CN1706846A - Synthesis process of 4,4'-diphenyl ether tetraformic acid dihydride - Google Patents
Synthesis process of 4,4'-diphenyl ether tetraformic acid dihydride Download PDFInfo
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- CN1706846A CN1706846A CN 200410048635 CN200410048635A CN1706846A CN 1706846 A CN1706846 A CN 1706846A CN 200410048635 CN200410048635 CN 200410048635 CN 200410048635 A CN200410048635 A CN 200410048635A CN 1706846 A CN1706846 A CN 1706846A
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- diphenyl ether
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- ether tetraformic
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Abstract
The present invention is new process of preparing 4, 4'-diphenyl ether tetraformic dihydride, and the preparation process has high purity 4-chlorophthalic anhydride as main material which is reacted with carbonate of alkali metal in 2, 6-dichloro benzene as solvent and under the action of phase transfer catalyst so as to eliminate one Cl2 molecule from two 4-chlorophthalic anhydride molecules. When high boiling point solvent is used, no catalyst is needed, 4-chlorophthalic anhydride and potassium carbonate react at 222-224 deg.c for 8-16 hr, and after filtering, crystallization and drying, coarse 4, 4'-diphenyl ether tetraformic dihydride is obtained in the yield of 66.5 %. The coarse 4, 4'-diphenyl ether tetraformic dihydride may be purified through hydrolysis into ether acid and dewatering to cyclize to purity of 99 %. Or, the coarse product may be re-crystallized in 2, 6-chlorotoluene to reach purity of 99.5 %.
Description
The present invention relates to a kind of gaseous product that directly generates from a chloro-o-xylene catalytic gas phase oxidation and sublimate through passive hot wall that to capture the high purity 4-chloro-benzoic anhydride that obtains be feedstock production 4, the novel method of 4 '-diphenyl ether tetraformic dianhydride.
4,4 '-diphenyl ether tetraformic dianhydride (abbreviation ODPA-M) is one of important monomer of synthetic ODPA-M type polyimide.ODPA-M type polyimide is a soluble polyimide, and it is a thermoplastic polymer.It has good physics, mechanical property, can be in 250 ℃ of use of-269 ∽, but at 230 ℃ of-180 ∽ life-time service down.Owing in the polyimide main chain, introduce flexible ehter bond, reduced softening temperature, thereby good processing properties is arranged.Its better solubility is easy to machine-shaping more than equal acid anhydride type polyimide, and the corrosion of anti-benzene, oil, organic solvent and hydrochloric acid.In aerospace and other hard-core technology field important purposes is arranged,, also constantly be used widely as industry such as electronics, electrical equipment, automobiles in sector of the national economy.In addition, ODPA-M also is the important source material of dyestuff intermediate and synthetic drugs.
The method of industrial production ODPA-M has (1) halo o-Xylol and 3, and 4-xylenol elder generation etherification oxidation becomes acid, and last acid is dehydrated into acid anhydride; (2) phthalic anhydride through amination, nitrated make the nitrophthalide imide after, carry out etherificate, hydrolysis, acidifying system ether acid again and be dehydrated into acid anhydride; (3) earlier with the nitrated synthesizing nitryl phthalic anhydride of phthalic anhydride, bimolecular is condensed into ether then; (4) monochloro-benzene acid anhydride and hydroxyl phthalic anhydride are condensed into the ether acid anhydride; (5) dechlorination in the presence of phase-transfer catalyst of monochloro-benzene acid anhydride and alkaline carbonate is condensed into the ether acid anhydride.The common drawback of first three methods is that synthetic route is long, causes total recovery not high, and the three wastes are more serious, the cost height.Some method need can produce carcinogenic substance and problem of environmental pollution through nitrated, and back two kinds of methods need not be nitrated, from halobenzoyl anhydride, can protect without imide, and this is favourable to shortened process undoubtedly.But used chloro-benzoic anhydride is with benzene anhydride oxidized and get, owing to generate the product complexity, is difficult to make with extra care, and general purity only is 88%, the highlyest also is no more than 93%, the chloro-benzoic anhydride of this purity be difficult to the ODPA-M of system polymerization-grade.In recent years, domestic Harbin City Time Technology Development Co., Ltd carries out liquid phase catalytic oxidation with chloro-o-xylene, makes the 4-chloro-benzoic anhydride that purity reaches 97-98%, and this has laid the raw material basis for synthetic ODPA-M.But liquid phase method production cost height is serious to equipment corrosion, need select the expensive titanium material equipment of valency for use, and will adopt decompression distillation that chloro-benzoic anhydride is purified, and this method weak point is that Production Flow Chart is long, investment cost and production cost height.
The present invention is that to propose a kind of gaseous product that generates from the chloro-o-xylene catalytic gas phase oxidation be the novel method that raw material synthesizes ODPA-M through the 4-chloro-benzoic anhydride that " passive hot wall sublimate captures " obtains purity 99%.This law and the liquid phase method equipment that compares does not have corrosion substantially, without the titanium material, reduces facility investment greatly, need not acid be dehydrated into acid anhydride and decompression distillation purification, and it is to simplify flow process, cuts down the consumption of energy, and is convenient to the desirable processing method that serialization is produced.
The present invention is to be that 99% 4-chloro-benzoic anhydride is that raw material is protected without imide with the purity that above-mentioned " passive hot wall sublimate capture " method gets, and with 2, the 6-dichlorobenzene is made solvent, under the phase-transfer catalyst effect, sloughs Cl with alkaline carbonate
2And directly make ODPA-M.
The present invention realizes like this.The 4-chloro-benzoic anhydride of high purity (99%) makes by " passive hot wall sublimate capture method ": a chloro-o-xylene, in the presence of catalyzer, carry out the fixed bed oxidation with air, and temperature of reaction 360-440 ℃, air speed 2500-3500h
-1, catalyst loading 70g/h.l, the gas-phase product of generation are mainly 4-chloro-benzoic anhydride and 3-chlorinated benzene, and it forms about 34/66.Also have by products such as phthalic anhydride in addition.This mixed gas is carried out heat exchange earlier reduce temperature, enter the passive hot wall device of sublimating, controlled temperature is at 85-95 ℃, and one goes on foot continuous high-efficient and obtains the 4-chloro-benzoic anhydride of purity 99% and 98.5% 3-chloro-benzoic anhydride respectively in capturing the district.
4, the synthetic method of 4 '-diphenyl ether tetraformic dianhydride is 4-chloro-benzoic anhydride and the alkaline carbonate with above-mentioned 99%, under the phase-transfer catalyst effect, with 2, the 6-dichlorobenzene is sloughed chlorine and is made ODPA-M as solvent reaction, the mol ratio of 4-chloro-benzoic anhydride and salt of wormwood is (2-4): 1, and temperature of reaction is 222-224 ℃, normal pressure reacted 8-16 hour down.Yield is 66.5%, if reaction uses high boiling solvent (as 1,3, the 5-trichlorobenzene) can not use catalyzer, 4-chloro-benzoic anhydride and salt of wormwood fed intake in 4: 1 in molar ratio, reacted 18 hours down at 224-225 ℃, product is treated, dry, and its yield is 64.6%, and coarse ODPA is through being hydrolyzed into ether acid, dehydration condensation gets smart ODPA-M then, and purity can reach 99%; Or can make product purity reach 99.5% with the toluene dichloride recrystallization, unreacted raw material and solvent can recycle and reuse.
An alkali metal salt of the present invention can be K
2CO
3, Na
2CO
3
The used phase-transfer catalyst of the present invention can be tetraphenylphosphonium chloride (TPPC), tetraphenylphosphonibromide bromide, tetrabutyl phosphonium bromide phosphine (TBPB) and 4-chloro-benzoic acid.
Specific embodiments of the invention are as follows:
Embodiment 1:
Take by weighing 50g 4-chloro-benzoic anhydride and 150ml dichlorobenzene, place the 500ml there-necked flask, stirring heats up down makes the dissolving of 4-chloro-benzoic anhydride, adds 0.24g tetraphenylphosphonibromide bromide and 0.06g Chlorodracylic acid, stirs and feed N then
2Gas, heat temperature raising has a small amount of solvent to reflux when temperature of charge is raised to about about 160-180 ℃, and just (purpose is to use N keeping about 1 hour under this temperature
2Gas is taken away the minor amount of water that exists in the solvent, because this test must the guarantee system exclusion), after 1 hour temperature is raised to 220-224 ℃, material is reddened by yellow, and a large amount of solvent refluxings are arranged.
Take by weighing 20gK
2CO
3, put into baking oven and dried by the fire 1 hour down in 110-120 ℃, taking-up adds in the reactor at twice then: add 15g for the first time, at this moment temperature may reduce, and heats when returning to 220-224 ℃ again with remaining 5gK
2CO
3Add, keep temperature of reaction at 220-224 ℃, N
2Gas 40ml/ branch, reaction is 14-16 hour under reflux state, stopped reaction; Add the 30ml trichlorobenzene to reaction mass again, be heated to 220 ℃, the suction strainer of under insulation, finding time while hot.Filtrate was placed in the ventilating frame naturally cooling 24 hours, promptly has large-tonnage product to crystallize out, cold filtration, pink solid coarse ODPA 33.4g (yield is 66.8%).
Embodiment 2:
Solvent uses 1,3 instead, and 5-trichlorobenzene high boiling solvent (150ml) need not add the tetraphenylphosphonibromide bromide phosphine catalyst, adds 50g 4-chloro-benzoic anhydride and 9.45g particle K
2CO
3(mol ratio is 4: 1), temperature of reaction 223-225 ℃, in 24 hours reaction times, other gets coarse ODPA 32.3g (yield is 64.6%) with embodiment 1 reaction result.
Embodiment 3:
Get the 20g coarse ODPA, be dissolved in the NaOH aqueous solution of 65g20%, be heated to 80 ℃ the ether acid anhydride is all dissolved, add 2.5 gacs again, remove by filter gac, use dense H 80-90 ℃ of decolouring 1 hour
2SO
4Carry out acidifying (PH≤1), leave standstill crystallisation by cooling, filter, dry smart ether acid, reflux was dehydrated into acid anhydride in 1 hour in 1: 2 aceticanhydride and acetic acid mixed solution 50g then, cooled and filtered gets white crystals ether acid anhydride, 100-120 ℃ of oven dry, gets the smart ODPA-M (yield 88.0%) of 17.6g.
Embodiment 4:
Get the 20g coarse ODPA, add 5-6 doubly to 1,3 of coarse ODPA amount, the 5-trichlorobenzene, make its whole dissolvings, use activated carbon decolorizing 1 hour down for 100 ℃, remove by filter gac in temperature, the filtrate crystallisation by cooling, filtration, filtrate get smart ODPA-M 17.0g (yield 85.0%) with normal hexane washing, oven dry.
Claims (8)
1. one kind synthetic 4; the novel method of 4 '-diphenyl ether tetraformic dianhydride; it is characterized in that: directly from a chloro-o-xylene catalyzed oxidation product; capturing the high purity 4-chloro-benzoic anhydride that obtains in conjunction with sublimating is raw material; blanketing with inert gas; under solvent and phase-transfer catalyst effect, slough a part Cl with alkaline carbonate
2And directly obtain 4,4 '-diphenyl ether tetraformic dianhydride.Reaction is at normal pressure, under 200-230 ℃, and reaction 6-18h, 4,4 '-diphenyl ether tetraformic dianhydride yield is 66.5%, reaches 99% through hydrolysis method purified product purity, can make product purity reach 99.5% with solvent recrystallization.
2. method according to claim 1 is characterized in that: phase-transfer catalyst can be used tetraphenylphosphonibromide bromide (TPPB), tetraphenylphosphonium chloride (TPPC), tetrabutyl phosphonium bromide phosphine (TBPB) and triphenylphosphine (TPP).
3. method according to claim 1 is characterized in that: 4-chloro-benzoic anhydride raw material is that a chloro-o-xylene catalyzed oxidation product sublimates directly that to capture the purity obtain be 99% elaboration.
4. method according to claim 1 is characterized in that: solvent can be with 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene, 2,6-dichlorobenzene.
5. method according to claim 1 is characterized in that: the dechlorinating agent alkaline carbonate can be used salt of wormwood, yellow soda ash.
6. method according to claim 1 is characterized in that: thick 4, and refining used water solution of 4 '-diphenyl ether tetraformic dianhydride or solvent recrystallization method.
7. method according to claim 6 is characterized in that: hydrolysis is that 4 '-diphenyl ether tetraformic dianhydride is dissolved in the NaOH aqueous solution, heats about 30 minutes, uses dense H again with the gac heat decoloring with thick 4
2SO
4Carry out acidifying, leave standstill the cooling separate out crystallization, filter, dry smart ether acid, get smart acid anhydride with aceticanhydride and acetic acid mixed solution dehydration condensation then.
8. method according to claim 6 is characterized in that: recrystallization solvent can be with 1,3,5-trichlorobenzene or 2, and the 6-dichlorobenzene is used activated carbon decolorizing down for 200 ℃ in temperature, gets the ether acid anhydride after cooling, crystallization, filtration.
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|---|---|---|---|
| CN 200410048635 CN1706846A (en) | 2004-06-06 | 2004-06-06 | Synthesis process of 4,4'-diphenyl ether tetraformic acid dihydride |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7674920B2 (en) | 2008-03-28 | 2010-03-09 | Sabic Innovative Plastics Ip B.V. | Methods for preparing oxydiphthalic anhydrides, oxydiphthalic anhydrides prepared thereby, and polyetherimides derived therefrom |
| US8013173B2 (en) | 2008-03-28 | 2011-09-06 | Sabic Innovative Plastics Ip B.V. | Method of purifying dianhydrides, the dianhydrides formed thereby, and polyetherimides formed therefrom |
| CN108117505A (en) * | 2016-11-27 | 2018-06-05 | 杜庶铭 | A kind of preparation method for synthesizing diphenyl ether imidodicarbonic diamide |
| CN108250168A (en) * | 2017-12-25 | 2018-07-06 | 上海固创化工新材料有限公司 | A kind of preparation method of diphenyl ether tetraformic dianhydride |
| CN115490658A (en) * | 2022-10-11 | 2022-12-20 | 天津众泰材料科技有限公司 | Preparation method of 4,4' -oxydiphthalic anhydride |
-
2004
- 2004-06-06 CN CN 200410048635 patent/CN1706846A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7674920B2 (en) | 2008-03-28 | 2010-03-09 | Sabic Innovative Plastics Ip B.V. | Methods for preparing oxydiphthalic anhydrides, oxydiphthalic anhydrides prepared thereby, and polyetherimides derived therefrom |
| US8013173B2 (en) | 2008-03-28 | 2011-09-06 | Sabic Innovative Plastics Ip B.V. | Method of purifying dianhydrides, the dianhydrides formed thereby, and polyetherimides formed therefrom |
| CN108117505A (en) * | 2016-11-27 | 2018-06-05 | 杜庶铭 | A kind of preparation method for synthesizing diphenyl ether imidodicarbonic diamide |
| CN108250168A (en) * | 2017-12-25 | 2018-07-06 | 上海固创化工新材料有限公司 | A kind of preparation method of diphenyl ether tetraformic dianhydride |
| CN115490658A (en) * | 2022-10-11 | 2022-12-20 | 天津众泰材料科技有限公司 | Preparation method of 4,4' -oxydiphthalic anhydride |
| CN115490658B (en) * | 2022-10-11 | 2023-11-14 | 天津众泰材料科技有限公司 | Preparation method of 4,4' -oxydiphthalic anhydride |
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