CN1215068C - Prepn process of 2,3,3',4'-diphenyl tetraformic dianhydride and its derivative - Google Patents
Prepn process of 2,3,3',4'-diphenyl tetraformic dianhydride and its derivative Download PDFInfo
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- CN1215068C CN1215068C CN 03105026 CN03105026A CN1215068C CN 1215068 C CN1215068 C CN 1215068C CN 03105026 CN03105026 CN 03105026 CN 03105026 A CN03105026 A CN 03105026A CN 1215068 C CN1215068 C CN 1215068C
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Abstract
The present invention belongs to a preparation method of 2, 3, 3', 4'-diphenyl tetraformic dianhydride and a derivative thereof, which comprises the following steps: adopting 3-and 4-chlorodiester phthalic or 3-and 4-chlorophthalimide as basic raw material; adopting nickel halogenide as a catalyst and trialkylphosphine as ligand; adopting zinc powder as a reducing agent; treating the material with coupling reaction in non-proton flare polar solvent to prepare diphenyl tetraformate or diphenyl tetraformyl diimide; hydrolyzing the diphenyl tetraformate or diphenyl tetraformyl diimide in a NaOH solution, and acidifying the hydrolysis product with concentrated HCl to prepare 2, 3, 3', 4'-diphenyl tetraformic acid; refluxing the 2, 3, 3', 4'-diphenyl tetraformic acid in toluene or xylene with water contained to prepare anhydride or high temperature subliming the 2, 3, 3', 4'-diphenyl tetraformic acid in vacuum to prepare 2, 3, 3', 4'-diphenyl dianhydride.
Description
Technical field
The invention belongs to 2,3, the preparation method of 3 ', 4 '-bibenzene tetracarboxylic dianhydride and derivative thereof.
Background technology
Bibenzene tetracarboxylic dianhydride and derivative thereof obtain extensive concern both domestic and external already as the synthetic and application of the important monomer of high performance aromatic polyimide.Wherein 3,3 ', 4, the synthetic method of 4 '-bibenzene tetracarboxylic and derivative thereof has many patent reports (United States Patent (USP): 5081281 very early; Japanese Patent 7352749,80141417,8551151,8020705).Comprise the dehalogenation linked reaction of halophthalic acid tetraalkyl ester and the oxidative coupling reaction of phthalic acid tetraalkyl ester.Related 2,3 in the patent of having reported, it is synthetic 3,3 ', 4,4 ' that 3 ', 4 '-bibenzene tetracarboxylic dianhydride is, a kind of by product during-bibenzene tetracarboxylic dianhydride, and yield is very low.
Summary of the invention
The purpose of this invention is to provide a kind of 2,3, the preparation method of 3 ', 4 '-bibenzene tetracarboxylic dianhydride and derivative thereof.
This method forms title complex two (trialkyl phosphine) nickel halogenide with nickel halogenide with trialkyl phosphine in polar aprotic solvent be catalyzer, carry out catalyzed coupling reaction with 3-and 4-chlorophthalic acid dialkyl or 3-and 4-chlorophthalimide again under the effect of reductive agent zinc powder, generate bibenzene tetracarboxylic tetraalkyl ester or biphenyl tetracarboxylic acyl diimine and generate 2 through acidication again, 3,3 ', 4 '-bibenzene tetracarboxylic then again cyclodehydration become acid anhydride.
Reaction process is as follows:
The reaction raw materials that adopts is:
The chlorophthalic acid diester:
Or the adjacent phthalide imide of chloro:
The position of substitution of chlorine atom can be 3 or 4, and the R representative contains 1～6 carbon atom straight chain or branched alkyl; R in the adjacent phthalide imide of chloro can also be phenyl, and used three chloro compounds and tetrachloro are 1 for the molar ratio of compound: 3-3: 1.
Catalyzer of the present invention is two (trialkyl phosphine) nickel halogenides or two (triaryl phosphine) nickel halogenide, and catalyzer is the orgnometallic catalyst by trialkyl phosphine or triaryl phosphine and dihalide nickel on-site preparation; Wherein trialkyl phosphine or triaryl phosphine (PR '
3) be catalyst ligand, dihalide nickel is Nickel Bromide or Nickel Chloride, substituent R ' can be alkyl, alkoxyl group, the aromatic base that aromatic base or alkoxyl group replace; Alkyl substituent is for containing 1～12 carbon atom; Aromatic substituent is for containing 6～10 carbon atoms; The add-on of catalyzer by adding feed molar number 2.5～12.5%; The add-on of catalyst ligand is 2～6 times that catalyzer adds mole number; The add-on of zinc powder is 1.1-2.5 a times of feed molar amount; When catalyzer was Nickel Chloride, the catalysis initiator was a Sodium Bromide, and add-on is for adding the 15-25% of feed molar number.
The solvent that is adopted is N, N '-dimethyl formamide (DMF), N, N '-N,N-DIMETHYLACETAMIDE (DMAc), N-N-methyl-2-2-pyrrolidone N-(NMP), dimethyl sulfoxide (DMSO) (DMSO) or tetramethylene sulfone; Temperature of reaction is 60-120 ℃; Reaction times is 0.2-6h.
Preparation process is as follows:
Under nitrogen protection, with chlorophthalic acid dimethyl ester or the adjacent phthalide imide of chloro; nickel halogenide and triphenylphosphine dissolved in polar aprotic solvent, be heated to 60-120 ℃ after; add excessive zinc powder again; after 0.5-6h is carried out in reaction, filtrate is poured in the big water gaging into the collecting precipitation thing; this throw out is added in the NaOH aqueous solution; behind the heating hydrolysis reaction 4-24h, cooling is filtered; filtrate is carried out acidifying with concentrated hydrochloric acid; filter out insolubles, after again filtrate being concentrated, directly with toluene or dimethylbenzene band water; after water Ex-all in the system; filter, solid is separated out in cooling, collects solid; after the thorough drying; the heating, vacuum distillation obtains 2,3; 3 ', 4 '-bibenzene tetracarboxylic dianhydride.
Characteristics of the present invention are by the direct Synthetic 2 of catalyzed coupling reaction, 3, and 3 ', 4 '-bibenzene tetracarboxylic dianhydride and various derivative thereof, separation method is simple, and yield is higher.
Embodiment
Embodiment 1
Under nitrogen protection; with 0.5mol 4-chlorophthalic acid dimethyl ester; 0.5mol 3-chlorophthalic acid dimethyl ester, 0.025mol Nickel Chloride, 0.15mol triphenylphosphine; 0.1mol Sodium Bromide; the DMAc solvent of 400ml adds in the 500ml there-necked flask, treats that temperature rises to 80 ℃, stirs the back and adds the 1.5mol zinc powder; solution becomes sorrel, and reaction is carried out can finishing behind the 2h.Reaction solution is poured in the water, filtered collecting precipitation, it is joined in the NaOH aqueous solution then, reacting by heating 4h, cooled and filtered is acidified to strongly-acid with filtrate with concentrated hydrochloric acid, after filtering out the solid of separating out, filtrate adds toluene and reflux band water, after the complete Ex-all of the water in the system, filtered while hot is separated out solid, obtain the solid thorough drying after, distil at 210 ℃, obtain 2,3,3 ', 4 '-bibenzene tetracarboxylic dianhydride 0.5mol.
Embodiment 2
Under nitrogen protection; with 0.3mol 4-chlorophthalic acid diethyl ester; 0.7mol 3-chlorophthalic acid diethyl ester; 0.04mol Nickel Bromide, 0.24mol trimethyl-phosphine, the DMSO solvent of 300ml add in the 500ml there-necked flask; treat that temperature rises to 60 ℃; stir adding 1.5mol zinc powder after ten minutes, solution becomes sorrel, and reaction is carried out can finishing behind the 0.5h.Liquid chromatography records 2,3, and 3 ', 4 '-bibenzene tetracarboxylic tetra-ethyl ester productive rate is 47.4%.
Embodiment 3
Under nitrogen protection; with 0.3mol 4-chlorophthalic acid di-n-propyl ester; 0.7mol 3-chlorophthalic acid di-n-propyl ester; 0.125mol Nickel Bromide, 0.15mol trimethyl-phosphine, the DMAc solvent of 300ml add in the 500ml there-necked flask; treat that temperature rises to 68 ℃; stir adding 1.1mol zinc powder after ten minutes, solution becomes sorrel, and reaction is carried out can finishing behind the 4h.Liquid chromatography records 2,3, and 3 ', 4 '-bibenzene tetracarboxylic, four n-propyl yields are 70%.
Embodiment 4
Under nitrogen protection; with 0.5mol 4-chlorophthalic acid diisopropyl ester; 0.5mol 4-chlorophthalic acid diisopropyl ester; 0.025mol Nickel Bromide, 0.09mol three dodecyl phosphines, the sulfolane solvent of 300ml add in the 500ml there-necked flask; treat that temperature rises to 100 ℃; stir adding 2.0mol zinc powder after ten minutes, solution becomes sorrel, and reaction is carried out can finishing behind the 6h.Liquid chromatography records 2,3, and 3 ', 4 '-bibenzene tetracarboxylic, four isopropyl ester yields are 49%.
Embodiment 5
Under nitrogen protection; with 0.6mol 4-chlorophthalic acid two just own esters; 0.4mol the just own ester of 4-chlorophthalic acid two; 0.025mol Nickel Bromide, 0.12mol three (methoxy ethyl) phosphine, the nmp solvent of 300ml add in the 500ml there-necked flask; treat that temperature rises to 75 ℃; stir adding 2.5mol zinc powder after ten minutes, solution becomes sorrel, and reaction is carried out can finishing behind the 6h.Liquid chromatography records 2,3, and the just own ester yield of 3 ', 4 '-bibenzene tetracarboxylic four is 75%.
Embodiment 6
Under nitrogen protection; with 0.3mol 4-chlorophthalic acid dimethyl ester; 0.7mol 3-chlorophthalic acid dimethyl ester, 0.05mol Nickel Chloride, the Sodium Bromide of 0.25mol; three 0.05mol (2-ethoxyl phenenyl) phosphine; the DMAc solvent of 300ml adds in the 500ml there-necked flask, treats that temperature rises to 60 ℃, stirs to add the 1.5mol zinc powder after ten minutes; solution becomes sorrel, and reaction is carried out can finishing behind the 4.5h.Liquid chromatography records 2,3, and 3 ', 4 '-bibenzene tetracarboxylic tetramethyl ester yield is 65%
Embodiment 7
Under nitrogen protection, with 0.25mol 4-chlorophthalic acid dimethyl ester, 0.75mol 3-chlorophthalic acid dimethyl ester; 0.025mol Nickel Chloride, the Sodium Bromide of 0.15mol, 0.15mol trimethyl-phosphine; the DMAc solvent of 500ml adds in the 500ml there-necked flask, treats that temperature rises to 60 ℃, stirs to add the 1.5mol zinc powder after ten minutes; solution becomes sorrel; after 1h was carried out in reaction, liquid chromatography recorded 2,3; 3 ', 4 '-bibenzene tetracarboxylic tetramethyl ester yield is 75%
Embodiment 8
Under nitrogen protection; with 0.5mol N-phenyl-4-chloro phthalimide; 0.5mol N-phenyl-3-chloro phthalimide; 0.025mol Nickel Bromide, 0.15mol three n-heptyl phosphines, the DMF solvent of 280ml add in the 500ml there-necked flask; treat that temperature rises to 70 ℃; stir adding 1.5mol zinc powder after ten minutes, solution becomes sorrel, and reaction is carried out can finishing behind the 2h.Filtrate is poured in the big water gaging, filter collecting precipitation, it is joined in the NaOH aqueous solution then, behind the reaction 12h, cooled and filtered is carried out acidifying with filtrate with concentrated hydrochloric acid, after filtering out the solid of separating out, add refluxing xylene band water, after water Ex-all in the system, filtered while hot is separated out solid, obtains 2,3,3 ', 4 '-bibenzene tetracarboxylic dianhydride 0.5mol, yield are 50%.
Embodiment 9
Under nitrogen protection; with 0.75mol N-methyl-3-chloro phthalamide; 0.25mol N-methyl-4-chloro phthalamide; 0.025mol Nickel Bromide, 0.08mol three (2-aminomethyl phenyl) phosphine, the DMAc solvent of 300ml add in the 500ml there-necked flask; treat that temperature rises to 80 ℃; stir adding 1.5mol zinc powder after ten minutes, solution becomes sorrel, and reaction is carried out can finishing behind the 1h.Promptly get N, N '-dimethyl-biphenyl tetracarboxylic acyl diimine.
Embodiment 10
Under nitrogen protection, with 0.6mol N-normal-butyl-3-chloro phthalamide, 0.4mol N-normal-butyl-4-chloro phthalamide; 0.025mol Nickel Chloride, the Sodium Bromide of 0.25mol, 0.1mol three (3-ethylphenyl) phosphine; the sulfolane solvent of 300ml adds in the 500ml there-necked flask; treat that temperature rises to 80 ℃, stir adding 1.5mol zinc powder after ten minutes, solution becomes sorrel; after 1.5h is carried out in reaction; filtrate is poured in the big water gaging, filter collecting precipitation, then it is joined in the NaOH water aqueous solution; behind the reflux 12h; cooled and filtered is carried out acidifying with filtrate with concentrated hydrochloric acid, filter out the solid of separating out after; add refluxing xylene band water; after water Ex-all in the system, filtered while hot is separated out solid; obtain 2; 3,3 ', 4 '-bibenzene tetracarboxylic dianhydride.
Embodiment 11
Under nitrogen protection; with 0.2mol N-normal-butyl-3-chloro phthalamide; 0.7mol N-normal-butyl-4-chloro phthalamide; 0.025mol Nickel Bromide, 0.15mol three (3-isopropyl phenyl) phosphine, the DMAc solvent of 300ml add in the 500ml there-necked flask; treat that temperature rises to 60 ℃; stir adding 1.5mol zinc powder after ten minutes, solution becomes sorrel, and reaction is carried out can finishing behind the 2.5h.Filtrate is poured in the big water gaging, filter collecting precipitation, it is joined in the NaOH aqueous solution then, behind the reflux 12h, cooled and filtered is carried out acidifying with filtrate with concentrated hydrochloric acid, after filtering out the solid of separating out, add refluxing xylene band water, after water Ex-all in the system, filtered while hot, separate out solid, obtain 2,3,3 ', 4 '-bibenzene tetracarboxylic dianhydride.
Embodiment 12
Under nitrogen protection; with 0.2mol N-ethyl-3-chloro phthalamide; 0.7mol N-ethyl-4-chloro phthalamide; 0.025mol Nickel Bromide, 0.05mol three (2-n-pentyl phenyl) phosphine, the DMAc solvent of 400ml add in the 500ml there-necked flask; treat that temperature rises to 65 ℃; stir adding 1.5mol zinc powder after ten minutes, solution becomes sorrel, and reaction is carried out can finishing behind the 3.5h.Filtrate is poured in the big water gaging, filter collecting precipitation, it is joined in the NaOH aqueous solution then, behind the reflux 24h, cooled and filtered is carried out acidifying with filtrate with concentrated hydrochloric acid, after filtering out the solid of separating out, add refluxing xylene band water, after water Ex-all in the system, filtered while hot, separate out solid, obtain 2,3,3 ', 4 '-bibenzene tetracarboxylic dianhydride.
Claims (12)
1. one kind 2,3,3 '; the preparation method of 4 '-bibenzene tetracarboxylic dianhydride and derivative thereof, wherein a kind of process of reaction is as follows: under nitrogen protection, with the chlorophthalic acid dimethyl ester; nickel halogenide and triphenylphosphine dissolved are in polar aprotic solvent; after being heated to 60-120 ℃; add excessive zinc powder again, after 0.5-6h is carried out in reaction, filtrate is poured in the big water gaging; the collecting precipitation thing; this throw out is added in the NaOH aqueous solution, behind the heating hydrolysis reaction 4-24h, cooling; filter; filtrate is carried out acidifying with concentrated hydrochloric acid, filter out insolubles, after again filtrate being concentrated; directly with toluene or dimethylbenzene band water; after water Ex-all in the system, filter; solid is separated out in cooling; collect solid; thorough drying; the heating, vacuum distillation obtains 2; 3; 3 ', 4 '-bibenzene tetracarboxylic dianhydride, reaction process is as follows:
The reaction raw materials that adopts is the chlorophthalic acid diester, and the position of substitution of chlorine atom is 3 or 4 in the raw material, and the R representative contains 1-6 carbon atom straight chain or branched alkyl; The position of substitution of chlorine atom can be 3 or 4, and the molar ratio of used 3-chlorinated compound and 4-chlorinated compound is 1: 3-3: 1.
2, as claimed in claim 1 a kind of 2,3, the preparation method of 3 ', 4 '-bibenzene tetracarboxylic dianhydride and derivative thereof is characterized in that, catalyzer is two (trialkyl phosphine) nickel halogenides or two (triaryl phosphine) nickel halogenide.
3, as claimed in claim 1 or 2 a kind of 2,3, the preparation method of 3 ', 4 '-bibenzene tetracarboxylic dianhydride and derivative thereof is characterized in that, described catalyzer is the orgnometallic catalyst by trialkyl phosphine or triaryl phosphine and dihalide nickel on-site preparation; Wherein trialkyl phosphine or triaryl phosphine (PR '
3) be catalyst ligand, substituent R ' can be the alkyl of 1-12 carbon atom, the alkoxyl group of 1-12 carbon atom, the aromatic base that the alkoxyl group of the aromatic base of a 6-10 carbon atom or 1-12 carbon atom replaces.
4, as claimed in claim 1 or 2 a kind of 2,3, the preparation method of 3 ', 4 '-bibenzene tetracarboxylic dianhydride and derivative thereof is characterized in that, the add-on of described catalyzer by the 2.5-12.5% of adding feed molar number; The add-on of catalyst ligand is 2-6 a times that catalyzer adds mole number; The add-on of zinc powder is 1.1-2.5 a times of feed molar amount, and catalyzer dihalide nickel is Nickel Bromide or Nickel Chloride.
5, as claimed in claim 1 a kind of 2,3, the preparation method of 3 ', 4 '-bibenzene tetracarboxylic dianhydride and derivative thereof is characterized in that, when catalyzer was Nickel Chloride, the catalysis initiator was a Sodium Bromide, and add-on is for adding the 15-25% of feed molar number.
6, as claimed in claim 1 a kind of 2,3,3 ', the preparation method of 4 '-bibenzene tetracarboxylic dianhydride and derivative thereof, it is characterized in that, described aprotic solvent is N, N '-dimethyl formamide (DMF), N, N '-N,N-DIMETHYLACETAMIDE (DMAc), N-N-methyl-2-2-pyrrolidone N-(NMP), dimethyl sulfoxide (DMSO) (DMSO) or tetramethylene sulfone.
7. as claimed in claim 12,3, the preparation method of 3 ', 4 '-bibenzene tetracarboxylic dianhydride and derivative thereof is characterized in that using following chlorophthalic acid diester component synthesizing bibenzene tetracarboxylic dianhydride and derivative thereof:
Wherein the position of substitution of chlorine atom can be 3 or 4, the R representative contains 1-6 carbon atom straight chain or branched alkyl, R in the chlorophthalimide can also be phenyl, and the molar ratio of used 3-chlorinated compound and 4-chlorinated compound is 1: 3-3: 1.
8. one kind 2,3,3 '; the preparation method of 4 '-bibenzene tetracarboxylic dianhydride and derivative thereof; it is characterized in that reaction process is as follows: under nitrogen protection, with chlorophthalic acid list imines; nickel halogenide and triphenylphosphine dissolved in polar aprotic solvent, be heated to 60-120 ℃ after; add excessive zinc powder again; after 0.5-6h is carried out in reaction, filtrate is poured in the big water gaging into the collecting precipitation thing; this throw out is added in the NaOH aqueous solution; behind the heating hydrolysis reaction 4-24h, cooling; filter, filtrate is carried out acidifying with concentrated hydrochloric acid; filter out insolubles; after again filtrate being concentrated, directly with toluene or dimethylbenzene band water, after water Ex-all in the system; filter; solid is separated out in cooling; collect solid; the vacuum-sublimation of thorough drying post-heating; obtain 2,3,3 '; 4 '-bibenzene tetracarboxylic dianhydride, reaction process is as follows:
The reaction raw materials that adopts is a chlorophthalic acid list imines, and the position of substitution of chlorine atom is 3 or 4 in the raw material, and the R representative contains 1-6 carbon atom straight chain or branched alkyl; The position of substitution of chlorine atom can be 3 or 4, and the molar ratio of used 3-chlorinated compound and 4-chlorinated compound is 1: 3-3: 1;
Catalyzer is two (trialkyl phosphine) nickel halogenides or two (triaryl phosphine) nickel halogenide, and catalyzer is the orgnometallic catalyst by trialkyl phosphine or triaryl phosphine and dihalide nickel on-site preparation; Wherein trialkyl phosphine or triaryl phosphine (PR '
3) be catalyst ligand, substituent R ' can be the alkyl of 1-12 carbon atom, the alkoxyl group of 1-12 carbon atom, the aromatic base that the alkoxyl group of the aromatic base of a 6-10 carbon atom or 1-12 carbon atom replaces; The add-on of catalyzer by the 2.5-12.5% of adding feed molar number; The add-on of catalyst ligand is 2-6 a times that catalyzer adds mole number; The add-on of zinc powder is 1.1-2.5 a times of feed molar amount; Catalyzer dihalide nickel is Nickel Bromide or Nickel Chloride, when catalyzer is Nickel Chloride, the catalysis initiator is a Sodium Bromide, add-on is for adding the 15-25% of feed molar number, solvent is N, N '-dimethyl formamide (DMF), N, N '-N,N-DIMETHYLACETAMIDE (DMAc), N-N-methyl-2-2-pyrrolidone N-(NMP), dimethyl sulfoxide (DMSO) (DMSO) or tetramethylene sulfone.
As claimed in claim 2,3, the preparation method of 3 ', 4 '-bibenzene tetracarboxylic dianhydride and derivative thereof is characterized in that using chlorophthalimide synthesizing bibenzene tetracarboxylic dianhydride and derivative thereof:
The position of substitution of chlorine atom can be 3 or 4, the R representative contains 1-6 carbon atom straight chain or branched alkyl, R in the chlorophthalimide can also be phenyl, and the molar ratio of used 3-chlorinated compound and 4-chlorinated compound is 1: 3-3: 1.
10. as claim 1 or 3 described 2,3,3 ', the preparation method of 4 '-bibenzene tetracarboxylic dianhydride and derivative thereof, it is characterized in that, described catalyzer is two (trialkyl phosphine) nickel halogenides or two (triaryl phosphine) nickel halogenide, and catalyzer is the orgnometallic catalyst by trialkyl phosphine or triaryl phosphine and dihalide nickel on-site preparation; Wherein trialkyl phosphine or triaryl phosphine (PR '
3) be catalyst ligand, substituent R ' aromatic base that can replace for the alkoxyl group of the aromatic base of the alkoxyl group of the alkyl of 1-12 carbon atom, a 1-12 carbon atom, a 6-10 carbon atom or 1-12 carbon atom; The add-on of catalyzer by the 2.5-12.5% of adding feed molar number; The add-on of catalyst ligand is 2-6 a times that catalyzer adds mole number; The add-on of zinc powder is 1.1-2.5 a times of feed molar amount.
11. as claim 1 or 3 described 2,3, the preparation method of 3 ', 4 '-bibenzene tetracarboxylic dianhydride and derivative thereof is characterized in that, when described catalyzer was Nickel Chloride, the catalysis initiator was a Sodium Bromide, and add-on is for adding the 15-25% of feed molar number.
12. as claim 1 or 3 described 2,3,3 ', the preparation method of 4 '-bibenzene tetracarboxylic dianhydride and derivative thereof, it is characterized in that, described solvent is N, N '-dimethyl formamide (DMF), N, N '-N,N-DIMETHYLACETAMIDE (DMAc), N-N-methyl-2-2-pyrrolidone N-(NMP), dimethyl sulfoxide (DMSO) (DMSO) or tetramethylene sulfone.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717374B (en) * | 2009-12-08 | 2011-12-14 | 四川大学 | Compound comprising fork biphenyl center and preparation method thereof |
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| CN101139436B (en) * | 2007-10-18 | 2010-05-19 | 吉林大学 | Amine imines zinc catalyst and preparation method and use thereof |
| CN102171176B (en) * | 2008-08-06 | 2014-12-10 | 宇部兴产株式会社 | Method for producing biphenyltetracarboxylic acid tetraester |
| CN101481366B (en) * | 2008-12-29 | 2012-07-04 | 中国科学院长春应用化学研究所 | Preparation of 2,3,3',4'-biphenyl-tetracarboxylic acid dianhydride and derivatives thereof |
| CN102249944B (en) * | 2009-12-08 | 2013-10-16 | 四川大学 | Compound containing staggered biphenyl center and preparation method thereof |
| CN108333269A (en) * | 2018-02-01 | 2018-07-27 | 上海固创化工新材料有限公司 | A kind of purity analysis method of bibenzene tetracarboxylic dianhydride |
| CN113603664B (en) * | 2021-08-03 | 2023-06-20 | 哈尔滨工业大学（威海） | Method for preparing biphenyl dianhydride by microwave-assisted catalytic coupling |
| CN113480505B (en) * | 2021-08-03 | 2023-06-20 | 哈尔滨工业大学（威海） | Method for preparing, separating and purifying biphenyl derivatives through catalytic coupling |
| CN113461646B (en) * | 2021-08-03 | 2023-05-23 | 哈尔滨工业大学（威海） | Preparation and separation method of biphenyl dianhydride isomer |
| CN113582954B (en) * | 2021-08-03 | 2023-07-07 | 哈尔滨工业大学（威海） | Method for preparing biphenyl dianhydride based on coupling of metal coordination halogenated phthalimide monomer |
| CN115894416A (en) * | 2022-12-02 | 2023-04-04 | 大连新阳光材料科技有限公司 | Method for selectively preparing 2, 3',4' -biphenyl tetracarboxylic dianhydride |
| CN116514750A (en) * | 2023-03-24 | 2023-08-01 | 安徽秀朗新材料科技有限公司 | Production process of 2, 3',4' -biphenyl tetracarboxylic dianhydride |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101717374B (en) * | 2009-12-08 | 2011-12-14 | 四川大学 | Compound comprising fork biphenyl center and preparation method thereof |
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