CN101492376B - Process for producing 3,3',5,5'-tetramethyl-4,4'-di(2-trifluoromethyl-4-nitrophenoxy)biphenyl - Google Patents
Process for producing 3,3',5,5'-tetramethyl-4,4'-di(2-trifluoromethyl-4-nitrophenoxy)biphenyl Download PDFInfo
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- CN101492376B CN101492376B CN2009100466265A CN200910046626A CN101492376B CN 101492376 B CN101492376 B CN 101492376B CN 2009100466265 A CN2009100466265 A CN 2009100466265A CN 200910046626 A CN200910046626 A CN 200910046626A CN 101492376 B CN101492376 B CN 101492376B
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Abstract
The invention relates to a preparation method of 3, 3', 5, 5'- tetramethyl -4, 4'-double (2-trifluoromethane-4-nitrobenzene oxy) diphenyl. The invention comprises the following steps: (1) mixing 3, 3', 5, 5'-tetramethyl-4, 4'-dihydroxy diphenyl and 2-chlorine-5-nitryl trifluoromethyl benzene by the mol ratio of 1.0:2.0-2.6, and then adding the mixture into a mixed solvent of salifying agent, soluble organic solvent and non-soluble organic solvent for reaction for 4 to 15 hours at 100 to 180 DEG C; (2) filtering when the solvent is hot, eliminating filter residue, condensing mother liquid, cooling and stewing to precipitate a butter yellow solid product, and then filtering, washing and drying the product to obtain the butter yellow solid powder of 3, 3', 5, 5'-tetramethyl-4, 4'-double(2- trifluoromethyl-4-nitrobenzene oxy) diphenyl. The method with simple process, low cost, environment-friendliness and high purity and yield is applicable to the industrial production.
Description
Technical field
The invention belongs to the preparation field of the fluorine-containing biphenyl of aromatic series, particularly relate to a kind of 3,3 ', 5,5 '-tetramethyl--4,4 '-preparation method of two (2-trifluoromethyl-4-nitrophenoxy) biphenyl.
Background technology
Aromatic polyimide has excellent thermostability, chemicalstability, excellent mechanical property, electric property and organic solvent resistance, has obtained widespread use in space flight and aviation, electronics microelectronics, field such as electric.Because characteristics such as it these are high temperature resistant, HS, anticorrosive, good insulating, film-forming process are simple, thereby be a kind of good functional materials.
The fluorinated polyimide material not only has above-mentioned excellent properties, but also has very excellent optical transparence, flame retardant resistance and good forming process property.In addition, its specific inductivity, dielectric loss and water-intake rate are all lower.
The fluorinated polyimide material has important use and is worth in some field, like the passivating coating of flexible solar radiation protector, liquid crystal orientation film, gas separation membrane, unicircuit or layer insulation medium, the waveguide material of communications connectors, the electric insulation deielectric-coating of flexible printed circuit board etc.
In addition; Contain the polymkeric substance of cyclohexyl biphenyl structure, rigidity is bigger, and the regularity of macromolecular chain is better; Help the crystallization of polymkeric substance; Therefore, contain cyclohexyl biphenyl structural polymer material and have some special performances, like low thermal coefficient of expansion, low-dielectric loss, low-k, low water absorption, high dielectric strength, high-modulus, high mechanical strength, high heat resistance etc.
Therefore, the fluorine-containing polyimide monomer that contains the cyclohexyl biphenyl structure of research and development has special significance.
At present, to fluorine-containing or contain existing report of polyimide raw material monomer of cyclohexyl biphenyl structure:
Yu Xinhai [the extraordinary monomeric synthetic and sign [J] of fluorinated polyimide. New Chemical Materials, 2003,31 (10): 24-27,31] disclose 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa and the fluorinated polyimide preparation methods thereof of 2-.
It is a kind of 2 that Chinese invention patent CN1876624A (2006-12-13) discloses, the preparation method of two [3-amino-4-(4-cyano-benzene oxygen) phenyl] HFC-236fas of 2-.
Yu Xinhai [4; 4 '-the surface property research [J] of the synthetic and Kapton of two (4-amino-benzene oxygen) biphenyl. insulating material; 2008,41 (2): 10-14] disclose 4,4 '-preparation method of two (4-amino-benzene oxygen) biphenyl and Kapton thereof.
3,3 ', 5,5 '-tetramethyl--4,4 '-two (2-trifluoromethyl-4-nitrophenoxy) biphenyl is fluorine-containing one of the monomeric important source material of cyclohexyl biphenyl structure polyimide that contains of synthetic aroma family.
Chin-Ping Yang, Sheng-Huei Hsiao, Kuei-Hung Chen [Organosoluble and opticallytransparent fluorine-containing polyimides based on 4,4 '-bis (4-amino-2-trifluoromethylphenoxy)-3,3 '; 5,5 '-tetramethylbiphenyl [J] .Polymer, 2002,43:5095-5104] disclose 3,3 '; 5,5 '-tetramethyl--4,4 '-preparation method of two (2-trifluoromethyl-4-nitrophenoxy) biphenyl, it is characterized in that: 3; 3 ', 5,5 '-tetramethyl--4,4 '-dihydroxybiphenyl and 2-chloro-5-nitro trifluoromethylbenzene are dissolved among the DMF earlier; Add salt of wormwood, be heated to 120 ℃ of reactions after 8 hours, reaction solution is poured in the water, separate out yellow solid product; And with a large amount of water washings, drying obtains bullion (yield is 97%), uses the mixed solution recrystallization of DMF and methyl alcohol again; Obtain lark (pale yellow) crystallized product (recrystallization yield 78%), promptly 3,3 ', 5; 5 '-tetramethyl--4,4 '-two (2-trifluoromethyl-4-nitrophenoxy) biphenyl crystal, 266 ℃-267 ℃ of fusing points (DSC, 2 ℃/min).
But the shortcoming of this method is: the yield of (1) product is on the low side, and the recrystallization yield is 78%, and total recovery has only 97%*78%＜76%; (2) the organic solvent kind that relates to is more, like DMF, methyl alcohol etc.This has not only increased material cost, but also has increased the Recovery of Organic Solvent cost; (3) reactant is directly poured in the water with the precipitating product, and with a large amount of water washings.This certainly will cause a large amount of waste water, increases the expense of wastewater treatment equally, is unfavorable for environment protection and reduces production costs; (4) bullion that separates out also needs in the DMF/ methyl alcohol mixed liquor, to make further recrystallization, with purified product.This has not only increased chemical engineering unit operation, has increased chemical plant and personal expenditures etc., and has improved material cost and production cost again, has also increased the three wastes simultaneously.
Summary of the invention
That technical problem to be solved by this invention provides is a kind of 3,3 ', 5; 5 '-tetramethyl--4; 4 '-preparation method of two (2-trifluoromethyl-4-nitrophenoxy) biphenyl, this method technology is simple, cost is low, environmental friendliness, purity and yield are high, is applicable to industrial production.
Chemical equation of the present invention is following:
Of the present invention a kind of 3,3 ', 5,5 '-tetramethyl--4,4 '-preparation method of two (2-trifluoromethyl-4-nitrophenoxy) biphenyl, comprise the steps:
(1) with 3,3 ', 5; 5 '-tetramethyl--4; 4 '-dihydroxybiphenyl and 2-chloro-5-nitro trifluoromethylbenzene are 1.0: 2.0～2.6 to mix in molar ratio, join in the mixed solution of salt forming agent, water-miscible organic solvent and water-insoluble organic solvent, in 100 ℃～180 ℃ reactions 4～15 hours; Wherein, salt forming agent and 3,3 ', 5,5 '-tetramethyl--4,4 '-ratio of the mole number of dihydroxybiphenyl is 0.8～4.5: 1.0; The mixed solvent of water-miscible organic solvent and water-insoluble organic solvent is 5 milliliters～50 milliliters with the envelope-bulk to weight ratio of total organic reactant: 1 gram; The weight of total organic reactant is meant 3; 3 '; 5,5 '-tetramethyl--4,4 '-the weight sum of dihydroxybiphenyl and 2-chloro-5-nitro trifluoromethylbenzene; The volume ratio of water-insoluble organic solvent and water-miscible organic solvent is 1: 0.5-15;
(2) filtered while hot is removed filter residue, concentrated mother liquor, and cooling is left standstill, and separates out the milk yellow solid product, filter, washing, drying, obtain 3,3 ', 5,5 '-tetramethyl--4,4 '-two (2-trifluoromethyl-4-nitrophenoxy) biphenyl milk yellow pressed powder.
Salt forming agent in the said step (1) is selected from one or more mixtures in Pottasium Hydroxide, Quilonum Retard, yellow soda ash, salt of wormwood, lithium bicarbonate, sodium hydrogencarbonate, saleratus, the sodium hydroxide;
Water-miscible organic solvent in the said step (1) is selected from N, one or more mixtures in dinethylformamide, DMAC N,N, N-N-methyl-2-2-pyrrolidone N-, N-ethyl-2-pyrrolidone, the DMSO 99.8MIN.;
Water-insoluble organic solvent in the said step (1) is selected from one or more mixtures in benzene,toluene,xylene, ethylbenzene, monochloro-benzene, the orthodichlorobenzene;
In the said step (1) 3,3 ', 5,5 '-tetramethyl--4,4 '-dihydroxybiphenyl, 2-chloro-5-nitro trifluoromethylbenzene be by the stable supply of Shanghai EMST Electron Material Co., Ltd.
The present invention utilizes water-insoluble organic solvent to be prone to the principle with water generates " azeotrope ", and " water " of reaction system in reaction process is in time got rid of, and the driving a reaction balance moves to positive reaction, farthest to improve productive rate; And make full use of the easy crystallinity of " the cyclohexyl biphenyl structure " of title product, design suitable Recipe, single stage method can obtain target product with high purity, removes the unit operation of " recrystallization " from.
Beneficial effect
(1) preparation method of the present invention is simple to operate, and equipment is not had particular requirement; Reaction process is carried out under normal pressure, and raw material sources are convenient, and cost is low, does not relate to also not producing corrosives; Organic solvent uses kind few, and Recycling repeatedly is environmentally friendly;
(2) this method need not recrystallization operation, has simplified technology, and product yield is up to more than 95%, and purity is applicable to suitability for industrialized production up to 99.8%.
Description of drawings
Fig. 1 is 3,3 ', 5,5 '-tetramethyl--4,4 '-molecular structure of two (2-trifluoromethyl-4-nitrophenoxy) biphenyl;
Fig. 2 be embodiment 1 prepared 3,3 ', 5,5 '-tetramethyl--4,4 '-differential scanning calorimeter (DSC) scanning spectra of two (2-trifluoromethyl-4-nitrophenoxy) biphenyl;
Fig. 3 be embodiment 1 prepared 3,3 ', 5,5 '-tetramethyl--4,4 '-fourier transform infrared spectrometry (FTIR) collection of illustrative plates of two (2-trifluoromethyl-4-nitrophenoxy) 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 the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to 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 '-dihydroxybiphenyl (3355TMBP), 47.4 gram (0.21 mole) 2-chloro-5-nitro trifluoromethylbenzenes (CNB-TF), 41.4 gram (0.30 mole) salt of wormwood, 800 milliliters of N; The mixed solvent of dinethylformamide and 400 milliliters of toluene is put into reaction kettle, stirs, and is heated to 100 ℃-120 ℃, and reflux water-dividing reaction 10 hours continues heat temperature raising; To 150 ℃ the reaction 1 hour after, filtered while hot is removed filter residue, concentrated mother liquor; Reclaim solvent to recycle, cooling is left standstill, and separates out the milk yellow solid crystallized product, filters; With pure water washing 2～3 times, drying, obtain 3,3 of 59.0 grams '; 5,5 '-tetramethyl--4,4 '-two (2-trifluoromethyl-4-nitrophenoxy) biphenyl (DNTMBP-2TF) milk yellow solid product (theoretical yield is 62.1 grams), purity is 99.8%; Fusing point is 267.5 ℃, and (10 ℃ of temperature rise rates/min), its DSC scanning spectra is as shown in Figure 2 for DSC DSC, nitrogen atmosphere; Figure is as shown in Figure 3 for fourier transform infrared spectrometry (FTIR).
According to theoretical yield with actual obtain 3,3 ', 5; 5 '-tetramethyl--4,4 '-amount of two (2-trifluoromethyl-4-nitrophenoxy) biphenyl (DNTMBP-2TF), calculate 3; 3 '; 5,5 '-tetramethyl--4,4 '-yield of two (2-trifluoromethyl-4-nitrophenoxy) biphenyl (DNTMBP-2TF) is 95%.
Embodiment 2
With 24.2 the gram (0.10 moles) 3,3 ', 5,5 '-tetramethyl--4; 4 '-dihydroxybiphenyl (3355TMBP), 58.6 gram (0.26 mole) 2-chloro-5-nitro trifluoromethylbenzenes (CNB-TF), 11.0 gram (0.08 mole) salt of wormwood, 200 milliliters of N-N-methyl-2-2-pyrrolidone N-s, 3600 milliliters of DMAC N,Ns and 260 milliliters of YLENE mixed solvents put into reaction kettle, stir, and are heated to 100 ℃-180 ℃; React after 15 hours, filtered while hot is removed filter residue, concentrated mother liquor; Reclaim solvent to recycle, cooling is left standstill, and separates out the milk yellow solid product, filters; With pure water washing 2～3 times, drying, obtain 57.7 grams 3,3 '; 5,5 '-tetramethyl--4,4 '-two (2-trifluoromethyl-4-nitrophenoxy) biphenyl (DNTMBP-2TF) milk yellow solid product (theoretical yield is 62.1 grams), purity is 99.5%.
According to theoretical yield with actual obtain 3,3 ', 5; 5 '-tetramethyl--4,4 '-amount of two (2-trifluoromethyl-4-nitrophenoxy) biphenyl (DNTMBP-2TF), calculate 3; 3 '; 5,5 '-tetramethyl--4,4 '-yield of two (2-trifluoromethyl-4-nitrophenoxy) biphenyl (DNTMBP-2TF) is 93%.
With 24.2 the gram (0.10 moles) 3,3 ', 5,5 '-tetramethyl--4; 4 '-mixed solvent of dihydroxybiphenyl (3355TMBP), 45.1 gram (0.20 mole) 2-chloro-5-nitro trifluoromethylbenzenes (CNB-TF), 10.6 gram (0.10 mole) yellow soda ash, 48.3 gram (0.35 mole) salt of wormwood, 350 milliliters of N-N-methyl-2-2-pyrrolidone N-s and 700 milliliters of toluene puts into reaction kettle, stirs, and is heated to 100 ℃ of-130 ℃ of reflux water-dividings reactions 8 hours, continues heat temperature raising; To 180 ℃ the reaction 0.5 hour after, filtered while hot is removed filter residue, concentrated mother liquor; Reclaim solvent to recycle, cooling is left standstill, and separates out the milk yellow solid product; Filter, with pure water washing 2～3 times, drying; Obtain 55.9 the gram 3,3 ', 5; 5 '-tetramethyl--4,4 '-two (2-trifluoromethyl-4-nitrophenoxy) biphenyl (DNTMBP-2TF) milk yellow solid product, purity is 99.6%.
According to reality obtain 3,3 ', 5; 5 '-tetramethyl--4,4 '-amount of two (2-trifluoromethyl-4-nitrophenoxy) biphenyl (DNTMBP-2TF) and theoretical yield (62.1 gram), calculate 3; 3 '; 5,5 '-tetramethyl--4,4 '-yield of two (2-trifluoromethyl-4-nitrophenoxy) biphenyl (DNTMBP-2TF) is 90%.
Embodiment 4
With 24.2 the gram (0.10 moles) 3,3 ', 5,5 '-tetramethyl--4; 4 '-dihydroxybiphenyl (3355TMBP), 47.4 restrains (0.21 mole) 2-chloro-5-nitro trifluoromethylbenzenes (CNB-TF), 10.6 gram (0.10 mole) yellow soda ash, 27.6 restrain (0.20 mole) salt of wormwood, 250 milliliters of N-N-methyl-2-2-pyrrolidone N-s, 60 milliliters of YLENE and 100 milliliters of toluene mixed solvents and put into reaction kettle, stirs, and is heated to 110 ℃ of-140 ℃ of reflux water-dividings reactions 3.5 hours, the continuation heat temperature raising; To 180 ℃ the reaction 0.5 hour after, filtered while hot is removed filter residue, concentrated mother liquor; Reclaim solvent to recycle, cooling is left standstill, and separates out the milk yellow solid product; Filter, with pure water washing 2～3 times, drying; Obtain 49.7 the gram 3,3 ', 5; 5 '-tetramethyl--4,4 '-two (2-trifluoromethyl-4-nitrophenoxy) biphenyl (DNTMBP-2TF) milk yellow solid product, purity is 99.0%.
According to reality obtain 3,3 ', 5; 5 '-tetramethyl--4,4 '-amount of two (2-trifluoromethyl-4-nitrophenoxy) biphenyl (DNTMBP-2TF) and theoretical amount (62.1 gram), calculate 3; 3 '; 5,5 '-tetramethyl--4,4 '-yield of two (2-trifluoromethyl-4-nitrophenoxy) biphenyl (DNTMBP-2TF) is 80%.
With 24.2 the gram (0.10 moles) 3,3 ', 5,5 '-tetramethyl--4; 4 '-dihydroxybiphenyl (3355TMBP), 51.9 restrains (0.23 mole) 2-chloro-5-nitro trifluoromethylbenzenes (CNB-TF), 10.6 gram (0.10 mole) yellow soda ash, 10.0 restrain (0.10 mole) saleratus, 13.8 gram (0.10 mole) salt of wormwood, 300 milliliters of N-N-methyl-2-2-pyrrolidone N-s, 500 milliliters of DMSO 99.8MIN.s and 300 milliliters of toluene mixed solvents and put into reaction kettle, stirs, and be heated to 110 ℃ of-130 ℃ of reflux water-dividings and react after 10 hours; Filtered while hot is removed filter residue, concentrated mother liquor; Reclaim solvent to recycle, cooling is left standstill, and separates out the milk yellow solid product; Filter, with pure water washing 2～3 times, drying; Obtain 55.3 the gram 3,3 ', 5; 5 '-tetramethyl--4,4 '-two (2-trifluoromethyl-4-nitrophenoxy) biphenyl (DNTMBP-2TF), purity is 99.6%.
According to reality obtain 3,3 ', 5; 5 '-tetramethyl--4,4 '-amount of two (2-trifluoromethyl-4-nitrophenoxy) biphenyl (DNTMBP-2TF) and theoretical amount (62.1 gram), calculate 3; 3 '; 5,5 '-tetramethyl--4,4 '-yield of two (2-trifluoromethyl-4-nitrophenoxy) biphenyl (DNTMBP-2TF) is 89%.
Claims (2)
1. one kind 3,3 ', 5,5 '-tetramethyl--4,4 '-preparation method of two (2-trifluoromethyl-4-nitrophenoxy) biphenyl, comprise the steps:
(1) with 3,3 ', 5; 5 '-tetramethyl--4; 4 '-dihydroxybiphenyl and 2-chloro-5-nitro trifluoromethylbenzene are 1.0: 2.0～2.6 to mix in molar ratio, join in the mixed solution of salt forming agent, water-miscible organic solvent and water-insoluble organic solvent, in 100 ℃～180 ℃ reactions 4～15 hours; Wherein, salt forming agent and 3,3 ', 5,5 '-tetramethyl--4,4 '-ratio of the mole number of dihydroxybiphenyl is 0.8～4.5: 1.0; The mixed solvent of water-miscible organic solvent and water-insoluble organic solvent is 5 milliliters～50 milliliters with the envelope-bulk to weight ratio of total organic reactant: 1 gram; The weight of total organic reactant is meant 3; 3 '; 5,5 '-tetramethyl--4,4 '-the weight sum of dihydroxybiphenyl and 2-chloro-5-nitro trifluoromethylbenzene; The volume ratio of water-insoluble organic solvent and water-miscible organic solvent is 1: 0.5-15; Water-miscible organic solvent is selected from N, one or more in dinethylformamide, DMAC N,N, N-N-methyl-2-2-pyrrolidone N-, N-ethyl-2-pyrrolidone, the DMSO 99.8MIN.; Water-insoluble organic solvent is selected from one or more in benzene,toluene,xylene, ethylbenzene, monochloro-benzene, the orthodichlorobenzene;
(2) filtered while hot is removed filter residue, concentrated mother liquor, and cooling is left standstill, and separates out the milk yellow solid product, filter, washing, drying, obtain 3,3 ', 5,5 '-tetramethyl--4,4 '-two (2-trifluoromethyl-4-nitrophenoxy) biphenyl milk yellow pressed powder.
2. according to claim 1 a kind of 3; 3 '; 5; 5 '-tetramethyl--4,4 '-preparation method of two (2-trifluoromethyl-4-nitrophenoxy) biphenyl, it is characterized in that: the salt forming agent in the said step (1) is selected from one or more in Pottasium Hydroxide, Quilonum Retard, yellow soda ash, salt of wormwood, lithium bicarbonate, sodium hydrogencarbonate, saleratus, the sodium hydroxide.
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| CN2009100466265A CN101492376B (en) | 2009-02-25 | 2009-02-25 | Process for producing 3,3',5,5'-tetramethyl-4,4'-di(2-trifluoromethyl-4-nitrophenoxy)biphenyl |
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Non-Patent Citations (2)
| Title |
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| Yang, Chin-Ping等.Organosoluble and optically transparent fluorine-containing polyimides based on 4,4"-bis(4-amino-2-trifluoromethylphenoxy)-3,3",5,5"-tetramethylbiphenyl.《Polymer》.2002,第43卷(第19期), |
| Yang, Chin-Ping等.Organosoluble and optically transparent fluorine-containing polyimides based on 4,4"-bis(4-amino-2-trifluoromethylphenoxy)-3,3",5,5"-tetramethylbiphenyl.《Polymer》.2002,第43卷(第19期), * |
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