CN1944419A - Process for synthesizing bibenzene tetracarboxylic dianhydride - Google Patents
Process for synthesizing bibenzene tetracarboxylic dianhydride Download PDFInfo
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- CN1944419A CN1944419A CN 200610117600 CN200610117600A CN1944419A CN 1944419 A CN1944419 A CN 1944419A CN 200610117600 CN200610117600 CN 200610117600 CN 200610117600 A CN200610117600 A CN 200610117600A CN 1944419 A CN1944419 A CN 1944419A
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- CN
- China
- Prior art keywords
- bibenzene tetracarboxylic
- tetracarboxylic dianhydride
- palladium
- chloro
- benzoic anhydride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 title claims abstract description 24
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 125000006158 tetracarboxylic acid group Chemical group 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 8
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 235000011187 glycerol Nutrition 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 33
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 28
- MWUSAETYTBNPDG-UHFFFAOYSA-N (4-chlorobenzoyl) 4-chlorobenzoate Chemical compound C1=CC(Cl)=CC=C1C(=O)OC(=O)C1=CC=C(Cl)C=C1 MWUSAETYTBNPDG-UHFFFAOYSA-N 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 229910052763 palladium Inorganic materials 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 9
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- BPKGOZPBGXJDEP-UHFFFAOYSA-N [C].[Zn] Chemical compound [C].[Zn] BPKGOZPBGXJDEP-UHFFFAOYSA-N 0.000 claims description 6
- 238000006210 cyclodehydration reaction Methods 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 239000012452 mother liquor Substances 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000002844 melting Methods 0.000 abstract description 5
- 230000008018 melting Effects 0.000 abstract description 5
- -1 bibenzene tetracarboxylic acid Chemical class 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 238000007363 ring formation reaction Methods 0.000 abstract description 2
- BTTRMCQEPDPCPA-UHFFFAOYSA-N 4-chlorophthalic anhydride Chemical compound ClC1=CC=C2C(=O)OC(=O)C2=C1 BTTRMCQEPDPCPA-UHFFFAOYSA-N 0.000 abstract 2
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 description 2
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical class OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- OLENANGIJWDOPG-UHFFFAOYSA-N (2-chlorobenzoyl) 2-chlorobenzoate Chemical compound ClC1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1Cl OLENANGIJWDOPG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 210000002469 basement membrane Anatomy 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000206 moulding compound Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The present invention is process of synthesizing bibenzene tetracarboxylic dianhydride. The present invention prepares bibenzene tetracarboxylic dianhydride through the reaction with 4-chloro phthalic anhydride as main material, PdC-Zn or PdC as catalyst and glycerin as reductant at 100 deg.c for 10-12 hr to produce bibenzene tetracarboxylic acid, and the subsequent dewatering and cyclization to form bibenzene tetracarboxylic dianhydride. The present invention has 4-chloro phthalic anhydride converting rate of 100 %, bibenzene tetracarboxylic dianhydride yield of 90-95 %, melting range of 299-301 deg.c, and product purity of 99.5-99.8 %.
Description
One, technical field
The present invention relates to a kind of synthetic method of bibenzene tetracarboxylic dianhydride, relate to 3,3 ', 4 or rather, the synthetic method of 4 '-bibenzene tetracarboxylic dianhydride.
Two, background technology
Bibenzene tetracarboxylic dianhydride is the important source material of the polyimide of synthetic biphenyl structural, is again the properties-correcting agent of other heat resistant polymers, for example as curing agent for epoxy resin.Biphenyl polyimide all has gratifying development at moulding compound and film field, and especially, film is as the flexible print circuit board basement membrane, and band is bonding carrying band and unicircuit packaging lead-frame ribbon strong market automatically.
With the 4-chloro-benzoic anhydride is the synthetic method of feedstock production bibenzene tetracarboxylic dianhydride, and the patent of invention of being had an optimistic view of by numerous scholars has US.Pat.No.5,081, and 281January14,1992.This prior art becomes 4-chlorophthalic acid ester with the esterification of 4-chloro-benzoic anhydride earlier, then at (Ph
3P)
2NiCl
2Coupling catalyst exists down, and coupling becomes the biphenyl tetracarboxylic acid esters, becomes bibenzene tetracarboxylic with the 20%NaOH aqueous hydrolysis again, then provides bibenzene tetracarboxylic dianhydride in 210～220 ℃ of slow thermal dehydration cyclisation, 299～302 ℃ of fusing points.The characteristics of this method are that technology is comparatively ripe, and the yield of bibenzene tetracarboxylic is higher, is up to 97%, and needing improved place probably is to shorten preparation technology, and present inventors just want to save de-esterifying and hydrolysing step.In addition, (Ph
3P)
2NiCl
2The catalyzer cost is higher, causes product cost also high, and it is also reasonable to seek better catalyzer.Go on foot acid by 4-chloro-benzoic anhydride one, cyclodehydration system 3 in the aceticanhydride solvent, and 3 ', 4,4 '-bibenzene tetracarboxylic dianhydride can reduce cost 20～30% like this.
Three, summary of the invention
Hitachi, Ltd is that the raw material palladium is that the highest yield of catalyzer system bibenzene tetracarboxylic is 57% with the chloro-benzoic anhydride.Present inventors have done research with great concentration to palladium-carbon catalyst or palladium carbon-zinc composite catalyst, and the result finds and improves the method that yield reduces cost, and has proposed complete technical scheme of the present invention.
The present invention is a raw material with the 4-chloro-benzoic anhydride, and in the presence of palladium carbon-zinc composite catalyst or palladium-carbon catalyst, glycerine is that reductive agent made bibenzene tetracarboxylic, yield 70～80%, purity＞99% in 10～12 hours in 100 ℃ of reactions.Continue it, in the aceticanhydride solvent, obtained bibenzene tetracarboxylic dianhydride, yield 90～95%, 299～301 ℃ of melting ranges, purity 99.5～99.8% in 4～5 hours in 140～143 ℃ of backflows.
Reaction formula of the present invention is as follows:
Reaction mass proportioning of the present invention is: the mol ratio of potassium hydroxide and 4-chloro-benzoic anhydride is 2-5: 1, add water 900～1000g corresponding to 1 mole of 4-chloro-benzoic anhydride, palladium carbon-zinc composite catalyst is 3～6% of a 4-chloro-benzoic anhydride weight, the atomic molar ratio of palladium and zinc is 1: 10～1: 20, palladium content is 5～7% of total quality in the palladium-carbon catalyst, and solvent glycerin is 70～90g corresponding to 1 mole of 4-chloro-benzoic anhydride add-on; After in reactor, adding 4-chloro-benzoic anhydride, palladium carbon-zinc composite catalyst or palladium-carbon catalyst and water, drip glycerine in 100 ℃, the dropping cycle is 2.5～5h, the reaction that continues 10～12 hours, the bibenzene tetracarboxylic (yield 70-80%) of filtration, salt acidifying mother liquor, filtration, drying, acquisition, the bibenzene tetracarboxylic that is obtained cyclodehydration in the aceticanhydride solvent becomes 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride.
The used hydrochloric acid of the present invention is the concentrated hydrochloric acid of concentration 37%.Bibenzene tetracarboxylic aceticanhydride solution, wherein the biphenyl tetracarboxylic acid content is 14-15%.In 140-143 ℃ of reflux dewatering cyclization 4-5 hour.
According to 3,3 ', 4 of the present invention's preparation, 4 '-bibenzene tetracarboxylic dianhydride, its yield 90～95%, 299～301 ℃ of melting ranges, purity 99.5～99.8%.
Four, embodiment
In order to implement the present invention better, especially exemplified by example it is described, but is not limitation of the present invention.
Embodiment 1
In the four-hole boiling flask that is equipped with nitrogen conduit, dropping funnel, thermometer and agitator, add 3.64g (0.02mol) 4-chloro-benzoic anhydride, 5.6g (0.1mol) potassium hydroxide, 0.095g/0.05g palladium charcoal-zinc composite catalyst or 0.095g palladium carbon catalyst and 19ml water, continue it, drip the 1.8g aqueous glycerin solution after being warming up to 100 ℃, the dropping cycle is 2.5 hours, dropwise and continue reaction 12 hours, filter, mother liquor obtains white precipitate with concentrated hydrochloric acid (37%) acidifying, filtered while hot, washing, dry bibenzene tetracarboxylic 2.6g, yield 80%, the purity 99.2% of getting.
Purity is that 99.2% bibenzene tetracarboxylic 33g refluxed 4.5 hours in 142 ℃ in the 236ml aceticanhydride, and cool to room temperature filters, after cleaning with small amount of toluene, get 27g3 in 140 ℃ of vacuum-dryings, 3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, yield 95%, 299～301 ℃ of fusing points, purity 99.6%.
Embodiment 2
Except adding potassium hydroxide 3.9g (0.07mol), palladium charcoal-zinc composite catalyst 0.143g/0.075g or palladium carbon catalyst 0.143g, 18ml water and glycerine 1.6g, feeding study on period is 3.5 hours, outside 11 hours reaction times, other prescriptions are the same with embodiment 1 with operation steps, bibenzene tetracarboxylic receipts amount 2.4g as a result, yield 75%.
Bibenzene tetracarboxylic is cyclodehydration system 3,3 ', 4 in the aceticanhydride solvent, the prescription and the control condition of 4 '-bibenzene tetracarboxylic dianhydride change to: add aceticanhydride 253ml, 143 ℃ of reflux temperatures, in 4 hours reaction times, other prescriptions are the same with embodiment 1 with operation steps, as a result 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride yield 90%, 299～301 ℃ of melting ranges, purity 99.8%.
Embodiment 3
Except adding potassium hydroxide 2.2g (0.04mol), palladium charcoal-zinc composite catalyst 0.071g/0.038g or palladium carbon catalyst 0.071g, water 20ml and glycerine 1.4g, feeding study on period is 5 hours, outside 10 hours reaction times, other prescriptions and operation steps are with embodiment 1-sample, bibenzene tetracarboxylic receipts amount 2.3g as a result, yield 70%.
Bibenzene tetracarboxylic is cyclodehydration system 3,3 ', 4 in the aceticanhydride solvent, the prescription and the control condition of 4 '-bibenzene tetracarboxylic dianhydride change to: add aceticanhydride 244ml, outside 140 ℃ of the reflux temperatures, return time 5 hours, other prescriptions are the same with embodiment 1 with operation steps, as a result 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride yield 93%, 299～301 ℃ of melting ranges, purity 99.5%.
Claims (3)
1, a kind of method of synthesizing bibenzene tetracarboxylic dianhydride, be characterised in that the reaction mass proportioning is: the mol ratio of potassium hydroxide and 4-chloro-benzoic anhydride is 2～5: 1, add water 900～1000g corresponding to 1 mole of 4-chloro-benzoic anhydride, palladium carbon-zinc composite catalyst is 3～6% of a 4-chloro-benzoic anhydride weight, the atomic molar ratio of palladium and zinc is 1: 10～1: 20, palladium content is 5～7% of total quality in the palladium-carbon catalyst, and solvent glycerin is 70～90g corresponding to 1 mole of 4-chloro-benzoic anhydride add-on; After in reactor, adding 4-chloro-benzoic anhydride, palladium carbon-zinc composite catalyst or palladium-carbon catalyst and water, drip glycerine in 100 ℃, the dropping cycle is 2.5～5h, the reaction that continues 10～12 hours, bibenzene tetracarboxylic cyclodehydration in the aceticanhydride solvent of filtration, salt acidifying mother liquor, filtration, drying, acquisition becomes bibenzene tetracarboxylic dianhydride.
2, according to the method for a kind of synthesizing bibenzene tetracarboxylic dianhydride of claim 1, be characterised in that described hydrochloric acid is 37% concentrated hydrochloric acid.
3, according to the method for a kind of synthesizing bibenzene tetracarboxylic dianhydride of claim 1, be characterised in that the content that described aceticanhydride cyclodehydration condition is a bibenzene tetracarboxylic is 14～15%, refluxed 4～5 hours in 140～143 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101176001A CN100460401C (en) | 2006-10-26 | 2006-10-26 | Process for synthesizing bibenzene tetracarboxylic dianhydride |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101176001A CN100460401C (en) | 2006-10-26 | 2006-10-26 | Process for synthesizing bibenzene tetracarboxylic dianhydride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1944419A true CN1944419A (en) | 2007-04-11 |
| CN100460401C CN100460401C (en) | 2009-02-11 |
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101659647B (en) * | 2008-08-26 | 2011-10-12 | 比亚迪股份有限公司 | Method for preparing diphenyl tetracarboxylic dianhydride |
| CN110563678A (en) * | 2019-10-15 | 2019-12-13 | 上海固创化工新材料有限公司 | Preparation method of 3,3',4,4' -biphenyl tetracarboxylic dianhydride |
| CN111620769A (en) * | 2020-06-04 | 2020-09-04 | 南通汇顺化工有限公司 | Method for preparing 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride |
| CN113717136A (en) * | 2021-07-27 | 2021-11-30 | 江西师范大学 | High-yield green safe synthesis method of 3,3',4,4' -biphenyl tetracarboxylic dianhydride |
| CN114315555A (en) * | 2021-12-31 | 2022-04-12 | 河北海力香料股份有限公司 | Synthetic method of 3,3',4, 4' -biphenyltetracarboxylic acid |
| CN117050042A (en) * | 2023-08-14 | 2023-11-14 | 上海固创化工新材料有限公司 | Preparation method of 3,3', 4' -biphenyl tetracarboxylic dianhydride |
-
2006
- 2006-10-26 CN CNB2006101176001A patent/CN100460401C/en active Active
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101659647B (en) * | 2008-08-26 | 2011-10-12 | 比亚迪股份有限公司 | Method for preparing diphenyl tetracarboxylic dianhydride |
| CN110563678A (en) * | 2019-10-15 | 2019-12-13 | 上海固创化工新材料有限公司 | Preparation method of 3,3',4,4' -biphenyl tetracarboxylic dianhydride |
| CN111620769A (en) * | 2020-06-04 | 2020-09-04 | 南通汇顺化工有限公司 | Method for preparing 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride |
| CN111620769B (en) * | 2020-06-04 | 2022-06-28 | 南通汇顺化工有限公司 | Method for preparing 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride |
| CN113717136A (en) * | 2021-07-27 | 2021-11-30 | 江西师范大学 | High-yield green safe synthesis method of 3,3',4,4' -biphenyl tetracarboxylic dianhydride |
| CN114315555A (en) * | 2021-12-31 | 2022-04-12 | 河北海力香料股份有限公司 | Synthetic method of 3,3',4, 4' -biphenyltetracarboxylic acid |
| CN117050042A (en) * | 2023-08-14 | 2023-11-14 | 上海固创化工新材料有限公司 | Preparation method of 3,3', 4' -biphenyl tetracarboxylic dianhydride |
| CN117050042B (en) * | 2023-08-14 | 2025-06-24 | 上海固创化工新材料有限公司 | A preparation method of 3,3',4,4'-biphenyltetracarboxylic dianhydride |
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| Publication number | Publication date |
|---|---|
| CN100460401C (en) | 2009-02-11 |
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