tetramethyl biphenyl, it is characterized in that, alcoholic solvent and 4 described in the step (2), 4 '-two (4-nitrophenoxy)-3,3 ', 5, the envelope-bulk to weight ratio of 5 '-tetramethyl biphenyl is 1 milliliter～100 milliliters: 1 gram.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491911A (en) * | 2011-12-01 | 2012-06-13 | 哈尔滨工业大学 | Diamine monomer, synthetic method thereof, and polyimide prepared from diamine monomer |
| CN101560162B (en) * | 2009-05-12 | 2012-09-05 | 东华大学 | Preparation method of 4,4'-bi(4-amino-2-trifluoromethylphenoxyl)-3,3'5,5'-tetramethylbiphenyl |
| CN101381335B (en) * | 2008-08-04 | 2013-04-17 | 东华大学 | 4,4'-bis(4-nitrophenoxy)phenyl sulfide preparation method |
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| JP3101644B2 (en) * | 1995-01-26 | 2000-10-23 | フランスベッド株式会社 | Sofa bed equipment |
| CN1472193A (en) * | 2003-07-11 | 2004-02-04 | 南通探索科技有限公司 | Preparation of 2,2-bi-[4-(4-aminophenoxy)phenyl]propane |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101381335B (en) * | 2008-08-04 | 2013-04-17 | 东华大学 | 4,4'-bis(4-nitrophenoxy)phenyl sulfide preparation method |
| CN101560162B (en) * | 2009-05-12 | 2012-09-05 | 东华大学 | Preparation method of 4,4'-bi(4-amino-2-trifluoromethylphenoxyl)-3,3'5,5'-tetramethylbiphenyl |
| CN102491911A (en) * | 2011-12-01 | 2012-06-13 | 哈尔滨工业大学 | Diamine monomer, synthetic method thereof, and polyimide prepared from diamine monomer |
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