CN101397254B - Method for preparing 2,2-bis[4-(2-trifluoromethyl-4-nitrophenoxy)phenyl] propane - Google Patents
Method for preparing 2,2-bis[4-(2-trifluoromethyl-4-nitrophenoxy)phenyl] propane Download PDFInfo
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- CN101397254B CN101397254B CN2008102017660A CN200810201766A CN101397254B CN 101397254 B CN101397254 B CN 101397254B CN 2008102017660 A CN2008102017660 A CN 2008102017660A CN 200810201766 A CN200810201766 A CN 200810201766A CN 101397254 B CN101397254 B CN 101397254B
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Abstract
The invention relates to a preparation method of 2, 2-bis (4-(2-trifluoromethyl-4-nitrophenoxy)phenyl) propane, which comprises the steps: (1) 2, 2-bis (4-hydroxyphenyl) propane and 2-chloro-5-nitrophenyl trifluoride with the molar ratio of 1.0: 2.0 to 2.2 are carried out the heating, the reflux and the water separation reaction for 4 to 10 hours in a system with a salt forming agent and an organic mixed solvent; and (2) the filtration is carried out while hot, filtration residues are removed, mother liquor is concentrated, the cooling, the still placement, the precipitation of crystallization products, the filtration, the washing and the drying are carried out, thereby obtaining 2, 2-bis (4-(2-trifluoromethyl-4-nitrophenoxy)phenyl) propane crystals. The product yield can reach more than 98 percent, the purity can be 99.9 percent, and the preparation method has simple operation, less equipment investment, low energy consumption, convenient solvent recycling, repeated use, less three wastes and environmentally friendly property, thereby being applicable to industrial production.
Description
Technical field
The invention belongs to the preparation field of aromatic organic compounds, particularly relate to a kind of 2, the preparation method of two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] propane of 2-.
Background technology
Aromatic polyimide has excellent thermostability, chemical stability, 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, high strength, anticorrosive, good insulating, film-forming process are simple, thereby be a kind of good functional materials, can satisfy the performance requriements of LCD (liquid-crystal display).
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.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, as 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.
Yu Xinhai [New Chemical Materials, 2003,31 (10): 24-27,31] discloses 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa and the fluorinated polyimide preparation methods thereof of 2-.
2, two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] propane of 2-are one of monomeric important source material of synthetic aroma family fluorinated polyimide.
People such as Chin-pingYang [Journal of Applied Polymer Science, 2005,95:922-935] disclose 2, the preparation method of two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] propane of 2-, it is characterized in that: 2, two (4-hydroxy phenyl) propane of 2-and 2-chloro-5-oil of mirbane trifluoride are dissolved among the DMAc earlier, add salt of wormwood, stirred under the room temperature 30 minutes, and be heated to 100 ℃ of reactions after 12 hours, reaction solution is poured in the mixed solution of first alcohol and water that volume ratio is 10:1, to separate out solid product, and with a large amount of methyl alcohol and hot wash, 60 ℃ of vacuum-dryings obtain crude product (yield 96.4%), use the mixed solution recrystallization of DMF and methyl alcohol again, obtain crystallized product (yield 93.4%), promptly 2, two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] the propane crystal of 2-.
The shortcoming of this method is:
(1) in 100 ℃ reaction process, there is portion water to produce, and remaines in the reaction system always, can't carrying out and remove with reaction, and water has bigger negative impact to this reaction, therefore, finally cause the total recovery of product on the low side, have only 96.4%X93.4%=90.0%;
(2) the organic solvent kind that relates to is more, as DMAc, 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 mixed solution of methyl alcohol and water with the precipitating product, and with a large amount of methyl alcohol and hot wash.This certainly will cause a large amount of waste water and consume a large amount of methyl alcohol, has increased the cost of Methanol Recovery and the expense of wastewater treatment equally, is unfavorable for environment protection and reduces production costs;
(4) crude product that separates out also needs to make further recrystallization in the DMF/ methyl alcohol mixed liquor, with purified product.This has not only increased chemical engineering unit operation, has increased chemical industry equipment and personal expenditures etc., and has improved material cost and production cost again, has also increased the three wastes simultaneously.
Summary of the invention
The purpose of this invention is to provide a kind of 2, the preparation method of two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] propane of 2-, this method technology is simple, cost is low, environmental friendliness, purity and yield height, is applicable to industrial production.
Chemical equation of the present invention is as follows:
Of the present invention 2, the preparation method of two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] propane of 2-comprises:
(1) mol ratio is 2 of 1.0:2.0～2.2, two (4-hydroxy phenyl) propane of 2-and 2-chloro-5-oil of mirbane trifluoride, and in salt forming agent, organic mixed solvent system, reflux is divided water reaction 4～10 hours;
(2) filtered while hot is removed filter residue, concentrated mother liquor, and cooling is left standstill, and separates out crystallized product, filter, washing, drying obtains 2, two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] the propane crystal of 2-.
The salt forming agent of described 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.
The salt forming agent and 2 of described step (1), the ratio of the mole number of two (4-hydroxy phenyl) propane of 2-is 1～4:1.
Organic mixed solvent of described step (1) is the mixture of water-insoluble organic solvent and strong polar non-proton organic solvent, and volume ratio is 1:0.5～10.
The mixture of the water-insoluble organic solvent of described step (1) and strong polar non-proton organic solvent, volume ratio is 1:1.6.
Described water-insoluble organic solvent is selected from one or more mixtures in benzene,toluene,xylene, monochloro-benzene, dichlorobenzene, trichloro-benzene, ethylbenzene, diethylbenzene, a chlorotoluene, the dichloro-toluene.
Described strong polar non-proton organic solvent is selected from N, one or more mixtures in dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, N-ethyl-2-pyrrolidone, the dimethyl sulfoxide (DMSO).
Described strong polar non-proton organic solvent is 5 milliliters～50 milliliters with the envelope-bulk to weight ratio of total organic reactant: 1 gram, wherein the weight of total organic reactant is meant 2, the weight sum of two (4-hydroxy phenyl) propane of 2-and 2-chloro-5-oil of mirbane trifluoride.
Described strong polar non-proton organic solvent is 26 milliliters with the envelope-bulk to weight ratio of total organic reactant: 1 gram
It is 100 ℃～180 ℃ that the reflux of described step (1) is divided the temperature of water reaction.
Description of drawings
Fig. 1 is 2, the molecular structure of two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] propane of 2-.
Fig. 2 is 2, differential scanning calorimeter (DSC) collection of illustrative plates of two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] propane of 2-.
Beneficial effect of the present invention:
(1) preparation method's product yield of the present invention and purity are all higher, are applicable to industrial production;
(2) need not the recrystallization operation, simplified technology, reduced production cost, reaction process is carried out under normal pressure, does not relate to also not producing corrosives, equipment is not had particular requirement, less investment;
(3) organic solvent uses kind few, and reclaims conveniently, Recycling repeatedly, and the three wastes are few, and energy consumption is low, and is environmentally friendly;
(4) reaction raw materials convenient sources, cost is lower, is convenient to further apply.
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 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.
Embodiment 1
With 22.8 gram (0.10 moles) 2, two (4-hydroxy phenyl) propane (BHPP) of 2-, 49.6 gram (0.22 mole) 2-chloro-5-oil of mirbane trifluoride (CNB-TF), 55.2 gram (0.40 mole) salt of wormwood, 500 milliliters of N, dinethylformamide and 200 milliliters of toluene are put into reactor, stir, reflux divides the water reaction after 10 hours, filtered while hot, remove filter residue, concentrated mother liquor reclaims solvent to recycle, cooling is left standstill, separate out crystallized product, filter, with pure water washing 2～3 times, dry, obtain 2 of 59.5 grams, two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] propane (BAPP-2TF) crystalline products of 2-(theoretical yield is 60.6 grams), purity is 99.5%, fusing point is 153.7 ℃ of (DSC method, N
2Atmosphere, 10 ℃/min; As shown in Figure 2).Obtain 2 according to theoretical yield with actual, the amount of two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] propane (BAPP-2TF) of 2-, calculate 2, the yield of two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] propane (BAPP-2TF) of 2-is 98.3%.
Embodiment 2
With 22.8 gram (0.10 moles) 2, two (4-hydroxy phenyl) propane (BHPP) of 2-, 45.1 gram (0.20 mole) 2-chloro-5-oil of mirbane trifluoride (CNB-TF), 55.2 gram (0.40 mole) salt of wormwood, 3395 milliliters of N, the N-N,N-DIMETHYLACETAMIDE, 300 milliliters of benzene and 40 milliliters of dimethylbenzene are put into reactor, stir, reflux divides the water reaction after 8 hours, filtered while hot, remove filter residue, concentrated mother liquor, reclaim solvent to recycle, cooling is left standstill, and separates out crystallized product, filter, with pure water washing 2～3 times, drying, obtain 56.8 grams 2, two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] propane (BAPP-2TF) crystalline products of 2-(theoretical yield is 60.6 grams), purity is 99.9%, obtains 2 according to theoretical yield with actual, the amount of two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] propane (BAPP-2TF) of 2-, calculate 2, the yield of two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] propane (BAPP-2TF) of 2-is 93.7%.
Embodiment 3
With 22.8 gram (0.10 moles) 2, two (4-hydroxy phenyl) propane (BHPP) of 2-, 47.4 gram (0.21 mole) 2-chloro-5-oil of mirbane trifluoride (CNB-TF), 10.6 gram (0.10 mole) yellow soda ash, 360 milliliters of N-N-methyl-2-2-pyrrolidone N-s, 700 milliliters of benzene and 20 milliliters of dichlorobenzenes are put into reactor, stir, reflux divides the water reaction after 10 hours, filtered while hot, remove filter residue, concentrated mother liquor, reclaim solvent to recycle, cooling is left standstill, separate out crystallized product, filter, with pure water washing 2～3 times, dry, obtain 56.1 grams 2, two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] propane (BAPP-2TF) crystalline products of 2-, purity is 99.4%, according to 2 of reality acquisition, amount of two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] propane (BAPP-2TF) of 2-and theoretical yield (60.6 gram) calculate 2, and the yield of two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] propane (BAPP-2TF) of 2-is 92.5%.
Embodiment 4
With 22.8 gram (0.10 moles) 2, two (4-hydroxy phenyl) propane (BHPP) of 2-, 11.8 gram (0.21 mole) potassium hydroxide, 500 milliliters of N-N-methyl-2-2-pyrrolidone N-s, 300 milliliters of benzene and 20 milliliters of dichlorobenzenes are put into reactor, stir, reflux divides the water reaction after 4 hours, add 47.4 gram (0.21 mole) 2-chloro-5-oil of mirbane trifluorides (CNB-TF), 10.6 gram (0.10 mole) yellow soda ash, reflux 6 hours, filtered while hot, remove filter residue, concentrated mother liquor, reclaim solvent to recycle, cooling is left standstill, separate out crystallized product, filter, with pure water washing 2～3 times, dry, obtain 57.3 grams 2, two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] propane (BAPP-2TF) crystalline products of 2-, purity is 99.7%, obtain 2 according to reality, amount of two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] propane (BAPP-2TF) of 2-and theoretical amount (60.6 gram) calculate 2, and the yield of two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] propane (BAPP-2TF) of 2-is 94.5%.
Embodiment 5
With 22.8 gram (0.10 moles) 2, two (4-hydroxy phenyl) propane (BHPP) of 2-, 47.4 gram (0.21 mole) 2-chloro-5-oil of mirbane trifluoride (CNB-TF), 20.0 gram (0.20 mole) saleratus, 13.8 gram (0.10 mole) salt of wormwood, 1000 milliliters of N-N-methyl-2-2-pyrrolidone N-s, 500 milliliters of dimethyl sulfoxide (DMSO), 300 milliliters of N, the N-N,N-DIMETHYLACETAMIDE, 450 milliliters of benzene and 150 milliliters of dimethylbenzene are put into reactor, stir, reflux divides the water reaction after 8 hours, filtered while hot, remove filter residue, concentrated mother liquor, reclaim solvent to recycle, cooling is left standstill, separate out crystallized product, filter, with pure water washing 2～3 times, dry, obtain 59.7 grams 2, two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] propane (BAPP-2TF) of 2-, purity is 99.2%, obtain 2 according to reality, amount of two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] propane (BAPP-2TF) of 2-and theoretical amount (60.6 gram), calculate 2, the yield of two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] propane (BAPP-2TF) of 2-is 98.5%.
Claims (7)
1.2 the preparation method of two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] propane of 2-comprises:
(1) mol ratio be 1.0: 2.0～2.2 2, two (4-hydroxy phenyl) propane of 2-and 2-chloro-5-nitro-trifluoromethyl toluene, in salt forming agent, organic mixed solvent system, reflux is divided water reaction 4～10 hours; Wherein organic mixed solvent is the mixture of water-insoluble organic solvent and strong polar non-proton organic solvent, and volume ratio is 1: 0.5～10; Described water-insoluble organic solvent is selected from one or more mixtures in benzene,toluene,xylene, monochloro-benzene, dichlorobenzene, trichloro-benzene, ethylbenzene, diethylbenzene, a chlorotoluene, the dichloro-toluene; Described strong polar non-proton organic solvent is selected from N, one or more mixtures in dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, N-ethyl-2-pyrrolidone, the dimethyl sulfoxide (DMSO);
(2) filtered while hot is removed filter residue, concentrated mother liquor, and cooling is left standstill, and separates out crystallized product, filter, washing, drying obtains 2, two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] the propane crystal of 2-.
2. according to claim 12, the preparation method of two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] propane of 2-, it is characterized in that: the salt forming agent of described 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.
3. according to claim 1 and 22, the preparation method of two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] propane of 2-is characterized in that: the salt forming agent and 2 of described step (1), the ratio of the mole number of 2-pair of (4-hydroxy phenyl) propane is 1～4: 1.
4. according to claim 12, the preparation method of two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] propane of 2-is characterized in that: the water-insoluble organic solvent in the described step (1) is 1: 1.6 with the volume ratio of strong polar non-proton organic solvent.
5. according to claim 12, the preparation method of two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] propane of 2-, it is characterized in that: described strong polar non-proton organic solvent is 5 milliliters～50 milliliters with the envelope-bulk to weight ratio of total organic reactant: 1 gram, wherein the weight of total organic reactant is meant 2, the weight sum of two (4-hydroxy phenyl) propane of 2-and 2-chloro-5-oil of mirbane trifluoride.
6. according to claim 52, the preparation method of two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] propane of 2-is characterized in that: described strong polar non-proton organic solvent is 26 milliliters with the envelope-bulk to weight ratio of total organic reactant: 1 gram.
7. according to claim 12, the preparation method of two [4-(2-trifluoromethyl-4-nitrophenoxy) phenyl] propane of 2-is characterized in that: it is that temperature is 100 ℃～180 ℃ reaction that the reflux of described step (1) is divided the water reaction.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
Non-Patent Citations (2)
| Title |
|---|
| Chin-Ping Yang等.Organosoluble and Light-Colored Fluorinated Polyimides Based on 2,2-Bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]propane and Aromatic Dianhydrides.《Journal of Applied Polymer Science》.2004,第95卷(第4期), * |
| Chin-PingYang等.OrganosolubleandLight-ColoredFluorinatedPolyimidesBasedon2 2-Bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]propane and Aromatic Dianhydrides.《Journal of Applied Polymer Science》.2004 |
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