CN101659647B - Method for preparing diphenyl tetracarboxylic dianhydride - Google Patents
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Abstract
The invention relates to a method for preparing diphenyl tetracarboxylic dianhydride. The diphenyl tetracarboxylic dianhydride is prepared by taking o-xylene as a raw material through halogenating, coupling, oxidation and dehydration. In the method, the conversion rate of the o-xylene is 100 percent; and the total yield of the diphenyl tetracarboxylic dianhydride is 55 percent, the melting range is between 298 and 301 DEG C, and the purity is between 99.5 and 99.8 percent. The diphenyl tetracarboxylic dianhydride uses the o-xylene as the raw material instead of chloro-anhydride by coupling first and then oxidizing, so the experimental route and the method are simple, economic and easy to operate. At the same time, because potassium permanganate with low price is adopted as an oxidant, an industrial preparation method, which is simple, convenient and economic and has low requirements on equipment, is provided.
Description
Technical field
The present invention relates to a kind of preparation method of bibenzene tetracarboxylic dianhydride, relating in particular to a kind of is the method for feedstock production bibenzene tetracarboxylic dianhydride with o-Xylol.
Background technology
Bibenzene tetracarboxylic dianhydride (being called for short BPDA) is very important polymkeric substance precursor, can become polyimide with multiple material polymerization.Polyimide is the highest kind of thermotolerance in the present industrialized macromolecular material, owing to have superior over-all properties, be widely used at high-technology field so can be used as film, coating, plastics, matrix material, tackiness agent, porous plastics, fiber, separatory membrane, liquid crystal aligning agent, photoresist material etc.Therefore, bibenzene tetracarboxylic dianhydride is as the important monomer of high-performance polyimide, and it synthesizes and application all is subjected to extensive concern both domestic and external.
The method that prepare at present bibenzene tetracarboxylic dianhydride is a lot, and for example Guchuang Chemical New Materials Co., Ltd., Shanghai reports with the 4-chloro-benzoic anhydride to be that feedstock production biphenyl dianhydride (CN1944419A), Chinese Academy of Sciences Changchun should be changed used electrochemical process and prepares biphenyl dianhydride (CN1410598).A lot of relevant reports are abroad also arranged.But these all are to be the raw material synthetic with the chloro-benzoic anhydride basically.
Yet the price of 4-chloro-benzoic anhydride is all very expensive both at home and abroad at present, and this has just increased the cost of producing biphenyl dianhydride.Thereby make and manyly want to utilize the company of biphenyl dianhydride to hang back.Be the feedstock production chloro-benzoic anhydride with phthalic anhydride or o-Xylol in addition, prepare BPDA with chloro-benzoic anhydride again, these method synthesis steps are many, and process is more loaded down with trivial details, and cost is higher.Though the organic spiral organic nickel of once utilizing in Chinese Academy of Sciences Shanghai is catalyzer, be feedstock production tetramethyl biphenyl (CN1660727A) with the Grignard reagent of dimethylbenzene.But, be difficult to large-scale production because of it requires harshness to equipment and reaction conditions.
Summary of the invention:
The objective of the invention is to overcome the defective that above-mentioned preparation bibenzene tetracarboxylic dianhydride exists, thereby the preparation method of a kind of cheapness, easy and simple to handle, the bibenzene tetracarboxylic dianhydride that is suitable for large-scale production is provided.
A kind of preparation method of bibenzene tetracarboxylic dianhydride comprises following reaction:
Halogenating reaction: be that raw material carries out halo and makes xylene halide with the o-Xylol;
Linked reaction: xylene halide makes 3 through coupling, and 3 ', 4,4 '-tetramethyl biphenyl;
Oxidizing reaction: 3,3 ', 4,4 '-tetramethyl biphenyl makes 3 through oxidation, and 3 ', 4,4 '-bibenzene tetracarboxylic;
Dehydration reaction: 3,3 ', 4,4 '-bibenzene tetracarboxylic obtains 3 through dehydration, and 3 ', 4,4 '-bibenzene tetracarboxylic dianhydride.
The present invention is to be that starting raw material prepares 3 by the tetramethyl biphenyl intermediate with the o-Xylol, 3 ', 4, and 4 '-bibenzene tetracarboxylic dianhydride, this method is produced bibenzene tetracarboxylic dianhydride, and is cheap, and production technique is simple simultaneously.
Description of drawings:
Fig. 1 be in the example 1 preparation 3,3 ', 4, the infrared spectrum of 4 '-tetramethyl biphenyl.
Fig. 2 be in the example 1 preparation 3,3 ', 4, the infrared spectrum of 4 '-bibenzene tetracarboxylic.
Fig. 3 be in the example 1 preparation 3,3 ', 4, the infrared spectrum of 4 '-bibenzene tetracarboxylic dianhydride.
Specific embodiment
A kind of preparation method of bibenzene tetracarboxylic dianhydride comprises following reaction:
Halogenating reaction: be that raw material carries out halo and makes xylene halide with the o-Xylol;
Linked reaction: xylene halide makes 3 through coupling, and 3 ', 4,4 '-tetramethyl biphenyl;
Oxidizing reaction: 3,3 ', 4,4 '-tetramethyl biphenyl makes 3 through oxidation, and 3 ', 4,4 '-bibenzene tetracarboxylic;
Dehydration reaction: 3,3 ', 4,4 '-bibenzene tetracarboxylic obtains 3 through dehydration, and 3 ', 4,4 '-bibenzene tetracarboxylic dianhydride.
Described halogenating reaction is to be raw material with the o-Xylol, the reaction in the presence of halogen and catalyzer.
Described catalyzer is iron and iodine, and wherein, the mol ratio of iron and iodine is greater than zero smaller or equal to 1: 1, wherein, good effect is all arranged in 0.1: 1,0.5: 1,1: 1.
The mol ratio of o-Xylol, catalyzer and halogen is 1 in the described halogenating reaction: 0.01-0.1: 0.6-1.
The temperature of described halogenating reaction is-20 ℃-10 ℃, is preferably-10 ℃-5 ℃, more preferably-5 ℃-0 ℃; Reaction times is 1-15 hour, is preferably 2-4 hour.
Halogen in the described halogenating reaction can be a chlorine or bromine, is preferably bromine.
Described halogenating reaction comprises that also the xylene halide to making carries out rectifying.By rectifying, the fractionation ratio is 1 with the thick product of xylene halide: 10-100, wherein, 1: 40,1: 50 and 1: 60 effect are best.Effectively raise the concentration of 4 position isomers.Make single halides of purity＞99.9%, 4 halo product purity＞87% wherein, product yield is between 90%-94%.
Described linked reaction is raw material with the xylene halide under the effect of the compound of nickel and triphenyl phosphorus in the organic solvent of nitrogen protection, reacts under the condition that promotor and reductive agent exist.
Described organic solvent can be N, one or more in dinethylformamide (DMF), N,N-dimethylacetamide (DMAC), the N-Methyl pyrrolidone aprotic polar solvents such as (NMP).Described promotor can be dipyridyl and/or alkali metal bromide.Described reductive agent can be one or more in zinc powder, hydrogen and the carbon monoxide.
The compound of described nickel can be one or both mixing in nickelous chloride and the nickel acetate.
The temperature of reaction of described linked reaction is 60 ℃-90 ℃, and the reaction mol ratio is recommended as xylene halide: triphenyl phosphorus: the compound of nickel: promotor: reductive agent is 1: 0.1-0.4: 0.01-0.1:0.01-0.1:1.5-3.
Described linked reaction also comprise to make 3,3 ', 4,4 '-tetramethyl biphenyl carries out recrystallization, the solvent of described recrystallization is a methyl alcohol.Gained 3,3 ', 4,4 '-tetramethyl biphenyl total recovery is at 75%-80%, purity behind the recrystallization〉99%.
Described oxidizing reaction is tetramethyl biphenyl adds second oxidant potassium permanganate and sodium hydroxide again after reaction under the condition of the aqueous solution coexistence of first oxidant potassium permanganate and pyridine a reactant aqueous solution, cools off again, filters, and drying is filtered in acidifying.Wherein, pyridine is the solvent as a dissolving raw material, and the environment of an alkalescence is provided.
The acidifying effect is and the sodium salt effect of bibenzene tetracarboxylic, generates bibenzene tetracarboxylic, and used hydrochloric acid is 20% concentrated hydrochloric acid, acidified effect, and the solution bottom obtains white solid.
The mol ratio that under the condition of described oxidizing reaction is tetramethyl biphenyl, first oxidant potassium permanganate, second oxidant potassium permanganate and sodium hydroxide is 1:8-12:4-6:15-25, and temperature of reaction is 100 ℃-130 ℃, and the reaction times is 24-36 hour.Product yield is 77%-85%, purity〉90%.
Described dehydration reaction is to be raw material with the bibenzene tetracarboxylic, thermal dehydration under protection of nitrogen gas, and Heating temperature is 60 ℃-300 ℃.
Described dehydration reaction is under protection of nitrogen gas, is that solvent carries out the reflux dewatering cyclisation with the lower aliphatic acid anhydrides, and the molar concentration rate of bibenzene tetracarboxylic and lower aliphatic acid anhydrides is 1:35.6.Described lower aliphatic acid anhydrides is a diacetyl oxide.
Product yield is 90%-95%, purity〉99%.
The present invention has realized first with the o-Xylol being that starting raw material prepares 3,3 ' by the tetramethyl biphenyl intermediate, 4, and 4 '-bibenzene tetracarboxylic dianhydride.In halogenating reaction,, effectively raise the ratio of 4 position isomers by utilizing the suitable fractionation ratio of rectifying tower control.In linked reaction, adopt simultaneously two kinds of catalyzer are added, need the trouble of prepared beforehand catalyzer before having avoided.And rationally utilize 2,2 '-dipyridyl is done promotor, effectively raises the productive rate of linked reaction.In the thick product of tetramethyl biphenyl, carry out recrystallization with methyl alcohol, obtain content〉99% 3,3 ', 4,4 '-tetramethyl biphenyl.In oxidizing reaction, adopt potassium permanganate under the condition of pyridine and sodium hydroxide, to react, avoided employing expensive catalysts and high-temperature high-pressure apparatus, simplified production technique.When acidifying prepared bibenzene tetracarboxylic, the solution of the HCl of employing 20% can effectively be avoided the injury of concentrated hydrochloric acid evaporable HCl gas to human body.
According to the present invention is 3,3 ', 4 of starting raw material preparation with the o-Xylol, and 4 '-bibenzene tetracarboxylic dianhydride, its total yield are 50%-60%, melting range 298-301 ℃, and purity〉99%.
(1) halogenating reaction prepares the preparation of halo o-Xylol
(569ml, 4.72moles), 2.5 gram iron powders and 2.5 restrain iodine to add o-Xylol 500g in the 1000ML four-hole bottle.Load onto dropping funnel, agitator, prolong, thermometer, the prolong top connects a gas absorbing device.Reaction mixture stirs and to be cooled to-5 ℃-5 ℃ under ice bath, and liquid bromine 660g (4.13moles) is by joining in the reaction flask slowly, is controlled in 3 hours to add.During this period, the temperature of reaction solution is controlled at-5 ℃-5 ℃ always, treats that the liquid bromine all adds, and reacting liquid temperature is allowed to rise to room temperature, and quiet to spending the night.Reaction solution is poured in the 500ML water then, stirs separatory.Wash twice with 3% sodium hydroxide solution afterwards.Clean twice with 500ML water again, separate organic phase, drying, rectification under vacuum gets the single bromo-derivative of 720g.Productive rate is 94% (amount with bromine is calculated).Thick product is purified through highly efficient distilling, and product purity reaches 99.9%, wherein 4-bromo-derivative purity 87% (HPLC).
(2) 3,3 ', 4, the preparation of 4 '-tetramethyl biphenyl
In the 250ML two-mouth bottle, add anhydrous chlorides of rase nickel 0.7g (5.4mmol), triphenyl phosphorus 5.38g (20.54mmol), zinc powder 16.24g (248.64mmol), 2 respectively, 2 '-dipyridyl 0.84g (5.4mmol).Load onto thermometer, rubber plug.Reaction flask is vacuumized, be full of nitrogen again, add the 100ML dry DMF to reaction flask, begin to stir, be warming up to 60 ℃ of reactions one hour, the solution becomes mazarine.Again 4-bromo o-Xylol 20g (108.1mmol) is dissolved in the 20ML dry DMF and slowly joins in the reaction flask, be controlled in 30 minutes and drip off.Again reaction solution is warming up to 90 ℃ and reacted 24 hours.Cooling is poured reaction solution in the 500ML aqueous hydrochloric acid of 2mol/L.Stir, filter, twice of the extracted with diethyl ether of water usefulness 200ML.Mix organic phase and use saturated NaHCO again
3Washing once.Use anhydrous MgSO
4Drying concentrates organic phase with Rotary Evaporators and gets 3, and 3 ', 4,4 '-tetramethyl biphenyl.Follow thick product anhydrous methanol recrystallization, vacuum-drying gets white needles solid phase prod yield 80%.Product purity 99% (HPLC).
(3) 3,3 ' 4, the preparation of 4 '-bibenzene tetracarboxylic
In 250ML single port bottle, add tetramethyl biphenyl 1.04g (4.95mmol), potassium permanganate 7.83g (49.5mmol), pyridine 60ML, deionized water 20ML respectively.Load onto reflux condensing tube, begin to stir and be warming up to 120 ℃.Question response carried out 24 hours, and the cooling reaction solution adds potassium permanganate 3.9g (24.75mmol), sodium hydroxide 3.762g (94.05mmol), deionized water 50ML and is warming up to 100 ℃ of reactions 12 hours to room temperature.Cooling is filtered, and filtrate is transferred to PH≤1 with 20% HCl solution.At this moment solution produces a large amount of white precipitates.Filter, add 6-10 deionized water and heated solution to 50 ℃ doubly in the filter cake, filtered while hot, solid in 100 ℃ of vacuum-dryings 1 hour 1.4g3,3 ' 4,4 '-bibenzene tetracarboxylic.Product yield 78% (product is by containing two crystal water conversions), product purity 95%.
(4) 3,3 ' 4, the preparation of 4 '-bibenzene tetracarboxylic dianhydride
In 250ML single port bottle, add bibenzene tetracarboxylic 11g (30mmol), anhydrous acetic acid acid anhydride 80ML that step (3) obtains respectively, load onto reflux condensing tube, under protection of nitrogen gas, be heated to 140 ℃ and reacted 4 hours.Be cooled to room temperature, filtration, filter cake washes three times with the small amount of acetic acid acid anhydride.Collect solid, get 8.2g3 in 100 ℃ of vacuum-dryings, 3 ' 4,4 '-bibenzene tetracarboxylic dianhydride, product yield 93% (raw material is by two crystal water conversions), 298～301 ℃ of melting ranges, purity 99.5%.
Fig. 1 be in the embodiments of the invention 1 preparation 3,3 ', 4, the infrared spectrum of 4 '-tetramethyl biphenyl.Simultaneously product is carried out mass spectrometric measurement, reading mass spectrum main peak value is 210,195,179,165,105,89,76,50, and our product of system is 3,3 ', 4 as can be known, 4 '-tetramethyl biphenyl.
Fig. 2 be in the example 1 of the present invention the preparation 3,3 ', 4, the infrared spectrum of 4 '-bibenzene tetracarboxylic.Simultaneously product is carried out hydrogen spectrum test, read hydrogen spectrum main peak value and be
1HNMR (DMSO-d
6, 500MHz) 7.961～7.935 (m, 4H); 7.801～7.774 (d, J=15Hz, 2H) as can be known we the system product be 3,3 ', 4,4 '-bibenzene tetracarboxylic.
Fig. 3 be in the example 1 preparation 3,3 ', 4, the infrared spectrum of 4 '-bibenzene tetracarboxylic dianhydride.Simultaneously product is carried out hydrogen spectrum test, read the hydrogen spectrum peak and be
1HNMR (DMSO-d
6, 500MHz) 8.59 (S, 2H); 8.475～8.443 (dd, J
1=15Hz, J
2=5Hz, 2H); 8.213～8.186 (d, J=15Hz, 2H) as can be known we the system product be 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride.
Claims (19)
1. the preparation method of a bibenzene tetracarboxylic dianhydride comprises following reaction:
Halogenating reaction: be that raw material carries out halo and makes xylene halide with the o-Xylol;
Linked reaction: xylene halide makes 3 through coupling, and 3 ', 4,4 '-tetramethyl biphenyl;
Oxidizing reaction: 3,3 ', 4,4 '-tetramethyl biphenyl makes 3 through oxidation, and 3 ', 4,4 '-bibenzene tetracarboxylic;
Dehydration reaction: 3,3 ', 4,4 '-bibenzene tetracarboxylic obtains 3 through dehydration, and 3 ', 4,4 '-bibenzene tetracarboxylic dianhydride.
2. the preparation method of bibenzene tetracarboxylic dianhydride according to claim 1, it is characterized in that: described halogenating reaction is to be raw material with the o-Xylol, the reaction in the presence of halogen and catalyzer.
3. the preparation method of bibenzene tetracarboxylic dianhydride according to claim 2, it is characterized in that: described catalyzer is iron and iodine, wherein, the mol ratio of iron and iodine is smaller or equal to 1: 1 greater than zero.
4. the preparation method of bibenzene tetracarboxylic dianhydride according to claim 2, it is characterized in that: the mol ratio of o-Xylol, catalyzer and halogen is 1 in the described halogenating reaction: 0.01-0.1: 0.6-1.
5. the preparation method of bibenzene tetracarboxylic dianhydride according to claim 2, it is characterized in that: the temperature of described halogenating reaction is-20 ℃-10 ℃, the reaction times is 1～15 hour.
6. the preparation method of bibenzene tetracarboxylic dianhydride according to claim 2, it is characterized in that: the halogen in the described halogenating reaction is a chlorine or bromine.
7. the preparation method of bibenzene tetracarboxylic dianhydride according to claim 2, it is characterized in that: the halogen in the described halogenating reaction is a bromine.
8. the preparation method of bibenzene tetracarboxylic dianhydride according to claim 2, it is characterized in that: described halogenating reaction comprises that also the xylene halide to making carries out rectifying.
9. the preparation method of bibenzene tetracarboxylic dianhydride according to claim 8, it is characterized in that: the fractionation ratio of described rectifying is 1: 10-100.
10. the preparation method of bibenzene tetracarboxylic dianhydride according to claim 1; it is characterized in that: described linked reaction is in the organic solvent of nitrogen protection; with the xylene halide raw material under the effect of the compound of nickel and triphenyl phosphorus, the reaction under the condition that promotor and reductive agent exist.
11. the preparation method of bibenzene tetracarboxylic dianhydride according to claim 10 is characterized in that: described organic solvent is N, one or more in dinethylformamide, N,N-dimethylacetamide and the N-Methyl pyrrolidone; Described promotor is dipyridyl and/or alkali metal halide; Described reductive agent is one or more in zinc powder, hydrogen and the carbon monoxide.
12. the preparation method of bibenzene tetracarboxylic dianhydride according to claim 11 is characterized in that: described dipyridyl is 2,2 '-dipyridyl.
13. the preparation method of bibenzene tetracarboxylic dianhydride according to claim 10 is characterized in that: the compound of described nickel is nickelous chloride and/or nickel acetate.
14. the preparation method of bibenzene tetracarboxylic dianhydride according to claim 10, it is characterized in that: the temperature of reaction of described linked reaction is 60 ℃-90 ℃, and the mol ratio of the compound of xylene halide, triphenyl phosphorus, nickel, promotor and reductive agent is 1: 0.1-0.4: 0.01-0.1: 0.01-0.1: 1.5-3.
15. the preparation method of bibenzene tetracarboxylic dianhydride according to claim 10 is characterized in that: described linked reaction also comprise to make 3,3 ', 4,4 '-tetramethyl biphenyl carries out recrystallization.
16. the preparation method of bibenzene tetracarboxylic dianhydride according to claim 1, it is characterized in that: described oxidizing reaction is tetramethyl biphenyl adds second oxidant potassium permanganate and sodium hydroxide again after reaction under the condition of the aqueous solution coexistence of first oxidant potassium permanganate and pyridine a reactant aqueous solution, cool off again, filter, acidifying, filter drying.
17. the preparation method of bibenzene tetracarboxylic dianhydride according to claim 16, it is characterized in that: the mol ratio of described tetramethyl biphenyl, first oxidant potassium permanganate, second oxidant potassium permanganate and sodium hydroxide is 1: 8-12: 4-6: 15-25, described oxidizing reaction temperature is 100 ℃-130 ℃, and the reaction times is 24-36 hour.
18. the preparation method of bibenzene tetracarboxylic dianhydride according to claim 1 is characterized in that: described dehydration reaction is to be raw material with the bibenzene tetracarboxylic, thermal dehydration under protection of nitrogen gas, and Heating temperature is 60 ℃-300 ℃.
19. the preparation method of bibenzene tetracarboxylic dianhydride according to claim 1; it is characterized in that: described dehydration reaction is under protection of nitrogen gas; with the lower aliphatic acid anhydrides is that solvent carries out the reflux dewatering cyclisation, and the molar concentration rate of bibenzene tetracarboxylic and lower aliphatic acid anhydrides is 1: 35.6.
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| CN102020622B (en) * | 2010-12-29 | 2012-09-05 | 中国科学院长春应用化学研究所 | Method for preparing 2,3,3',4'-biphenyltetracarboxylic di-anhydride |
| CN102329289A (en) * | 2011-07-19 | 2012-01-25 | 中国科学院长春应用化学研究所 | Method for preparing biphenyltetracarboxylic dianhydride (BPDA) |
| CN103086837B (en) * | 2013-02-07 | 2016-03-23 | 中国科学院长春应用化学研究所 | A kind of preparation method of tetramethyl biphenyl |
| CN104193580B (en) * | 2014-09-18 | 2017-02-15 | 哈尔滨工业大学（威海） | Separating and purifying method for tetramethyl biphenyl isomer mixture |
| CN106518820A (en) * | 2016-10-07 | 2017-03-22 | 常州创索新材料科技有限公司 | Synthesis method of 3,3',4,4'-biphenyltetracarboxylic anhydride |
| CN108333269A (en) * | 2018-02-01 | 2018-07-27 | 上海固创化工新材料有限公司 | A kind of purity analysis method of bibenzene tetracarboxylic dianhydride |
| CN108623544A (en) * | 2018-07-10 | 2018-10-09 | 江西师范大学 | A kind of preparation method of 4,4 '-two (3,4- dicarboxylic acid anhydrides benzoyl) biphenyl |
| CN109438470A (en) * | 2018-12-24 | 2019-03-08 | 山东盛华新材料科技股份有限公司 | One kind is containing two compound anhydride of thiophene and its synthetic method and application |
| CN110818551B (en) * | 2019-11-19 | 2022-06-24 | 常州市阳光药业有限公司 | Synthetic method of 3,3',4,4' -biphenyltetracarboxylic acid |
| CN115521280B (en) * | 2021-06-25 | 2024-03-26 | 中国石油化工股份有限公司 | Method for preparing 3,3', 4' -biphenyl tetracarboxylic acid and dianhydride thereof and obtained product |
| CN113651784B (en) * | 2021-08-30 | 2023-05-30 | 大连新阳光材料科技有限公司 | Synthesis method of 3,3', 4' -biphenyl tetracarboxylic dianhydride |
| CN114230540A (en) * | 2022-01-06 | 2022-03-25 | 西安爱德克美新材料有限公司 | Method for synthesizing alpha-BPDA |
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