CN108299457A - A kind of preparation method of the tetracarboxylic dianhydride of twin nuclei - Google Patents
A kind of preparation method of the tetracarboxylic dianhydride of twin nuclei Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 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 16
- 125000006158 tetracarboxylic acid group Chemical group 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- 125000002619 bicyclic group Chemical group 0.000 claims abstract description 30
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005886 esterification reaction Methods 0.000 claims abstract description 4
- 230000018044 dehydration Effects 0.000 claims abstract 2
- 238000006297 dehydration reaction Methods 0.000 claims abstract 2
- 238000005809 transesterification reaction Methods 0.000 claims abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 13
- 150000004702 methyl esters Chemical class 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 9
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical compound C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
- 239000012024 dehydrating agents Substances 0.000 claims description 3
- 230000032050 esterification Effects 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical group CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims 2
- 239000013067 intermediate product Substances 0.000 claims 2
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 150000008064 anhydrides Chemical class 0.000 claims 1
- 230000005611 electricity Effects 0.000 claims 1
- 239000000543 intermediate Substances 0.000 claims 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims 1
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000011017 operating method Methods 0.000 abstract 1
- 150000007524 organic acids Chemical class 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 238000001291 vacuum drying Methods 0.000 description 19
- 239000007787 solid Substances 0.000 description 15
- 238000013019 agitation Methods 0.000 description 12
- 238000010792 warming Methods 0.000 description 12
- 239000004642 Polyimide Substances 0.000 description 11
- 238000001816 cooling Methods 0.000 description 11
- 229920001721 polyimide Polymers 0.000 description 11
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 10
- 238000002425 crystallisation Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 125000006159 dianhydride group Chemical class 0.000 description 3
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 3
- 229960001826 dimethylphthalate Drugs 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000012453 solvate Substances 0.000 description 3
- 150000004075 acetic anhydrides Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- -1 mistake Filter Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical class CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/08—Bridged systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses a kind of preparation methods of the tetracarboxylic dianhydride of twin nuclei, and the invention belongs to fine chemicals preparation method fields.Its main technical schemes is reacted through five steps such as electroreduction, Isosorbide-5-Nitrae addition, esterification reaction of organic acid, hydrogenating reduction, transesterification dehydration closed-loops using phthalic acid as starting material, and a kind of bicyclic tetracarboxylic dianhydride of full appearance structure is synthesized.This programme has many advantages, such as that operating procedure is few, reaction condition is mild, high income, is suitble to large-scale industrial production relative to traditional preparation process.
Description
Technical field
The invention belongs to fine chemicals preparation method field more particularly to the preparation sides of the tetracarboxylic dianhydride of twin nuclei
Method.
Background technology
Applied from Du Pont companies the 1950s in the world first patent about polyimides (PI) with
Come, this kind of material is obtained with the advantages that its excellent heat resistance, insulation and dielectric properties, mechanics mechanical performance, chemical-resistance
To being widely applied.And the polyimides of early stage is mainly synthesized with aromatic dianhydride and aromatic diamine monomer, this kind of fragrance
Race PI is influenced by pi-electron cloud, is easy to form charge transfer complex (CTC) between electron donor and receptor, is led to PI materials
Color it is deeper, light transmission is poor, while being influenced by big pi bond, causes this kind of PI materials are insoluble not melt, and forming temperature is high, returns
It receives using difficult, it is difficult to meet the application of the high-performance PI materials of specific area, for this purpose, being closed by synthesis of alicyclic dianhydride
The extensive concern of people has been obtained at alicyclic and half alicyclic PI materials.
In initial research, as T M and T Kurosaki exist《Macromolecules》1997,30 (4)：993-1000
Middle report mainly synthesizes bicyclic [2.2.2] octyl- 7- alkene -2,3, and 5,6- tetracarboxylic dianhydrides are this to contain carbon-carbon double bond unsaturation two
Acid anhydride, the PI materials prepared from different diamine reactants with this dianhydride monomer, it is found that the thermal stability of the PI materials is poor, such as
It is just thermally decomposed when under nitrogen atmosphere, higher than 360 DEG C.It further proves to find, this undersaturated dianhydride monomer, in height
(it is more than 350 DEG C) under temperature and is easy to happen Isosorbide-5-Nitrae-addition back reaction, sees reaction equation 1.
In order to improve the thermal stability of PI materials, try the undersaturated dianhydride hydrogenating reduction obtaining a kind of saturation
Dianhydride is solved the above problems with this.T M and T Kurosaki et al. tries bicyclic [2.2.2] octyl- 7- alkene -2- external forms, outside 3-
Type, 5- external forms, 6- external forms-tetrabasic carboxylic acid -2,3:5,6- dianhydride direct hydrogenations restore to obtain bicyclic [2.2.2] octane -2- external forms, 3-
External form, 5- external forms, 6- external forms-tetrabasic carboxylic acid -2,3:5,6- dianhydrides, but do not succeed.Since catalytic hydrogenation reaction is one two
Phase reaction, reactant are all to be carried out in catalyst surface, and above-mentioned dianhydride monomer dissolubility is poor, and common low boiling point solvent is several
It is in insoluble state so that hydrogenation reduction is difficult to carry out.Although high boiling solvent can dissolve a small amount of above-mentioned dianhydride,
Be high boiling solvent suction hydrogen effect it is poor, while may be due to bicyclic [2.2.2] octyl- 7- alkene -2,3,5,6- tetracarboxylic dianhydrides
Pi-electron cloud in middle carbon-carbon double bond is influenced by four carbonyls, and steric hindrance is larger, this 2 points comprehensive, in high boiling solvent
Middle hydrogenation reduction is also difficult to carry out.
Existed according to T Matsumoto and T Kurosaki《Reactive&Functional Polymers》1996,30
(1)：The report and Japan Patent JP2008100979A of 55-59 proposes a kind of bicyclic [2.2.2] octane -2,3 of synthesis, and 5,
The preparation method of 6- tetracarboxylic dianhydrides is shown in reaction equation 2.In the program, in (±)-trans- 1,2- dihydros dimethyl phthalate (2) and richness
During horse dimethyl phthalate reacts, since (±)-trans- 1,2- dihydros dimethyl phthalate (2) is influenced by two ester groups, reaction
Activity is poor, it is therefore desirable to which higher reaction temperature (180 DEG C of ＞) can just be such that reaction is smoothed out.Bicyclic [2.2.2] octane -2-
External form, 3- inner mold, 5- external forms, 6- external forms-four methyl esters of tetrabasic carboxylic acid (4) hydrolyze at different conditions, can finally obtain various configuration
Dianhydride, hydrolyze under alkaline condition, will eventually get bicyclic [2.2.2] octane -2- inner mold, 3- inner mold, 5- external forms, 6-
External form-tetrabasic carboxylic acid -2,3:5,6- dianhydrides (6a), hydrolyze in acid condition, will eventually get bicyclic [2.2.2] octane-
2- inner mold, 3- inner mold, 5- external forms, 6- external forms-tetrabasic carboxylic acid -2,3:5,6- dianhydrides (6b), but as the dianhydride of this configurations of 6a is molten
Point is relatively low, and the PI thermal stabilities synthesized by it are relatively poor, it is therefore desirable to as this full appearance structure dianhydride monomers of 6b, and 4
Hydrolysis is difficult in acid condition, and the reaction time grows (＞ 18h), and the 6b yields finally synthesized are too low.
Invention content
In order to overcome above-mentioned difficulties, the present invention to provide one kind bicyclic [2.2.2] octane -2- external forms, 3- external forms, 5- external forms,
6- external forms-tetrabasic carboxylic acid -2,3:The preparation method of 5,6- dianhydrides is shown in reaction equation 3.The low in raw material price that the present invention uses, reaction
Mild condition is swift in response, and has to a kind of bicyclic [2.2.2] octane -2,3 of full appearance structure, 5,6- tetracarboxylic dianhydrides, and
Yield significantly improves (yield ＞ 93%), while obtaining alkyl acid methyl esters byproduct, and atom utilization is high.
Bicyclic [2.2.2] octane -2- external forms of the present invention, 3- external forms, 5- external forms, 6- external forms-tetrabasic carboxylic acid -2,3:5,
The process of the preparation method of 6- dianhydrides includes the following steps：
1) preparation of (±)-trans- 1,2- dihydros phthalandione：The mixing that phthalic acid, diluted acid and organic solvent are formed is molten
Liquid is placed in the electrolytic cell with diaphragm, and using lead electrode, 20 DEG C~80 DEG C of electrolysis temperature, current density is controlled in 100~600A/
m2, electroreduction generates (±)-trans- 1,2- dihydros phthalandione, by reacted electrolyte vacuum distillation precipitation white solid, mistake
Filter, deionized water recrystallization, vacuum drying obtain white solid, yield 90% or so；mp：212 DEG C~213 DEG C；1H NMRδ
(DMSO-d6)：3.53 (2H, CH), 5.81 (2H ,=CH-), 6.00 (2H ,-CH=), 12.73 (2H, COOH).
2) bicyclic [2.2.2] octyl- 7- alkene -2- external forms, 3- external forms, 5- external forms, 6- external forms-tetrabasic carboxylic acid -2,3:5,6- dianhydrides
Preparation：1) white solid and maleic anhydride that prepare are placed in band condenser pipe reaction unit, in nitrogen atmosphere, second
Acid anhydrides or propionic andydride do solvent and dehydrating agent, are warming up to 70 DEG C~85 DEG C dissolution of raw material, are continuously heating to 85 DEG C~140 DEG C, instead
It answers 0.5~3 hour, white solid, filtering, acetone washing is constantly precipitated in reaction process, and vacuum drying obtains white solid powder,
Yield 85% or so；mp：351 DEG C~352 DEG C；1H NMRδ(DMSO-d6)：3.48 (2H, CH), 3.61 (4H, CH), 6.38
(2H ,-CH=CH-).
3) bicyclic [2.2.2] octyl- 7- alkene -2- external forms, 3- external forms, 5- external forms, the preparation of 6- external forms-four methyl esters of tetrabasic carboxylic acid：
2) white powder, methanol solvate, the concentrated sulfuric acid that prepare are placed in band condenser pipe reaction unit, 30 DEG C~70 DEG C of reaction temperature is extremely
Reflux state reacts 3~7 hours, and after reaction, white needle-like crystals, filtering vacuum drying, yield is precipitated in crystallisation by cooling
97% or so；mp：130 DEG C~132 DEG C；1H NMRδ(DMSO-d6)：3.07 (2H, CH), 3.22 (4H, CH), 3.48 (12H,
CH3), 6.14 (2H ,-CH=CH-).
4) bicyclic [2.2.2] octane -2- external forms, 3- external forms, 5- external forms, the preparation of 6- external forms-four methyl esters of tetrabasic carboxylic acid：By 3)
White needle-like crystals, methanol or alcohol solvent, 5% palladium-carbon catalyst of preparation are placed in 500ml autoclaves, hydrogen displacement
Air in reaction kettle (displacement is three times), Hydrogen Vapor Pressure is 2MPa~5MPa, 60 DEG C~120 DEG C of reaction temperature, reaction in reaction kettle
6~12 hours time was filled into palladium-carbon catalyst with diatomite after reaction, was evaporated under reduced pressure cooling precipitation white granular
Crystal, filtering vacuum drying, yield 85% or so；mp：150 DEG C~152 DEG C；1H NMRδ(DMSO-d6)：1.48 (4H, CH2),
2.30 (2H, CH), 3.12 (4H, CH), 3.56 (12H, CH3)。
5) bicyclic [2.2.2] octane -2- external forms, 3- external forms, 5- external forms, 6- external forms-tetrabasic carboxylic acid -2,3:The system of 5,6- dianhydrides
It is standby：The white granular crystal that will 4) prepare, alkyl acid, the concentrated sulfuric acid are placed in the reactor with spinosity row still, reaction temperature
80 DEG C~130 DEG C of degree reacts 1~3 hour, and white powder solid is constantly precipitated in reaction process, and filtering vacuum drying is distilled simultaneously
Go out low fraction byproduct, yield 96% or so；mp：389 DEG C~391 DEG C；1H NMRδ(DMSO-d6)：1.37 (4H, CH2), 2.47
(2H, CH), 3.52 (4H, CH).
Further, the electrolysis temperature described in step (1) of the present invention be 20 DEG C~50 DEG C, current density be 200~
500A/m2。
Further, the reaction temperature described in step (2) of the present invention is 80 DEG C~120 DEG C.
Further, the catalytic amount of the concentrated sulfuric acid described in step (3) of the present invention be account for raw material gross mass 2%~
5%, the reaction temperature of esterification is 50 DEG C~70 DEG C.
Further, the reaction temperature of the hydrogenation reaction described in step 4) of the present invention is 80 DEG C~120 DEG C, 5% palladium
The catalytic amount of carbon accounts for the 2%~10% of raw material gross mass, and Hydrogen Vapor Pressure is 4MPa~5MPa in reaction kettle.
Further, the alkyl sour solvent described in step 5) of the present invention can be selected formic acid, acetic acid, it is a kind of in propionic acid or
It is several.
Further, the molar ratio of the raw material described in step 5) of the present invention and the concentrated sulfuric acid is 1：0.5~1：1, reaction
Temperature is 100 DEG C~130 DEG C.
Specific implementation mode
In order to further illustrate the detailed process of the bicyclic alkene tetracarboxylic dianhydride preparation process of this programme, it is listed below specific
Experimental program, but this programme is not limited to the specific number enumerated in experiment case study, and the quality of identical proportioning zooms in or out
Scheme also belong to experiment case study disclosure.
Embodiment 1
Cathode plate：Pb；Length 100mm, width 40mm, thickness 2mm.
Anode plate：Pb；Length 80mm, width 40mm, thickness 2mm.
Catholyte：300ml 5%H2SO4Aqueous solution, 200ml dioxane, 40g (240mmol) phthalic acid.
Anolyte：5%H2SO4Aqueous solution, liquid level maintain an equal level with catholyte liquid level.
Diaphragm：N324 cation-exchange membranes
Current density：200A/m2
Reaction temperature：30℃
HPLC detects reaction process, reacts and terminates after 17 hours, cooling after reaction solution is evaporated under reduced pressure out a part of solvent
White solid is precipitated in crystallization, filters, distillation water washing 1 to 2 time, and filtering, vacuum drying obtain 36.84g products, yield 91%,
It is 99.6% that HPLC, which detects purity,.
By the trans- 1,2- dihydros phthalandiones of 36.84g (220mmol) (±)-, 21.48g (220mmol) maleic anhydride, 60g
Acetic anhydride is placed in the reaction unit with condenser pipe, and dissolution of raw material after 70 DEG C are warming up in nitrogen atmosphere is continuously heating to
120 DEG C, white solid is constantly precipitated in magnetic agitation in reaction solution after half an hour, reacts and stops after 2 hours, filters, acetic acid washing
1 to 2 time, vacuum drying obtains 46.27g white powders, yield 85%.
By bicyclic [2.2.2] the octyl- 7- alkene -2- external forms of 46.27g (190mmol), 3- external forms, 5- external forms, 6- external forms-tetracarboxylic acid
Acid -2,3:5,6- dianhydrides, 9.25g (90mmol) concentrated sulfuric acid, 140g methanol are placed in the reaction unit with condenser pipe, are warming up to
Reflux temperature, magnetic agitation, TLC contact plates detect reaction process, react and terminate after 5 hours, it is brilliant that white needles are precipitated in crystallisation by cooling
Body filters, vacuum drying obtains 61.67g products, yield 97%.
By bicyclic [2.2.2] the octyl- 7- alkene -2- external forms of 61.67g (180mmol), 3- external forms, 5- external forms, 6- external forms-tetracarboxylic acid
Sour four methyl esters, 5% palladium carbons of 3g (1.41mmol), 180g methanol are placed in 500ml autoclaves, and hydrogen replacement reaction kettle is hollow
Gas (is replaced 2 to 3 times), and Hydrogen Vapor Pressure is 5MPa in reaction kettle, is warming up to 100 DEG C and starts to react, mechanical agitation, the inspection of TLC contact plates
Reaction process is surveyed, reacts and terminates after 6 hours, filter out palladium carbon in solution with diatomite, be evaporated under reduced pressure out a part of methanol solvate
Afterwards, white granular crystal is precipitated in crystallisation by cooling, filters, vacuum drying obtains 54.78g products, yield 88%.
By bicyclic [2.2.2] octane -2- external forms of 54.78g (160mmol), 3- external forms, 5- external forms, 6- external forms-tetrabasic carboxylic acid four
Methyl esters, 16.5g (160mmol) concentrated sulfuric acid, 160g acetic acid are placed in the reactor with spinosity row still, are warming up to 120 DEG C and are opened
Begin to react, magnetic agitation, white solid is constantly precipitated after half an hour in reaction solution, and collects 55 DEG C of low fraction component acetic acid first
Ester stops reaction after 1 hour, filter, and acetic acid washs 1 to 2 time, and vacuum drying obtains 38.47g white powders, and yield 94% is low
The quality of fraction colourless liquid is 46.47g, and yield 98%, vapor detection purity is 99.8%.
Embodiment 2
Cathode plate：Pb；Length 100mm, width 40mm, thickness 2mm.
Anode plate：Pb；Length 80mm, width 40mm, thickness 2mm.
Catholyte：250ml 10%H2SO4Aqueous solution, 250ml isopropanols, 60g (360mmol) phthalic acid.
Anolyte：10%H2SO4Aqueous solution, liquid level maintain an equal level with catholyte liquid level.
Diaphragm：N324 cation-exchange membranes
Current density：300A/m2
Reaction temperature：25℃
HPLC detects reaction process, reacts and terminates after 17 hours, cooling after reaction solution is evaporated under reduced pressure out a part of solvent
White solid is precipitated in crystallization, filters, distillation water washing 1 to 2 time, and filtering, vacuum drying obtain 54.05g products, yield 89%,
It is 99.6% that HPLC, which detects purity,.
By the trans- 1,2- dihydros phthalandiones of 54.05g (320mmol) (±)-, 31.52g (320mmol) maleic anhydride,
160g acetic anhydrides are placed in the reaction unit with condenser pipe, dissolution of raw material after 70 DEG C are warming up in nitrogen atmosphere, after of continuing rising
For temperature to 80 DEG C, white solid is constantly precipitated in magnetic agitation in reaction solution after 1 hour, reacts and stops after 3 hours, filter, acetic acid is washed
It washs 1 to 2 time, vacuum drying obtains 70.20g white powders, yield 88%.
By bicyclic [2.2.2] the octyl- 7- alkene -2- external forms of 70.20g (283mmol), 3- external forms, 5- external forms, 6- external forms-tetracarboxylic acid
Acid -2,3:5,6- dianhydrides, 14.04g (151mmol) concentrated sulfuric acid, 220g methanol are placed in the reaction unit with condenser pipe, heating
To reflux temperature, magnetic agitation, TLC contact plates detect reaction process, react and terminate after 5 hours, white needles are precipitated in crystallisation by cooling
Crystal filters, vacuum drying obtains 93.37g products, yield 97%.
By bicyclic [2.2.2] the octyl- 7- alkene -2- external forms of 93.37g (274mmol), 3- external forms, 5- external forms, 6- external forms-tetracarboxylic acid
Sour four methyl esters, 5% palladium carbons of 2.8g (1.31mmol), 270g methanol are placed in 500ml autoclaves, in hydrogen replacement reaction kettle
Air (is replaced 2 to 3 times), and Hydrogen Vapor Pressure is 5MPa in reaction kettle, is warming up to 120 DEG C and starts to react, mechanical agitation, TLC contact plates
Reaction process is detected, 3 hydrogen are supplemented during reaction, reacts and terminates after 10 hours, filter out palladium carbon in solution with diatomite, subtract
After pressure distills out a part of methanol solvate, white granular crystal is precipitated in crystallisation by cooling, filters, vacuum drying obtains 81.71g productions
Product, yield 87%.
By bicyclic [2.2.2] octane -2- external forms of 81.71g (239mmol), 3- external forms, 5- external forms, 6- external forms-tetrabasic carboxylic acid four
Methyl esters, 36.9g (358mmol) concentrated sulfuric acid, 240g formic acid are placed in the reactor with spinosity row still, are warming up to 100 DEG C and are opened
Begin to react, magnetic agitation, white solid is constantly precipitated after 1 hour in reaction solution, and collects 30 DEG C of low fraction component formic acid first
Ester stops reaction after 2 hours, filter, and acetic acid washs 1 to 2 time, and vacuum drying obtains 54.34g white powders, and yield 91% is low
The quality of fraction colourless liquid is 55.61g, and yield 97%, vapor detection purity is 99.9%.
Embodiment 3
Cathode plate：Pb；Length 100mm, width 40mm, thickness 2mm.
Anode plate：Pb；Length 80mm, width 40mm, thickness 2mm.
Catholyte：400ml 15%H2SO4Aqueous solution, 200ml DMF, 80g (480mmol) phthalic acid.
Anolyte：15%H2SO4Aqueous solution, liquid level maintain an equal level with catholyte liquid level.
Diaphragm：N324 cation-exchange membranes
Current density：400A/m2
Reaction temperature：50℃
HPLC detects reaction process, reacts and terminates after 17 hours, cooling after reaction solution is evaporated under reduced pressure out a part of solvent
White solid is precipitated in crystallization, filters, distillation water washing 1 to 2 time, and filtering, vacuum drying obtain 75.30g products, yield 93%,
It is 99.8% that HPLC, which detects purity,.
By the trans- 1,2- dihydros phthalandiones of 75.30g (448mmol) (±)-, 43.91g (448mmol) maleic anhydride,
220g acetic anhydrides are placed in the reaction unit with condenser pipe, dissolution of raw material after 70 DEG C are warming up in nitrogen atmosphere, after of continuing rising
White solid is constantly precipitated in temperature to 140 DEG C of reflux states, magnetic agitation after ten minutes in reaction solution, react and stop after half an hour,
It filters, acetone washs 1 to 2 time, and vacuum drying obtains 86.69g white powders, yield 78%.
By bicyclic [2.2.2] the octyl- 7- alkene -2- external forms of 86.69g (350mmol), 3- external forms, 5- external forms, 6- external forms-tetracarboxylic acid
Acid -2,3:5,6- dianhydrides, 13g (140mmol) concentrated sulfuric acid, 250g methanol are placed in the reaction unit with condenser pipe, are warming up to
Reflux temperature, magnetic agitation, TLC contact plates detect reaction process, react and terminate after 7 hours, it is brilliant that white needles are precipitated in crystallisation by cooling
Body filters, vacuum drying obtains 114.12g products, yield 96%.
By bicyclic [2.2.2] the octyl- 7- alkene -2- external forms of 114.12g (335mmol), 3- external forms, 5- external forms, 6- external forms-tetracarboxylic acid
Sour four methyl esters, 5% palladium carbons of 11.4g (5.36mmol), 230g ethyl alcohol are placed in 500ml autoclaves, hydrogen replacement reaction kettle
Middle air (displacement 2 to 3 times), Hydrogen Vapor Pressure is 5MPa in reaction kettle, is warming up to 110 DEG C and starts to react, mechanical agitation, TLC points
Plate detects reaction process, and 5 hydrogen are supplemented during reaction, reacts and terminates after 3 hours, palladium carbon in solution is filtered out with diatomite,
After being evaporated under reduced pressure out a part of alcohol solvent, white granular crystal is precipitated in crystallisation by cooling, filters, vacuum drying obtains
103.31g products, yield 90%.
By bicyclic [2.2.2] octane -2- external forms of 103.31g (300mmol), 3- external forms, 5- external forms, 6- external forms-tetrabasic carboxylic acid
Four methyl esters, 15.56g (150mmol) concentrated sulfuric acid, 200g propionic acid are placed in the reactor with spinosity row still, are warming up to 130 DEG C
Start to react, magnetic agitation, white solid is constantly precipitated after half an hour in reaction solution, and collects 78 DEG C of low fraction component propionic acid
Methyl esters stops reaction after 1 hour, filter, and acetic acid washs 1 to 2 time, is dried in vacuo and obtains 72.48g white powders, yield 96%,
The quality of low fraction colourless liquid is 98.9g, and yield 93%, vapor detection purity is 98.9%.
Claims (10)
1. a kind of preparation method of the tetracarboxylic dianhydride of twin nuclei, the method is characterized in that including the following steps：
1) mixed solution that phthalic acid, diluted acid and organic solvent form is placed in the electrolytic cell with diaphragm, using lead electricity
Pole, electroreduction generate (±)-trans- 1,2- dihydros phthalandione, and the product after electrolysis is the racemic mixing of two different isomers
Object (1S, 2S and 1R, 2R).
2) in nitrogen atmosphere, acetic anhydride or propionic andydride do solvent and dehydrating agent, (±)-trans- 1,2- dihydros phthalandione and maleic
Diacid anhydride reactant generates a kind of bicyclic [2.2.2] octyl- 7- alkene -2,3 of full appearance structure, 5,6- tetracarboxylic dianhydrides
3) solvent is made with methanol, the concentrated sulfuric acid makees catalyst, and intermediate products esterification prepared by step 2) generates bicyclic
[2.2.2] octyl- 7- alkene -2- external forms, 3- external forms, 5- external forms, 6- external forms-four methyl esters of tetrabasic carboxylic acid；
4) in autoclave, methanol makees solvent, and 5% palladium carbon makees catalyst, and intermediate products prepared by step 3) are added hydrogen also
Original, reaction generate bicyclic [2.2.2] octane -2- external forms, 3- external forms, 5- external forms, 6- external forms-four methyl esters of tetrabasic carboxylic acid；
5) in being fractionated reactor, alkyl acid makees solvent, and the concentrated sulfuric acid does catalyst, dehydrating agent, intermediate production prepared by step 4)
Product transesterification, dehydration closed-loop generate bicyclic [2.2.2] octane -2- external forms, 3- external forms, 5- external forms, 6- external forms-tetrabasic carboxylic acid -2,3:
5,6- dianhydrides, while fractionating out low end components alkyl acid methyl esters.
2. preparation process according to claim 1, which is characterized in that the tetracarboxylic dianhydride of the twin nuclei specifically ties
Structure formula is,
3. preparation process according to claim 1, which is characterized in that in step 1), electrolysis temperature is 20 DEG C~80 DEG C,
Current density is 100~600A/m2。
4. preparation process according to claim 1, which is characterized in that in step 1), dilute acid soln be sulfuric acid, nitric acid,
One or more of aqueous solution in phosphoric acid, p-methyl benzenesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, the wherein quality of dilute acid solution
Score is 5%~20%.
5. preparation process according to claim 1, which is characterized in that in step 1), dioxy six can be selected in organic solvent
It is one or more of in ring, tetrahydrofuran, ether, isopropanol, methanol, ethyl alcohol, dimethylformamide, dimethylacetylamide.
6. preparation process according to claim 1, which is characterized in that in step 2), acetic anhydride can be selected in acid anhydrides solvent
Or propionic andydride, reaction temperature are 60 DEG C~140 DEG C.
7. preparation process according to claim 1, which is characterized in that in step 3), the catalytic amount of the concentrated sulfuric acid is to account for original
Expect the 1%~10% of gross mass, the reaction temperature of esterification is 30 DEG C~70 DEG C.
8. preparation process according to claim 1, which is characterized in that in step 4), the reaction temperature of hydrogenation reaction is
60 DEG C~120 DEG C, the catalytic amount of 5% palladium carbon accounts for the 2%~20% of raw material gross mass, in reaction kettle Hydrogen Vapor Pressure be 2MPa~
5MPa。
9. preparation process according to claim 1, which is characterized in that in step 5), alkyl sour solvent can be selected formic acid,
One or more of acetic acid, propionic acid, n-butyric acie, tertiary butyric acid.
10. preparation process according to claim 1, which is characterized in that in step 5), the molar ratio of raw material and the concentrated sulfuric acid
It is 1：0.5~1：2, reaction temperature is 80 DEG C~130 DEG C.
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| CN115894512A (en) * | 2022-12-21 | 2023-04-04 | 大连奇凯医药科技有限公司 | Synthesis and detection method of 1,2,4,5-cyclohexanetetracarboxylic dianhydride |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07304870A (en) * | 1994-05-09 | 1995-11-21 | Maruzen Petrochem Co Ltd | Production of both bicyclo(2.2.2)octanetetracarboxylic dianhydride and polyimide using the same tetracarboxylic dianhydride |
| JP5666076B2 (en) * | 2006-09-19 | 2015-02-12 | 和光純薬工業株式会社 | Bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic dianhydride, its production method, said bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic Polyimide obtained from acid dianhydride and use thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07304870A (en) * | 1994-05-09 | 1995-11-21 | Maruzen Petrochem Co Ltd | Production of both bicyclo(2.2.2)octanetetracarboxylic dianhydride and polyimide using the same tetracarboxylic dianhydride |
| JP5666076B2 (en) * | 2006-09-19 | 2015-02-12 | 和光純薬工業株式会社 | Bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic dianhydride, its production method, said bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic Polyimide obtained from acid dianhydride and use thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115894512A (en) * | 2022-12-21 | 2023-04-04 | 大连奇凯医药科技有限公司 | Synthesis and detection method of 1,2,4,5-cyclohexanetetracarboxylic dianhydride |
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