CN101607894B - Preparation method of 3,3',4,4'-tetra carboxylic acid biphenyl - Google Patents
Preparation method of 3,3',4,4'-tetra carboxylic acid biphenyl Download PDFInfo
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- CN101607894B CN101607894B CN 200910074886 CN200910074886A CN101607894B CN 101607894 B CN101607894 B CN 101607894B CN 200910074886 CN200910074886 CN 200910074886 CN 200910074886 A CN200910074886 A CN 200910074886A CN 101607894 B CN101607894 B CN 101607894B
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Abstract
The invention provides a preparation method of 3,3',4,4'-tetra carboxylic acid biphenyl and relates to the technical field of organic material preparation. The method mainly comprises the following steps: preparing 3-10% of alkali solution, adding 4-halogenated phthalic acid in the alkali solution, dissolving; adding palladium carbon-potassium iodide binary compound catalyst, dripping alcohols at 80-100 DEG C for 3-8h, after completing the reaction filtrating the solution to obtain the palladium carbon-potassium iodide catalyst; adding the filtrate in 5-10% of sulfuric acid, filtrating the solution to obtain raw tetra carboxylic acid biphenyl and finally refining the raw product; wherein, the molar ratio of COOH in 4-halogenated phthalic acid to OH- in the alkali solution is 1 to 2-3 and the molar ratio of the additive functional hydroxyl of alcohols to 4-halogenated phthalic acid is 1 to 1-3. The invention overcomes the defects of the prior art, and has the outstanding advantages of unique method, simple process, easy operation, high yield, low cost, high production efficiency and economic benefit and the like.
Description
Technical field
The invention belongs to the preparing technical field of fine chemistry industry organic materials, be specifically related to 4,4 '-preparation method of bibenzene tetracarboxylic.
Background technology
3,3 ', 4; 4 '-bibenzene tetracarboxylic (BPTA) dehydration obtains 3,3 ', 4; 4 '-bibenzene tetracarboxylic dianhydride (BPDA) is an important polymer---the precursor of polyimide can aggregate into polyimide with multi-functional amine; Polyimide is the highest ultra heat stable resin of heat resisting temperature up to now; And have good hydrolytic resistance, mechanicalness and snappiness, can be used for making thermostable photosensitive resin, spectral filter, liquid-crystal display, conductor and semi-conductive cross-linked binder, the protective material that also can be used for laser, lithium cell and in space, use.
Relevant BPTA synthetic reported in literature is a lot; The disclosed compound method of US5095144 for example; With Pd-Fe/C is catalyzer, the disposable adding of reductive agent glycerine; Carry out self dehalogenation coupling of 4-chlorophthalic acid sodium salt (mixture), the transformation efficiency 100% of 4-chlorophthalic acid sodium salt, the yield of BPTA is up to 74.2%; This method is simple, but the Pd large usage quantity, and the yield of BPTA also has much room for improvement.The oxidative coupling method of dimethyl phthalate, p-phthaloyl chloride coupling method, electrolysis coupling method and anhydrous trimellitic acid list chloride method; Domestic preparation research to BPTA is at present also fewer; Employing 4-chlorophthalic acid dimethyl esters such as Ding Mengxian are raw material; Carry out coupled reaction with two (triphenyl phosphine)-Nickel Chlorides as catalyzer, synthesized the bibenzene tetracarboxylic methyl esters, alkaline hydrolysis prepares BPTA then.All there is the low and higher deficiency of cost of yield in aforesaid method, and production efficiency and economic benefit are relatively poor.
Summary of the invention
The purpose of this invention is to provide a kind of preparation 3,3 ', 4,4 '-method of bibenzene tetracarboxylic, have the method uniqueness, technological process is simple, easy to operate, yield is high and cost is lower, production efficiency and economic benefit be than advantages such as height.
The present invention seeks to realize like this: a kind of preparation 3,3 ', 4,4 '-method of bibenzene tetracarboxylic, it is characterized in that the 4-halophthalic acid under palladium charcoal-potassiumiodide binary composite catalyst effect, carries out linked reaction with the alcohols reductive agent, its step comprises:
A, preparation 3-10% alkaline solution add the 4--halophthalic acid in the alkaline solution, its-COOH: OH
-Mol ratio=1: 1-3, dissolving;
B, adding palladium charcoal-potassiumiodide binary composite catalyst; Drip alcohols material down at 80-100 ℃, alcohols material available hydroxyl add-on and 4-halophthalic acid mol ratio=1: 1-3, the dropping time is 3-8 hour; Reaction finishes, and filters palladium charcoal-potassium iodide catalyst;
C, gained filtrating is added drop-wise in the 5-10% sulphuric acid soln, filters, promptly obtain the bullion bibenzene tetracarboxylic.
Described 4-halophthalic acid also can be 4-fluorine phthalic acid or 4-phthalate bromine, 4-iodine phthalic acid for the 4-chloro-o-phthalic acid is good.
Described alcohols material is methyl alcohol, terepthaloyl moietie or glycerine etc.
Described alkali is alkali-metal oxyhydroxide, like sodium hydroxide or Pottasium Hydroxide etc.
The preferable method for making of described palladium charcoal-potassiumiodide binary composite catalyst is: solid K I is dissolved in≤50% methanol aqueous solution in; Getting 1～4% palladium carbon catalyst adds in the solution; 40～70 ℃ of stirrings that heat up add gac again and stir cooling, KI: 1～4% palladium carbon catalyst: gac=1: 2～5: 2～5; Filter, oven dry promptly obtains palladium charcoal-potassiumiodide binary composite catalyst.
Described preparation 3,3 ', 4,4 '-method of bibenzene tetracarboxylic, it is characterized in that can be with the bullion processing of re-refining, obtain elaboration 3,3 ', 4,4 '-bibenzene tetracarboxylic.
The present invention has following unusual effect: overcome the deficiency of prior art, had the method uniqueness, technological process is simple, easy to operate, yield is high and cost is lower, production efficiency and the more high outstanding advantage of economic benefit.
Be described further below in conjunction with embodiment, but not as to qualification of the present invention.
Embodiment
One, lay-by material: the preparation technology of binary composite catalyst palladium charcoal-potassiumiodide:
Solid K I is dissolved in≤50% methanol aqueous solution in; Getting 1～4% palladium carbon catalyst adds in the solution; 40～70 ℃ of stirrings that heat up add gac again and stir cooling, KI: 1～4% palladium carbon catalyst: gac=1: 2～5: 2～5; Filter, oven dry promptly obtains palladium charcoal-potassiumiodide binary composite catalyst.
Preparation binary composite catalyst palladium charcoal-potassiumiodide gives an example 1:
Weighing 3g solid K I is dissolved in 50 milliliter of 20% methanol aqueous solution, gets the 10g3% palladium carbon catalyst and adds in the solution, is warmed up to 60 ℃; Stirred 2 hours, and added 200 order gac 5g again, stirred 3 hours; Cooling is filtered, and drains; 50 ℃ of vacuum dryings 2 hours, gained is binary composite catalyst palladium charcoal-potassiumiodide, and is subsequent use.
Preparation binary composite catalyst palladium charcoal-potassiumiodide gives an example 2:
Weighing 5g solid K I is dissolved in 100 milliliter of 50% methanol aqueous solution, gets the 10g1% palladium carbon catalyst and adds in the solution, is warmed up to 40 ℃; Stirred 2 hours, and added 200 order gac 10g again, stirred 2 hours; Cooling is filtered, and drains; 50 ℃ of vacuum dryings 2 hours, gained is binary composite catalyst palladium charcoal-potassiumiodide, and is subsequent use.
Preparation binary composite catalyst palladium charcoal-potassiumiodide gives an example 3:
Weighing 4g solid K I is dissolved in 50 milliliter of 10% methanol aqueous solution, gets the 20g4% palladium carbon catalyst and adds in the solution, is warmed up to 70 ℃; Stirred 2 hours, and added 200 order gac 20g again, stirred 3 hours; Cooling is filtered, and drains; 50 ℃ of vacuum dryings 2 hours, gained is binary composite catalyst palladium charcoal-potassiumiodide, and is subsequent use.
Two, the embodiment of the invention 1:
In the four-hole reaction flask that is equipped with tap funnel, TM and stirring, add 18g (0.45mol) sodium hydroxide, 200ml water, be warmed up to 80 ℃, dissolve transparent after, add 15g (0.075mol) 4-chloro-o-phthalic acid in batches, add the above-mentioned Pd/carbon catalyst of 0.3g; Be warmed up to 90 ℃, drip 3g methyl alcohol, 4 hours dropping time is after dropwising; Insulation reaction 3 hours is filtered, and mother liquor is added drop-wise in 10% sulphuric acid soln, obtains white crystals; Filtered while hot, washing obtains the bullion bibenzene tetracarboxylic.
The bullion bibenzene tetracarboxylic is placed in 10 times of purified water, 100 ℃ of poach 5 hours, cooling, washing, drying obtain bibenzene tetracarboxylic 10.1g, record yield 82%, purity 99.7%, fusing point 298-300 ℃.
The embodiment of the invention 2:
In the four-hole reaction flask that is equipped with tap funnel, TM and stirring, add 14g (0.25mol) Pottasium Hydroxide, 250ml water, be warmed up to 80 ℃, dissolve transparent after; Gradation adds 4-phthalate bromine 12.3g (0.05mol), adds the above-mentioned catalyzer of 0.1g, is warmed up to 95 ℃, Dropwise 5 g aqueous glycerin solution; 2-5 hour dropping time, after dropwising, insulation reaction 5 hours; Filter, mother liquor is added drop-wise in 10% sulphuric acid soln, obtains white crystals; Filtered while hot, washing obtains the bullion bibenzene tetracarboxylic.
The bullion bibenzene tetracarboxylic is placed in 8 times of purified water, 100 ℃ of poach 4 hours, filtration, washing, drying obtain bibenzene tetracarboxylic 7.4g, record yield 89.7%, purity 99.6%, fusing point 297-299 ℃.
The embodiment of the invention 3:
In the four-hole reaction flask that is equipped with tap funnel, TM and stirring, add 14g (0.25mol) Pottasium Hydroxide, 220ml water, be warmed up to 80 ℃, dissolve transparent after; Gradation adds 4-iodine phthalic acid 11.7g (0.04mol), adds the above-mentioned catalyzer of 0.1g, is warmed up to 95 ℃, drips the 1g methanol solution; 2-5 hour dropping time, after dropwising, insulation reaction 5 hours; Filter, mother liquor is added drop-wise in 10% sulphuric acid soln, obtains white crystals; Filtered while hot, washing obtains the bullion bibenzene tetracarboxylic.
The bullion bibenzene tetracarboxylic is placed in 8 times of purified water, 100 ℃ of poach 3 hours, filtration, washing, drying obtain bibenzene tetracarboxylic 5.95g, record yield 90%, purity 99.5%, fusing point 297-299 ℃.
The embodiment of the invention 4:
In the four-hole reaction flask that is equipped with tap funnel, TM and stirring, add 7g (0.175mol) sodium hydroxide, 200ml water, be warmed up to 80 ℃, dissolve transparent after, add 15g (0.075mol) 4-chloro-o-phthalic acid in batches, add the above-mentioned Pd/carbon catalyst of 0.5g; Be warmed up to 95 ℃, drip 7g methyl alcohol, 4 hours dropping time is after dropwising; Insulation reaction 3 hours is filtered, and mother liquor is added drop-wise in 10% sulphuric acid soln, obtains white crystals; Filtered while hot, washing obtains the bullion bibenzene tetracarboxylic.
The bullion bibenzene tetracarboxylic is placed in 10 times of purified water, 100 ℃ of poach 5 hours, cooling, washing, drying obtain bibenzene tetracarboxylic 10.3g, record yield 83%, purity 99.7%, fusing point 298-300 ℃.
The embodiment of the invention 5:
In the four-hole reaction flask that is equipped with tap funnel, TM and stirring, add 7.3g (0.13mol) Pottasium Hydroxide, 230ml water, be warmed up to 80 ℃, dissolve transparent after; Gradation adds 4-phthalate bromine 12.3g (0.05mol), adds the above-mentioned catalyzer of 0.3g, is warmed up to 85 ℃, drips the 11g aqueous glycerin solution; 2-5 hour dropping time, after dropwising, insulation reaction 3 hours; Filter, mother liquor is added drop-wise in 5% sulphuric acid soln, obtains white crystals; Filtered while hot, washing obtains the bullion bibenzene tetracarboxylic.
The bullion bibenzene tetracarboxylic is placed in 8 times of purified water, 100 ℃ of poach 4 hours, filtration, washing, drying obtain bibenzene tetracarboxylic 7.5g, record yield 91%, purity 99.5%, fusing point 297-299 ℃.
The embodiment of the invention 6:
In the four-hole reaction flask that is equipped with tap funnel, TM and stirring, add 5.4g (0.096mol) Pottasium Hydroxide, 170ml water, be warmed up to 80 ℃, dissolve transparent after; Gradation adds 4-iodine phthalic acid 11.7g (0.04mol), adds the above-mentioned catalyzer of 0.5g, is warmed up to 90 ℃, drips the 3.2g methanol solution; 3 hours dropping time, after dropwising, insulation reaction 3 hours; Filter, mother liquor is added drop-wise in 5% sulphuric acid soln, obtains white crystals; Filtered while hot, washing obtains the bullion bibenzene tetracarboxylic.
The bullion bibenzene tetracarboxylic is placed in 8 times of purified water, 100 ℃ of poach 3 hours, filtration, washing, drying obtain bibenzene tetracarboxylic 6.0g, record yield 91.5%, purity 99.6%, fusing point 297-299 ℃.
The embodiment of the invention 7:
In the four-hole reaction flask that is equipped with tap funnel, TM and stirring, add 18g (0.45mol) sodium hydroxide, 280ml water, be warmed up to 80 ℃, dissolve transparent after, add 15g (0.075mol) 4-chloro-o-phthalic acid in batches, add the above-mentioned Pd/carbon catalyst of 0.6g; Be warmed up to 90 ℃, drip 7g terepthaloyl moietie, 2 hours dropping time is after dropwising; Insulation reaction 3 hours is filtered, and mother liquor is added drop-wise in 6% sulphuric acid soln, obtains white crystals; Filtered while hot, washing obtains the bullion bibenzene tetracarboxylic.
The bullion bibenzene tetracarboxylic is placed in 10 times of purified water, 100 ℃ of poach 5 hours, cooling, washing, drying obtain bibenzene tetracarboxylic 10.3g, record yield 83%, purity 99.5%, fusing point 298-300 ℃.
Three, other embodiment:
A (with the 4-halophthalic acid without this catalyzer time):
In the four-hole reaction flask that is equipped with tap funnel, TM and stirring, add 20g (0.5mol) sodium hydroxide, 180ml water, be warmed up to 80 ℃, dissolve transparent after, gradation adds 4-chlorophthalic acid g (0.1mol), adds 5% palladium carbon catalyst 0.25g; Be warmed up to 90 ℃, drip 30g methyl alcohol, dripped time 2-5 hour, after dropwising; Insulation reaction 5 hours is filtered, and mother liquor is added drop-wise in 10% sulphuric acid soln, obtains white crystals; Filtered while hot, washing obtains the bullion bibenzene tetracarboxylic.
The bullion bibenzene tetracarboxylic is placed in 10 times of purified water, 100 ℃ of poach 3 hours, filtration, washing, drying obtain bibenzene tetracarboxylic 11.5g, record yield 70%, purity 99.5%, fusing point 297-300 ℃.
B (with the 4-halophthalic acid without this catalyzer time):
In the four-hole reaction flask that is equipped with tap funnel, TM and stirring, add 14g (0.25mol) Pottasium Hydroxide, 220ml water, be warmed up to 80 ℃, dissolve transparent after; Gradation adds 4-phthalate bromine 12.3g (0.05mol), adds 4% palladium carbon catalyst 0.15g, is warmed up to 95 ℃, Dropwise 5 g aqueous glycerin solution; 2-5 hour dropping time, after dropwising, insulation reaction 5 hours; Filter, mother liquor is added drop-wise in 10% sulphuric acid soln, obtains white crystals; Filtered while hot, washing obtains the bullion bibenzene tetracarboxylic.
The bullion bibenzene tetracarboxylic is placed in 8 times of purified water, 100 ℃ of poach 4 hours, filtration, washing, drying obtain bibenzene tetracarboxylic 6.7g, record yield 81%, purity 99.5%, fusing point 297-299 ℃.
De1 reaction equation of the present invention is exemplified below:
Effect of the present invention is significant.Is raw material like Hitachi, Ltd with the chloro-benzoic anhydride, uses palladium to be merely 57% as the highest yield of Preparation of Catalyst bibenzene tetracarboxylic.
Claims (6)
- One kind prepare 3,3 ', 4,4 '-method of bibenzene tetracarboxylic, it is characterized in that the 4-halophthalic acid under palladium charcoal-potassiumiodide binary composite catalyst effect, carries out linked reaction with the alcohols reductive agent, its step comprises:A, preparation 3-10% alkaline solution add the 4-halophthalic acid in the alkaline solution its COOH: OH -Mol ratio=1: 2-3, dissolving;B, adding palladium charcoal-potassiumiodide binary composite catalyst; Drip alcohols material down at 80-100 ℃, alcohols material available hydroxyl add-on and 4-halophthalic acid mol ratio=1: 1-3, the dropping time is 3-8 hour; Reaction finishes, and filters palladium charcoal-potassium iodide catalyst;C, gained filtrating is added drop-wise in the 5-10% sulphuric acid soln, filters, promptly obtain the bullion bibenzene tetracarboxylic.
- 2. a kind of preparation 3,3 according to claim 1 ', 4,4 '-method of bibenzene tetracarboxylic, it is characterized in that described 4-halophthalic acid is the 4-chloro-o-phthalic acid.
- 3. a kind of preparation 3,3 according to claim 1 ', 4,4 '-method of bibenzene tetracarboxylic, it is characterized in that described alcohols material is methyl alcohol, terepthaloyl moietie or glycerine.
- 4. a kind of preparation 3,3 according to claim 1 ', 4,4 '-method of bibenzene tetracarboxylic, it is characterized in that described alkali is alkali-metal oxyhydroxide, said alkali-metal oxyhydroxide is sodium hydroxide or Pottasium Hydroxide.
- 5. a kind of preparation 3,3 according to claim 1 ', 4; 4 '-method of bibenzene tetracarboxylic, it is characterized in that the method for making of described palladium charcoal-potassiumiodide binary composite catalyst is: solid K I is dissolved in≤50% methanol aqueous solution in, get 1～4% palladium carbon catalyst and add in the solution; 40～70 ℃ of stirrings that heat up add gac again and stir cooling, KI: 1～4% palladium carbon catalyst: gac=1: 2～5: 2～5; Filter, oven dry promptly obtains palladium charcoal-potassiumiodide binary composite catalyst.
- According to claim 1,2,3,4 or 5 described a kind of preparations 3,3 ', 4,4 '-method of bibenzene tetracarboxylic, it is characterized in that crude product refining processing, obtain elaboration 3,3 ', 4,4 '-bibenzene tetracarboxylic.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701964B (en) * | 2012-05-09 | 2014-01-01 | 江西师范大学 | Method for synthesizing 4,4'-diphenic acid |
| 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 |
| CN110818551B (en) * | 2019-11-19 | 2022-06-24 | 常州市阳光药业有限公司 | Synthetic method of 3,3',4,4' -biphenyltetracarboxylic acid |
| 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 |
| CN111943922B (en) * | 2020-09-01 | 2022-07-08 | 上海固创化工新材料有限公司 | Method for recycling 3,3', 4,4' -diphenyl ether tetracarboxylic dianhydride from adsorption activated carbon and reusing activated carbon |
| CN113750994B (en) * | 2021-10-21 | 2023-12-26 | 西安凯立新材料股份有限公司 | Catalyst for producing 3,3',4,4' -biphenyl tetracarboxylic acid and preparation method thereof |
| CN114478315B (en) * | 2022-02-25 | 2023-10-31 | 山东艾孚特科技有限公司 | Method for catalytic reduction of irosartan biphenyl waste residues by using halogen-modified Pd/C catalyst |
| CN114773178A (en) * | 2022-04-24 | 2022-07-22 | 河北海力香料股份有限公司 | Method for reactive crystallization of 3,3 ', 4, 4' -biphenyltetracarboxylic acid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4727185A (en) * | 1985-01-21 | 1988-02-23 | Hitachi, Ltd. | Process for preparation of 3,3',4,4'-biphenyltetracarboxylic acid salts |
| CN1041754A (en) * | 1988-10-11 | 1990-05-02 | 中科院长春应用化学研究所 | 3,3 ', 4,4 '-bibenzene tetracarboxylic and derivative thereof synthetic |
| US5081291A (en) * | 1990-09-21 | 1992-01-14 | E. I. Du Pont De Nemours And Company | Process for manufacture of 3,3',4,4'-biphenyltetracarboxylic acid |
| CN101031535A (en) * | 2005-04-14 | 2007-09-05 | 杰富意化学株式会社 | Process for producing biphenyltetracarboxylic acid |
-
2009
- 2009-07-15 CN CN 200910074886 patent/CN101607894B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4727185A (en) * | 1985-01-21 | 1988-02-23 | Hitachi, Ltd. | Process for preparation of 3,3',4,4'-biphenyltetracarboxylic acid salts |
| CN1041754A (en) * | 1988-10-11 | 1990-05-02 | 中科院长春应用化学研究所 | 3,3 ', 4,4 '-bibenzene tetracarboxylic and derivative thereof synthetic |
| US5081291A (en) * | 1990-09-21 | 1992-01-14 | E. I. Du Pont De Nemours And Company | Process for manufacture of 3,3',4,4'-biphenyltetracarboxylic acid |
| CN101031535A (en) * | 2005-04-14 | 2007-09-05 | 杰富意化学株式会社 | Process for producing biphenyltetracarboxylic acid |
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