CN101016284A - Preparing method of 3,4,3',4'-biphenyltetracarbosylic dianhydride - Google Patents
Preparing method of 3,4,3',4'-biphenyltetracarbosylic dianhydride Download PDFInfo
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Abstract
The invention discloses a making method of 3.4.3'.4'-biphenyl tetracarboxylic dianhydride, which comprises the following steps: adopting 4-chlorophthalandione anhydride as raw material; preparing 4-chlorophthalandione dimethyl ester, 3.3'.4.4'-biphenyl tetracarboxylic tetramethyl ester, 3.3'.4.4'-biphenyl tetracarboxylic acid and 3.3'.4.4'-biphenyl tetracarboxylic dianhydride; coupling; hydrolyzing; refining; (1) adopting p-toluenesulfonic acid as esterifying catalyst in the preparing procedure of 4-chlorophthalandione dimethyl ester; (2) adopting acetonitrile as solvent in the coupling procedure; (3) purifying hydrolytic 3.3'.4.4'-biphenyl tetracarboxylic acid through deionized water in the refining procedure; (4) washing and purifying 3.3'.4.4'-biphenyl tetracarboxylic dianhydride through acetone.
Description
Technical field
The present invention relates to the preparation method of a kind of 3.4.3 ' .4 '-BPDA.
Background technology
3.4.3 ' to be called for short BPDA be important fine chemicals for .4 '-BPDA, is widely used in heat-proof macromolecule material, for example as polyimide synthetic monomer, also can be used as curing agent for epoxy resin and medicine intermediate etc.It is most widely used aspect synthetic at the fire resistant polyimide material.
Have only at present several companies few in number to produce BPDA in the world, and synthetic method is comparatively complicated.
Foremost in the BPDA base polyimide promptly is high-performance polyimide film-Upilex that Zhu Shi commercial firm of Ube Industries Ltd. succeeded in developing the eighties in last century.Because the equal benzene type polyimide film Kapton of the performance of polyimide film biphenyl type and the exploitation of company of U.S. Du group, similarity is arranged, even more be better than equal benzene type film at some aspect of performance, therefore very fast in development aspect the variety yield since the nineteen eighty-three suitability for industrialized production.
This product is mainly used in flexible print circuit board, high-tech area such as the microelectronics that the high-density magnetic recording has higher requirements to safe reliability with base band etc., Aeronautics and Astronautics.
The electric property of biphenyl type PI film: under the dielectric strength room temperature of 25 μ m thick film up to 280kv/mm; Do not reduce under 200 ℃ yet.K dielectric loss tangent value temperature influence is bigger, but nonetheless, dielectric loss is also less than 0.01 in the time of 200 ℃.
Biphenyl type PI film also has dimensional stability, and this characteristic is fit to be applied on the intensive large-sized print wiring board very much, and the linear expansivity of Upilex-S film also is minimum, almost similar with the linear expansivity of copper foil material.
Polyimide is a kind of fabulous high temperature material, has good mechanical performance, dielectric properties, radiation resistance and solvent resistance.
The synthetic of relevant 3.4.3 ' 4 '-BPDA at first is the synthetic of intermediate 3.3 ' 4.4 '-bibenzene tetracarboxylic, the this respect reported in literature is a lot, the report of Pd/C catalysis synthesizing bibenzene tetracarboxylic (Japanese Patent JP7352749 for example, 80141417,8551151,8020705) coupling of halo aromatic ring Ni (O) catalysis in addition, zinc powder is as reductive agent, for example as catalyzer, zinc powder is as reductive agent with the triphenylphosphine nickelous chloride for the linked reaction of monochloro aromatic ring.And inorganic salt are as promotor [US.3.263.466 (1981)].Reported the linked reaction of chloro aromatic ring afterwards again, and used triaryl phosphine and trialkyl phosphine as dentate, wherein triphenylphosphine is best dentate, contains NiCl in reaction mixture
2With Sodium Bromide and zinc powder [J.org.chem 51, NO.14 (1986) 2627-2637].
Linked reaction is as follows:
This place R:C1-4 alkyl
Solvent adopts aprotic polar solvent such as dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMAC), N-Methyl pyrrolidone (NMP), methyl-sulphoxide (DMSO), hexamethyl phosphoric triamide (HMPA).Changchun should change patent report promptly be the synthetic of the synthetic method of biphenyl tetracid and derivative thereof about " 3.3 ' 4.4 '-biphenyl tetracid and derivative thereof synthetic " (patent No. 88107107) [EP.0363922], this patent report should be the method for more feasible synthetic 3.4.3 ' .4 '-BPDA till 1988.It is with the 4-monochloro phthalic anhydride be starting raw material in the presence of mineral acid with the synthetic 4-chlorophthalic acid dimethyl ester of methanol esterification.This synthetic method, the consumption of mineral acid is big, and by product causes a large amount of spent acid, is difficult for handling, and there is big difficulty in industrialization, and is also unfavorable to environmental protection, particularly is not sneezed at the dry hydrogen chloride environmental pollution.Though in this patent, mention and can use Catalyzed by p-Toluenesulfonic Acid, do not see but specifically implement report, do not see follow-up relevant report yet.
Its second step reaction is under the catalysis of triphenylphosphine nickelous chloride, with the Sodium Bromide is promotor, and zinc powder is a reductive agent, is that solvent carries out linked reaction with N,N-DIMETHYLACETAMIDE (DMAC), synthetic 3.3 ' .4.4 '-biphenyl four esters obtains the biphenyl tetracid by basic hydrolysis then.Select for use on the catalyzer with nickel in linked reaction to substitute precious metals such as palladium, platinum, this is significant improvement really.Yet remain N,N-DIMETHYLACETAMIDE (DMAC), dimethyl formamide (DMF), N-Methyl pyrrolidone (NMP), methyl-sulphoxide (DMSO), hexamethyl phosphoric triamide (HMPA) with regard to the solvent that it adopts, and these solvents are high boiling non-proton property polar solvent entirely, in handling, reaction product must adopt vacuum distilling, because temperature of reaction is at 40-100 ℃, can not be higher than this scope so steam the temperature of solvent, this reciprocal of duty cycle of will looking for the truth must be high, and this is trouble in suitability for industrialized production.Moreover the temperature height, will have a negative impact to product quality.Also having above-mentioned solvent all is more valuable solvents, must reclaim, and dehydration is a trouble in recovery.That is to say with above-mentioned these solvents are both uneconomical and also be unfavorable for technological operation.
About three acid of impurity that 3.3 ' .4.4 '-biphenyl tetracid refining pure is eliminated and mineral ion etc., mineral ion especially, this is step of key very, is related to into the quality of BPDA behind the acid anhydride.
Japanese Patent JP.91-74379 report 3.4.3 ' 4 '-bibenzene tetracarboxylic can be in 130-170 ℃ water recrystallization, the concentration of biphenyl tetracid is at 10-25%, the pka value of medium is below 2.5.Can remove mineral ion effectively, prepare highly purified biphenyl tetracid, alkali-metal content is below 1ppm; JP.95-206845 report biphenyl tetracid can make purity bring up to 99.8%, Na with the mixed solvent recrystallization of dioxane
+Content 0.9ppm.The former must carry out above purification process in potheater, and owing to be that the diluted acid medium apparatus should be glass lined potheater, there is hidden danger in this on safety.And the latter uses the expensive like this solvent of dioxane can strengthen the cost of PBDA.
About synthesizing of 3.4.3 ' .4 '-BPDA, existing method is roughly two classes, is dehydrated into acid anhydride under the first high temperature; It two is to be dehydrated into acid anhydride with the low carbon fatty acid anhydride reactant.The former is for example: JP.92-82859 is reported under the rough vacuum and becomes acid anhydride in 220 ℃ of thermal dehydrations; JR.96-134057 is reported under the 2700Pa vacuum tightness, is dehydrated into acid anhydride under 300-350 ℃; JR.89-50876 is reported under the protection of inert gas, and at the 40mmHg post, decompression is down in 255-280 ℃ of dehydration etc., appointed condition is required relatively stricter, realizes that industrialization acquires a certain degree of difficulty; The latter report be mostly with aceticanhydride altogether heat be dehydrated into acid anhydride, for example: JP.86-249977 report biphenyl tetracid press currently known methods, for example heats the generation dehydration reaction with the aceticanhydride of 2-10 times of weight under 100 ℃-boiling point and is easy to obtain BPDA; JP.87-116572 is reported in and adopts the aceticanhydride dehydration in the preparation of BPDA, and what adopt is the mixture of 3.4.3 ' 4 '-biphenyl tetracid and 2.3.3 ' 4 '-biphenyl tetracid, and reaction ends, and to separate what obtain be 3.4.3 ' .4 '-BPDA.
Summary of the invention
In order to overcome above-mentioned all shortcomings in the BPDA preparation, the invention provides a kind of easy, practical, effective method for preparing 3.4.3 ' .4 '-bibenzene tetracarboxylic dianhydride.
The present invention is achieved in that
A kind of 3.4.3 ' .4-BPDA preparation method, it is a raw material with the 4-monochloro phthalic anhydride, comprise the preparation of preparation, 3.3 ' .4.4 '-bibenzene tetracarboxylic tetramethyl ester and 3.3 ' the .4.4 '-bibenzene tetracarboxylic of 4-chlorophthalic acid dimethyl ester, the preparation process of 3.4.3 ' 4 '-bibenzene tetracarboxylic dianhydride, preparation at 3.3 ' .4.4 '-bibenzene tetracarboxylic tetramethyl ester and 3.3 ' .4.4 '-bibenzene tetracarboxylic comprises linked reaction, hydrolysis reaction, purification step again, it is characterized in that:
(1), in the preparation process of 4-chlorophthalic acid dimethyl ester, with right-toluenesulphonic acids as catalyst for esterification reaction:
(2), in linked reaction, adopt acetonitrile as solvent;
(3), in refining, be that 3.3 ' the .4.4 '-bibenzene tetracarboxylic that makes in the hydrolysis reaction is handled purifying with deionized water;
(4), in the preparation of 3.4.3 ' .4 '-bibenzene tetracarboxylic dianhydride, also comprise purification step, this purification step be will the preparation 3.4.3 ' .4 '-BPDA crude product washing with acetone purifying.
Described 3.4.3 ' .4 '-BPDA preparation method, in the preparation process of 4-chlorophthalic acid dimethyl ester, methyl alcohol be reactant be again solvent; Catalyst for esterification reaction is right-and the consumption of toluenesulphonic acids is the 5%-15% of raw material 4-chloro-benzoic anhydride weight; After the back flow reaction four hours, after distillation recovery methyl alcohol is extremely a certain amount of, in reaction mixture, add the equivalent fresh methanol again, so carry out adding for 4 times, at last residual methanol is all reclaimed, add water washing once after in resistates, adding the chloroform stirring and dissolving, during secondary water washing, add the solid sodium bicarbonate and be neutralized to PH=7, tell water again through the washing secondary, organic phase is distilled the recovery chloroform after drying, then under 80 ℃, vacuum distilling eliminates residual impurity, promptly gets 4-chlore O-phthalic acid dimethyl phthalate crude product.Content is at (GC mensuration) more than 96%, yield 85-90%.
In linked reaction, the consumption of solvent acetonitrile is 6-10 a times of 4-chlore O-phthalic acid dimethyl phthalate weight, and cross through molecular sieve drying, catalyzer adopts the co-ordination complex of triphenylphosphine nickelous chloride, promotor is Sodium Bromide, zinc powder is as reductive agent, and temperature of reaction is 78-83 ℃, reaction times 5-8 hour, collect filtrate behind the cold filtration and reclaim acetonitrile, resistates dissolves with chloroform, and it is inferior to give a baby a bath on the third day after its birth through saturated aqueous common salt, and organic phase reclaims chloroform after drying, then with resistates in below 80 ℃, vacuum is taken out most residual impurity in blowing below 50 ℃, and very fast crystallization promptly gets crude product 3.3 ' .4.4 '-bibenzene tetracarboxylic tetramethyl ester, and yield is more than 90%.
Described 3.4.3 ' .4 '-BPDA preparation method, 3.3 ' preparation process of .4.4 '-bibenzene tetracarboxylic also comprises, 3.3 ' .4.4 '-bibenzene tetracarboxylic tetramethyl ester crude product that linked reaction is obtained, refluxed 4 hours with the 20%NaOH aqueous solution, cooling back acid out promptly gets 3.3 ' .4.4 '-biphenyl tetracarboxylic acid crude.Crude product 3.4.3 ' .4 '-bibenzene tetracarboxylic is added to stirring heating refluxed 1 hour in 0.6% aqueous sulfuric acid of deionized water preparation of 6-10 times of weight, stop to stir to leave standstill being cooled to 50 ℃ of suction filtrations.Filter cake is added in the deionized water of 6 times of its weight again, stir and be warming up to 80-90 ℃, stop heating, leave standstill and be cooled to 50 ℃ of suction filtrations.Same operation repeats once, at last with the filter cake centrifuge dripping and under 70-80 ℃, dries 8 hours, promptly gets the dihydrate of elaboration 3.3 ' .4.4 '-bibenzene tetracarboxylic, and in 4-chlorophthalic acid dimethyl ester, yield is 75-80%.Na and Cl all are lower than 1ppm.
3.4.3 ' preparation of .4 '-bibenzene tetracarboxylic dianhydride is that purified 3.3 ' .4.4 '-bibenzene tetracarboxylic and aceticanhydride are heated with stirring to 120 ℃ under nitrogen protection, keeps 4 hours, be cooled to then below 40 ℃, suction filtration both crude product biphenyl acid anhydride.
3.4.3 ' purification step of .4 '-bibenzene tetracarboxylic dianhydride is: crude product 3.3 ' .4.4 '-BPDA is weighed, it is added to agitator treating in the acetone of 5-6 times of weight, with the mixture suction filtration, use acetone drip washing secondary again, drain the back under 70-80 ℃, decompression oven dry 6-8 hour, promptly get elaboration 3.4.3 ' .4 '-bibenzene tetracarboxylic dianhydride, yield 83-86%, fusing point: 301 ℃, Na
+All be no more than 1ppm with Cl, its infrared spectra and H-NMR spectrum are seen accompanying drawing.
Advantage of the present invention is:
(1) 4-monochloro phthalic anhydride esterification does not have spent acid formation, has saved the processing to a large amount of spent acid; Resultant also need not the molecular distillation purifying, and crude product promptly can be used for the linked reaction of bottom.Content is more than 96%, and yield is at 85%-90%.
(2) owing to adopt the solvent of acetonitrile as linked reaction, its boiling point is 81.6 ℃, just in the temperature of reaction of needs, as long as reflux the fabulous control of temperature of reaction.Moreover because but the low air distillation of its boiling point is reclaimed, and solvent recovering rate can reach more than 80%, solvent is reusable after repurity.Owing to adopt decompress filter can reclaim catalyzer, promotor and excessive zinc powder easily, triphenylphosphine, zinc powder and Sodium Bromide are reclaimed in mixture useable solvents and water treatment.
(3) the resultant 3.3 ' .4.4 ' of linked reaction-bibenzene tetracarboxylic tetramethyl ester crude product can not purified direct saponification hydrolysis, obtain the wet product of 3.3 ' .4.4 '-bibenzene tetracarboxylic and directly handle purifying with deionized water, the yield of 3.3 ' .4.4 '-bibenzene tetracarboxylic elaboration is 75%-80% with the 4-chlorophthalic acid dimethyl ester rate of collecting; Na
+Be lower than 1ppm with the content of Cl-.
(4) elaboration 3.3 ' the .4.4 '-bibenzene tetracarboxylic dihydrate that obtains is processed into acid anhydride with aceticanhydride, and the excessive aceticanhydride and the acetic acid of generation can reclaim acetic acid and aceticanhydride by fractionation.3.3 ' .4.4 '-BPDA crude product obtains elaboration 3.4.3 ' .4 '-BPDA through the acetone treatment purifying.Yield is 83%-86%; Na
+All be no more than 1ppm with the content of Cl-, fusing point is 301 ℃.
Below in conjunction with embodiment the present invention is done to specify, but the present invention is not limited only to scope of embodiments
Description of drawings
Fig. 1 is for making the infrared spectrogram of material among the embodiment 1
Fig. 2 is for making the H-NMR spectrum of material among the embodiment 1
Fig. 3 is the H-NMR spectrum enlarged view of Fig. 2
Embodiment
Embodiment
The preparation of A, 4-chlorophthalic acid dimethyl ester:
Add 4-monochloro phthalic anhydride 91.2g (0.5mol) in the 2000ml four-hole bottle, tosic acid 9.1g and methyl alcohol 800ml load onto reflux exchanger, thermometer, agitator and 250ml dropping funnel.Start stirring, electric mantle is heated to backflow, keep refluxing 4 hours, change backflow into distillation then, whenever steam 100ml methyl alcohol, add the 100ml fresh methanol, so add four times by dropping funnel, at last residual methanol is all reclaimed (still bottle temperature must not above 80 ℃), the decompression of boiling water pump was taken out 1 hour then, and cooling back emptying adds deionized water 800ml stirring and is transferred to standing demix in the 1000ml separating funnel after 5 minutes, branch vibration layer, oil reservoir adds chloroform 600ml, adds water 300ml after the dissolving, and adding sodium bicarbonate a bit is neutralized to PH7 a bit to shake up the back, branch vibration layer, organic layer is cleaned with the deionized water of 300ml * 3.Use anhydrous magnesium sulfate drying then, filter, steam except that behind the chloroform, raffinate promptly gets 4-chlorophthalic acid dimethyl ester crude product after 80 ℃ half an hour is taken out in decompression down, and it is 96.8% that GC measures content.Receipts amount 103.0g, yield 90%.
B, about the preparation of 3.3 ' .4.4 '-bibenzene tetracarboxylic tetramethyl ester and 3.3 ' .4.4 '-bibenzene tetracarboxylic and refining:
(1) linked reaction
(2) hydrolysis reaction
Feed intake
4-chlore O-phthalic acid dimethyl phthalate 42.6g (0.186mol)
Anhydrous Sodium Bromide 49.2g
Triphenylphosphine nickelous chloride co-ordination complex 5.0g
Acetonitrile (crossing) 378.4ml (297.4g) through molecular sieve drying
Zinc powder 25.2g
Operation:
In the 1000ml four-hole bottle, drop into 4-chlore O-phthalic acid dimethyl phthalate; triphenyl phosphine nickelous chloride co-ordination complex and acetonitrile are opened nitrogen (purity nitrogen) through surge flask; sulfuric acid wash bottle and hydroxide flake potassium drying tower enter reaction flask; start agitator under nitrogen protection, the logical nitrogen of stirring drops into the zinc powder restir and began heat up (electric mantle heating) in 5 minutes after 10 minutes.Connect the Calcium Chloride Powder Anhydrous drying tube on the reflux exchanger, when temperature rises to 78 ℃, begin to reflux.Warm 78-80 ℃ was refluxed 4 hours down in the still bottle, and after stopping heating and being cooled to room temperature, filtration under diminished pressure is collected filtrate, and behind filtrate distillation (still bottle temperature must not above 80 ℃) recovery acetonitrile, resistates is being no more than under 80 ℃, and vacuum is drained half an hour.After the resistates cooling, be transferred in the separating funnel with the stripping of 400ml chloroform, chloroformic solution washs with saturated aqueous common salt 200ml * 3, filter through anhydrous magnesium sulfate drying then, collect filtrate, distillation concentrates reclaims chloroform, then with resistates decompressing and extracting (below 80 ℃).
(2) hydrolysis
In resistates, add 20% aqueous sodium hydroxide solution 400g, reflux is 4 hours under stirring, cooling drops into trash ice 200g then, after under stirring, adding the reagent concentrated hydrochloric acid and being acidified to PH2 and leaving standstill 0.5 hour, and suction strainer, leach crystallization, add the 200ml deionized water, making beating washing, decompress filter, so use deionized water wash 3 times, get the wet crude product of 3.3 ' .4.4-bibenzene tetracarboxylic through centrifuge dripping again after draining at last.
(3) refining
Wet tetracid crude product weighed be transferred to 0.6% aqueous sulfuric acid of the deionized water preparation that adds 8 times of amounts of crude product weight in the four-hole bottle that has agitator thermometer and nitrogen access tube, start behind the logical nitrogen and be heated with stirring to 80-90 ℃, and under this temperature, kept 1 hour, stop then stirring and leave standstill nature and be cooled to below 50 ℃, filtration under diminished pressure, collect crystallization, again with 200ml deionized water making beating washing three times, after draining, centrifuge dripping again, place baking oven to dry 8 hours down, promptly get 3.3 ' .4.4 '-bibenzene tetracarboxylic dihydrate elaboration 27.3g, yield 80.0% (by 4-chlore O-phthalic acid dimethyl phthalate) in 70-80 ℃.Assay: 99.8%, Na
+With Cl less than 1ppm.C, about the preparation of 3.4.3 ' .4 '-bibenzene tetracarboxylic dianhydride:
Charging capacity
3.3 '-4.4 '-biphenyl tetracid dihydrate 22.0g (0.0655mol)
Aceticanhydride 100ml (108.2g)
Operation:
In the 250ml four-hole bottle, drop into 3.3 ' .4.4 '-biphenyl tetracid dihydrate, feed access tube by nitrogen and feed nitrogen adding aceticanhydride 100ml, start stirring, under stirring, be warming up to 120 ℃, and under 120-115 ℃, stirred 4 hours, stop heating, be cooled to below 40 ℃, with G-4 frosted funnel decompress filter; Collect crystallization, with acetone making beating washing, suction strainer is washed secondary with acetone more again, places vacuum drying oven 70-80C vacuum-drying 8 hours then, obtains off-white color crystalline powder 15.2g, yield: 86.0%.Fusing point: 301 ℃, Na
+All be no more than 1ppm with Cl.Its infrared spectra and H-NMR spectrum are seen accompanying drawing 1 and accompanying drawing 2.
Wherein, accompanying drawing l is the infrared spectra of 3.4.3 ' .4 '-BPDA
Resolve: wave number 1855cm
-1Be vc=O1785cm
-1Be vc=O
No carboxylic hydroxyl peak on the infrared spectrogram.
Conclusion: the vc=O of infrared spectra promptly proves in the chemical structure
The existence of base, and on spectrogram, do not see the carboxylic hydroxyl peak.
Accompanying drawing 2 is the H-NMR spectrum of 3.4.3 ' .4 '-BPDA
Conclusion: proton nmr spectra, 6 protons in the chemical structure respectively have ownership, prove the structural formula such as the following formula of this compound, and the material that promptly makes is 3.3 ' .4.4 '-BPDA.
Comparative example:
The preparation of A, 4-dimethyl phthalate
Feed intake: 4-monochloro phthalic anhydride 150g
Methyl alcohol 200mL
Tetracol phenixin 80mL
Sulfuric acid 60mL
In the 1000mL four-hole bottle, drop into tetrachlorobenzene acid anhydride, methyl alcohol and tetracol phenixin, installation agitator, thermometer, reflux exchanger and dropping funnel, start stirring, the electric mantle heat temperature raising, 25 ℃ rise beginning by dropping funnel drip sulfuric acid to 60 ℃ solution become transparent, with adding sulfuric acid in 15 minutes.Add sulfuric acid 10mL then under 68 ℃, after this kept 4.5 hours down in 70-77 ℃, stop heating, cooling slowly drips water 500mL, finishes to be transferred in the 1000mL separating funnel, divides water-yielding stratum, carbon tetrachloride solution 10%NaCO
3Wash with water behind the solution washing to neutrality again, divide water-yielding stratum, tetracol phenixin is transferred in the matrass, removes tetracol phenixin under reduced pressure, receive crude product 142g.Yield 76%.
B, about the preparation of 3.3 ' .4.4 '-bibenzene tetracarboxylic tetramethyl ester and 3.3 ' .4.4 '-bibenzene tetracarboxylic.
(1) 4-chlorophthalic acid dimethyl ester linked reaction
Feed intake:
4-chlorophthalic acid dimethyl ester 30g
Triphenylphosphine nickelous chloride complex compound 3.5g
Sodium Bromide 28.5g
Zinc powder 18g
N,N-DIMETHYLACETAMIDE 150mL
Operation: in the 1000mL four-hole bottle, drop into 4-dimethyl phthalate, triphenylphosphine nickelous chloride complex compound, Sodium Bromide and N,N-DIMETHYLACETAMIDE, load onto agitator, reflux exchanger and thermometer.Start stirring, drop into zinc powder under the room temperature, be warming up to 58 ℃ naturally after no longer heat release, 80 ℃ of beginning heat temperature raisings, and under this temperature, kept 4 hours, heating stopped, when temperature is reduced to 68 ℃, heat efficiency is collected filtrate, is transferred in the matrass, under-0.098MPa, remove N,N-DIMETHYLACETAMIDE under reduced pressure and do not remove to there being the fraction steaming, cooling emptying, resistates i.e. 3.3 ' 4.4 '-bibenzene tetracarboxylic tetramethyl ester crude product.
(2) hydrolysis preparation 3.3 ' 4.4 '-bibenzene tetracarboxylic.
Feed intake: 3.3 ' 4.4 '-bibenzene tetracarboxylic tetramethyl ester crude product that above-mentioned reaction obtains is whole.
20%NaOH aqueous solution 100ml
Operation: crude product 3.3 ' 4.4 '-bibenzene tetracarboxylic tetramethyl ester all is transferred in the 250ml there-necked flask, loads onto agitator, reflux exchanger and thermometer.Start stirring, electric mantle reflux (95 ℃) 3.5 hours, stop to add water 150ml, decompress filter is collected filtrate and is used the concentrated hydrochloric acid acidifying, separates out the crystallization decompress filter, washing three was dried 6 hours down inferior to 70-80 ℃, get white crystalline powder 3.3 ' 4.4 '-biphenyl tetracid dihydrate 17.4g, 315 ℃ of fusing points, yield 72.4% (in 4-chlorophthalic acid dimethyl ester).
C, about the preparation of 3.4.3 ' .4 '-bibenzene tetracarboxylic dianhydride.
Charging capacity:
3.3 ' .4.4 '-biphenyl tetracid dihydrate 9.0g
Aceticanhydride 114ml
Operation: 3.3 ' .4.4 '-bibenzene tetracarboxylic is dropped in the 250ml four-hole bottle, load onto agitator, thermometer and reflux exchanger, start agitator, the electrically heated cover is heated to 124 ℃, under 124 ℃-128 ℃, stirred 1 hour, cooling is cooled to below 40 ℃, decompress filter, and leaching crystallization is that yellow crystal washs with a small amount of aceticanhydride, in 70 ℃-80 ℃ drying baker, dried 8 hours behind the suction filtration, get 3.4.3 ' .4 '-BPDA 5g, 295 ℃-300 ℃ of fusing points, yield: 69.1%.Na
+Content 95ppm with Cl-.
Claims (5)
1, a kind of 3.4.3 ' .4 '-BPDA preparation method, it is a raw material with the 4-monochloro phthalic anhydride, comprise the preparation of preparation, 3.3 ' .4.4 '-bibenzene tetracarboxylic tetramethyl ester and 3.3 ' the .4.4 '-bibenzene tetracarboxylic of 4-chlorophthalic acid dimethyl ester, the preparation process of 3.4.3 ' .4 '-bibenzene tetracarboxylic dianhydride, preparation at 3.3 ' .4.4 '-bibenzene tetracarboxylic tetramethyl ester and 3.3 ' .4.4 '-bibenzene tetracarboxylic comprises linked reaction, hydrolysis reaction, purification step again, it is characterized in that:
(1), in the preparation process of 4-chlorophthalic acid dimethyl ester, with right-toluenesulphonic acids as catalyst for esterification reaction;
(2), in linked reaction, adopt acetonitrile as solvent;
(3), in refining, be that 3.3 ' the .4.4 '-bibenzene tetracarboxylic that makes in the hydrolysis reaction is handled purifying with deionized water;
(4), in the preparation of 3.4.3 ' .4 '-bibenzene tetracarboxylic dianhydride, refining be will preparation 3.4.3 ' .4 '-BPDA crude product washing with acetone purifying.
2,3.4.3 ' .4 ' according to claim 1-BPDA preparation method is characterized in that, in the preparation process of 4-chlorophthalic acid dimethyl ester, methyl alcohol be reactant be again solvent; Catalyst for esterification reaction is right-toluenesulphonic acids, and its consumption is the 5%-15% of raw material 4-chloro-benzoic anhydride weight; After the back flow reaction four hours, after distillation recovery methyl alcohol is extremely a certain amount of, in reaction mixture, add the equivalent fresh methanol again, so carry out adding for 4 times, at last residual methanol is all reclaimed, add water washing once after in resistates, adding the chloroform stirring and dissolving, during secondary water washing, add the solid sodium bicarbonate and be neutralized to PH=7, tell water again through the washing secondary, organic phase is distilled the recovery chloroform after drying, then under 80 ℃, vacuum distilling eliminates residual impurity, promptly gets 4-chlore O-phthalic acid dimethyl phthalate crude product.
3,3.4.3 ' .4 ' according to claim 1-BPDA preparation method, it is characterized in that, in linked reaction, the solvent acetonitrile, its consumption is 6-10 a times of 4-chlore O-phthalic acid dimethyl phthalate weight, catalyzer adopts the co-ordination complex of triphenylphosphine nickelous chloride, promotor is Sodium Bromide, zinc powder is as reductive agent, temperature of reaction is 78-83 ℃, and reaction times 4-6 hour, acetonitrile was reclaimed in air distillation behind the cold filtration, resistates dissolves with chloroform, give a baby a bath on the third day after its birth time through saturated aqueous common salt, organic phase reclaims chloroform after drying, then with resistates in below 80 ℃, vacuum is taken out most residual impurity in blowing below 50 ℃, and very fast crystallization promptly gets crude product 3.3 ' .4.4 '-bibenzene tetracarboxylic tetramethyl ester.
4,3.4.3 ' .4 ' according to claim 1-bibenzene tetracarboxylic preparation method, it is characterized in that, crude product 3.4.3 ' .4 '-bibenzene tetracarboxylic is added to stirring heating refluxed 1 hour in 0.6% aqueous sulfuric acid of deionized water preparation of 6-10 times of weight, stop to stir to leave standstill being cooled to 50 ℃ of suction filtrations.Filter cake is added in the deionized water of 6 times of its weight again, stir and be warming up to 80-90 ℃, stop heating, leave standstill and be cooled to 50 ℃ of suction filtrations.Same operation repeats once, at last with the filter cake centrifuge dripping and under 70-80 ℃, dries 8 hours, promptly gets the dihydrate of elaboration 3.3 ' .4.4 '-bibenzene tetracarboxylic.
5,3.4.3 ' .4 ' according to claim 1-BPDA preparation method, it is characterized in that, at the refining of 3.4.3 ' .4 '-bibenzene tetracarboxylic dianhydride be, crude product 3.3 ' .4.4 '-BPDA is weighed, it is added to agitator treating in the acetone of 5-6 times of weight, the mixture suction filtration, use acetone drip washing secondary again, drain the back under 70-80 ℃, decompression oven dry 6-8 hour promptly gets elaboration 3.4.3 ' .4 '-bibenzene tetracarboxylic dianhydride.
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