CN101508642B - Method for preparing 2,5-dihydroxy p-benzene dicarboxylic acid - Google Patents
Method for preparing 2,5-dihydroxy p-benzene dicarboxylic acid Download PDFInfo
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- CN101508642B CN101508642B CN2009100302157A CN200910030215A CN101508642B CN 101508642 B CN101508642 B CN 101508642B CN 2009100302157 A CN2009100302157 A CN 2009100302157A CN 200910030215 A CN200910030215 A CN 200910030215A CN 101508642 B CN101508642 B CN 101508642B
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- phthalic acid
- dihydric para
- gac
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- resorcinol
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
A method for the carboxylation preparation of 2,5-dihydroxyterephthalic acid by taking n-octane as solvent to Pd(II)/C-catalyze the hydroquinone is disclosed, specifically comprising the steps of: in a high-pressure reaction kettle, taking sodium phenolate, potassium hydroxide and carbon dioxide as reactants, performing Pd(II)/C-catalysis to prepare 2,5-dihydroxyterephthalic acid sylvite, and obtaining the 2,5-dihydroxyterephthalic acid by means of recrystallization and acidification. The inventive catalyst is simply prepared, the solvent is easy for recovery and the product is high in purity.
Description
Technical field
The present invention relates to a kind of catalytic preparation 2,5-dihydric para-phthalic acid's method, refering in particular to the octane is solvent; Adopting Pd (II)/C is the catalyst Resorcinol; Behind Pottasium Hydroxide and the carbonic acid gas carboxylation reaction, again through acidifying preparation 2,5-dihydric para-phthalic acid.
Background technology
2, the 5-dihydric para-phthalic acid is important organic synthesis intermediate, can be used to synthetic polymer, title complex, tinting material and fluorescent substance.2, the mixture of 5-dihydric para-phthalic acid and terephthalic acid can with glycol reaction, the copolyether that is used to produce linear polyester or has fiber, film forming character.2; Non-homopolymerization takes place and generates high-molecular weight linear polyester and multipolymer in 5-diaminostilbene, 4-phenylene dimercaptan in polyphosphoric acid, with 2; 3; 5,6-4-aminopyridine (TAP) but direct polymerization become to have the good insulation performance performance, be applicable to the M5 polymkeric substance of out of use field of some thomel such as electron trade etc.Other 2,5-dihydric para-phthalic acid and 1, n-dialkyl group glycol and 6 valency coordinate Mg
2+, Ca
2+, Sn
2+, Pb
2+, Ga
2+, In
2+, Bi
2+, Si
2+, Mn
2+, Co
2+Form title complex with special performance Deng metals ion.
2; 5-dihydric para-phthalic acid's building-up reactions belongs to the Kolbe-Schmitt reaction; In its preparation process, in order to alleviate the sticking still wall of reaction mass caking, reaction times weak point, shortcomings such as transformation efficiency and yield height; Investigators are solvent with YLENE often both at home and abroad, but have the big shortcoming of solvent toxicity.In addition, few people with catalyst applications in Kolbe-Schmitt carboxylation process.Schmeling, Narmandakh etc. " Journal ofBacteriology " 2004 the 23rd phase articles " Phenylphosphate synthase:a newphosphotransferase catalyzing the first step in anaerobic phenol metabolism inThauera aromatica " and 2006 22 the phase article " Phosphorylation of phenol byphenylphosphate synthase:role of histidine phosphate in catalysis " studied the anaerobic metabolism (claiming biological Kolbe-Schmitt reaction again) of phenol in the enzyme catalysis denitrifying bacterium body; Other researcher was reported the carboxylation reaction of compounds such as Pd (II) catalytic chlorination benzyl, biphenyl, methyl-phenoxide, furans, thiophene, for example article " the Synthesis of 2-arylpropionic acids by electrocarboxylation of benzylchloridescatalysed by PdCl that delivers in " Electrochemistry Communications " the 12nd phase of calendar year 2001 of people such as Damodar
2(PPh
3)
2" reported Pd (II) catalytic chlorination benzyl carboxylation reaction; Pd (II) catalysis biphenyl carboxylation reaction reported in the article that people such as Yamada delivered at " Journal of Molecular Catalysis A:Chemical " in 2007 " Carboxylationand hydroxylation of biphenyl by the Pd/molybdovanadophosphoric acid/dioxygensystem "; But do not see with the octane to be solvent; Adopt the catalyst Resorcinol to obtain 2,5-dihydric para-phthalic acid's report.
Summary of the invention
The purpose of this invention is to provide a kind of catalytic preparation 2,5-dihydric para-phthalic acid's method promptly is solvent with the octane; Adopt Pd (II)/C catalysis Resorcinol; Behind Pottasium Hydroxide and the carbonic acid gas carboxylation reaction, again through acidifying preparation 2,5-dihydric para-phthalic acid.
Octane is solvent Pd (II)/C catalysis Resorcinol carboxylation preparation 2, and the 5-dihydric para-phthalic acid may further comprise the steps:
(1) with after the carried by active carbon body and function Hydrogen chloride stir process, extremely neutral with the zero(ppm) water washing, vacuum-drying; The gained gac is sieved; Use dissolving with hydrochloric acid PdCl
2, the gac that adds after sieving then adsorbs, and promptly gets catalyst P d (II)/C after the thorough drying;
(2) in autoclave, add 5%～20%Pd (the II)/C catalyzer of Resorcinol, Pottasium Hydroxide, octane and Resorcinol quality, feed dioxide gas, be warming up to 200～220 ℃, still is pressed reach 9.5～11.5MPa, react more than 4 h;
(3) with post reaction mixture cooling, suction filtration; Gained filtrating is reclaimed; It is that heated and boiled is removed residual solvent in 0.1% the aqueous solution of sodium bisulfite that filter cake is dissolved in mass percentage concentration, after thing to be mixed fully dissolves while hot suction filtration remove impurity and catalyzer; To filtrate is cooled to crystallization below 8 ℃ in ice-water bath, and uses the frozen water washing leaching cake;
(4) after the gained filter cake is dissolved in hot water, adds concentrated hydrochloric acid and regulate pH less than 2, suction filtration, washing leaching cake promptly gets 2 after the vacuum-drying, the 5-dihydric para-phthalic acid.
Above-mentioned preparation method, use in the step 1 mass percentage concentration be 5% Hydrogen chloride behind 80 ℃ of stir process gac 3h, vacuum-drying 12h crosses 200 mesh sieves with the gained gac; Dissolving with hydrochloric acid PdCl with 6mol/L
2, the gac that adds after sieving then adsorbs PdCl
2With the mass ratio of gac be 1: 50, promptly get catalyst P d (II)/C in 120 ℃ of thorough dryings.
Above-mentioned preparation method, the mass ratio of Resorcinol and Pottasium Hydroxide is 13.75: 35 (being that mol ratio is 1: 5) in the step 2.
Above-mentioned preparation method, the add-on of octane is as the criterion to fill it up with reaction kettle in the step 2.
Above-mentioned preparation method, the mass percentage concentration of sodium sulfite anhy 96 is 0.1% in the step 3.
Distinguishing feature of the present invention is 2, and 5-dihydric para-phthalic acid's yield is high, and purity is high.2,5-dihydric para-phthalic acid's yield＞70%, the highest yield can reach 85%, purity＞99%.
Another distinguishing feature of the present invention is to be the solvent Synthetic 2 with the octane, 5-dihydric para-phthalic acid, solvent low toxicity and be easy to reclaim.
Embodiment
Below in conjunction with the practical implementation instance the present invention is further specified.
Instance 1
In having the 0.5L autoclave of heating, stirring and temperature controlling system, add 5%Pd (the II)/C catalyzer of 13.75g Resorcinol, 35g Pottasium Hydroxide, 150ml octane and Resorcinol quality.Feed dioxide gas, be warming up to 200 ℃, still is pressed reach 9.5MPa, reaction 4h.With post reaction mixture cooling, suction filtration; Gained filtrating is reclaimed; It is that heated and boiled is removed residual solvent in 0.1% the aqueous solution of sodium bisulfite that filter cake is dissolved in the 500ml mass percentage concentration, after thing to be mixed fully dissolves while hot suction filtration remove a little impurity and catalyzer; To filtrate is cooled to crystallization below 8 ℃ in ice-water bath, and uses the small amount of ice water washing leaching cake.After the gained filter cake is dissolved in 300ml hot water, adds concentrated hydrochloric acid and regulate pH, leave standstill 1h after the stirring less than 2, suction filtration again, washing leaching cake, at 80 ℃ of vacuum-drying filter cakes, 2,5-dihydric para-phthalic acid 17.5g, yield are 70.7%.
Instance 2
In having the 0.5L autoclave of heating, stirring and temperature controlling system, add 5%Pd (the II)/C catalyzer of 13.75g Resorcinol, 35g Pottasium Hydroxide, 150ml octane and Resorcinol quality.Feed dioxide gas, be warming up to 200 ℃, still is pressed reach 11.5MPa, reaction 4h.With post reaction mixture cooling, suction filtration; Gained filtrating is reclaimed; It is that heated and boiled is removed residual solvent in 0.1% the aqueous solution of sodium bisulfite that filter cake is dissolved in the 500ml mass percentage concentration, after thing to be mixed fully dissolves while hot suction filtration remove a little impurity and catalyzer; To filtrate is cooled to crystallization below 8 ℃ in ice-water bath, and uses the small amount of ice water washing leaching cake.After the gained filter cake is dissolved in 300ml hot water, adds concentrated hydrochloric acid and regulate pH, leave standstill 1h after the stirring less than 2, suction filtration again, washing leaching cake, at 80 ℃ of vacuum-drying filter cakes, 2,5-dihydric para-phthalic acid 20.7g, yield are 83.6%.Instance 3
In having the 0.5L autoclave of heating, stirring and temperature controlling system, add 5%Pd (the II)/C catalyzer of 13.75g Resorcinol, 35g Pottasium Hydroxide, 150ml octane and Resorcinol quality.Feed dioxide gas, be warming up to 220 ℃, still is pressed reach 9.5MPa, reaction 4h.With post reaction mixture cooling, suction filtration; Gained filtrating is reclaimed; It is that heated and boiled is removed residual solvent in 0.1% the aqueous solution of sodium bisulfite that filter cake is dissolved in the 500ml mass percentage concentration, after thing to be mixed fully dissolves while hot suction filtration remove a little impurity and catalyzer; To filtrate is cooled to crystallization below 8 ℃ in ice-water bath, and uses the small amount of ice water washing leaching cake.After the gained filter cake is dissolved in 300ml hot water, adds concentrated hydrochloric acid and regulate pH, leave standstill 1h after the stirring less than 2, suction filtration again, washing leaching cake, at 80 ℃ of vacuum-drying filter cakes, 2,5-dihydric para-phthalic acid 17.8g, yield are 71.9%.
Instance 4
In having the 0.5L autoclave of heating, stirring and temperature controlling system, add 5%Pd (the II)/C catalyzer of 13.75g Resorcinol, 35g Pottasium Hydroxide, 150ml octane and Resorcinol quality.Feed dioxide gas, be warming up to 220 ℃, still is pressed reach 11.5MPa, reaction 4h.With post reaction mixture cooling, suction filtration; Gained filtrating is reclaimed; It is that heated and boiled is removed residual solvent in 0.1% the aqueous solution of sodium bisulfite that filter cake is dissolved in the 500ml mass percentage concentration, after thing to be mixed fully dissolves while hot suction filtration remove a little impurity and catalyzer; To filtrate is cooled to crystallization below 8 ℃ in ice-water bath, and uses the small amount of ice water washing leaching cake.After the gained filter cake is dissolved in 300ml hot water, adds concentrated hydrochloric acid and regulate pH, leave standstill 1h after the stirring less than 2, suction filtration again, washing leaching cake, at 80 ℃ of vacuum-drying filter cakes, 2,5-dihydric para-phthalic acid 21.0g, yield are 85%.
Instance 5
In having the 0.5L autoclave of heating, stirring and temperature controlling system, add 10%Pd (the II)/C catalyzer of 13.75g Resorcinol, 35g Pottasium Hydroxide, 150ml octane and Resorcinol quality.Feed dioxide gas, be warming up to 220 ℃, still is pressed reach 11.5MPa, reaction 4h.With post reaction mixture cooling, suction filtration; Gained filtrating is reclaimed; It is that heated and boiled is removed residual solvent in 0.1% the aqueous solution of sodium bisulfite that filter cake is dissolved in the 500ml mass percentage concentration, after thing to be mixed fully dissolves while hot suction filtration remove a little impurity and catalyzer; To filtrate is cooled to crystallization below 8 ℃ in ice-water bath, and uses the small amount of ice water washing leaching cake.After the gained filter cake is dissolved in 300ml hot water, adds concentrated hydrochloric acid and regulate pH, leave standstill 1h after the stirring less than 2, suction filtration again, washing leaching cake, at 80 ℃ of vacuum-drying filter cakes, 2,5-dihydric para-phthalic acid 19.85g, yield are 80.2%.
Instance 6
In having the 0.5L autoclave of heating, stirring and temperature controlling system, add 20%Pd (the II)/C catalyzer of 13.75g Resorcinol, 35g Pottasium Hydroxide, 150ml octane and Resorcinol quality.Feed dioxide gas, be warming up to 220 ℃, still is pressed reach 11.5MPa, reaction 4h.With post reaction mixture cooling, suction filtration; Gained filtrating is reclaimed; It is that heated and boiled is removed residual solvent in 0.1% the aqueous solution of sodium bisulfite that filter cake is dissolved in the 500ml mass percentage concentration, after thing to be mixed fully dissolves while hot suction filtration remove a little impurity and catalyzer; To filtrate is cooled to crystallization below 8 ℃ in ice-water bath, and uses the small amount of ice water washing leaching cake.After the gained filter cake is dissolved in 300ml hot water, adds concentrated hydrochloric acid and regulate pH, leave standstill 1h after the stirring less than 2, suction filtration again, washing leaching cake, at 80 ℃ of vacuum-drying filter cakes, 2,5-dihydric para-phthalic acid 19.8g, yield are 80%.
Claims (6)
1. catalytic preparation 2,5-dihydric para-phthalic acid's method, concrete steps are:
(1) with after the carried by active carbon body and function Hydrogen chloride stir process, extremely neutral with the zero(ppm) water washing, vacuum-drying; The gained gac is sieved; Use dissolving with hydrochloric acid PdCl
2, the gac that adds after sieving then adsorbs, and promptly gets catalyst P d (II)/C after the thorough drying;
(2) in autoclave, add 5%～20%Pd (the II)/C catalyzer of Resorcinol, Pottasium Hydroxide, octane and Resorcinol quality, feed dioxide gas, be warming up to 200～220 ℃, still is pressed reach 9.5～11.5MPa, more than the reaction 4h;
(3) with post reaction mixture cooling, suction filtration; Gained filtrating is reclaimed; Filter cake is dissolved in the aqueous solution of sodium bisulfite, dissolve post-heating fully and boil and remove residual solvent, after thing to be mixed fully dissolves while hot suction filtration remove impurity and catalyzer; To filtrate is cooled to crystallization below 8 ℃ in ice-water bath, and uses the frozen water washing leaching cake;
(4) after the gained filter cake is dissolved in hot water, adds concentrated hydrochloric acid and regulate pH less than 2, suction filtration, washing leaching cake promptly gets 2 after the vacuum-drying, the 5-dihydric para-phthalic acid.
2. a kind of catalytic preparation 2 as claimed in claim 1; 5-dihydric para-phthalic acid's method; It is characterized in that: use in the step 1 mass percentage concentration be 5% Hydrogen chloride behind 80 ℃ of stir process gac 3h, vacuum-drying 12h crosses 200 mesh sieves with the gained gac; Dissolving with hydrochloric acid PdCl with 6mol/L
2, the gac that adds after sieving then adsorbs PdCl
2With the mass ratio of gac be 1: 50, promptly get catalyst P d (II)/C in 120 ℃ of thorough dryings.
3. a kind of catalytic preparation 2 as claimed in claim 1,5-dihydric para-phthalic acid's method is characterized in that: the mass ratio of Resorcinol and Pottasium Hydroxide is 13.75: 35 (being that mol ratio is 1: 5) in the step 2.
4. a kind of catalytic preparation 2 as claimed in claim 1,5-dihydric para-phthalic acid's method is characterized in that: the add-on of octane is as the criterion to fill it up with reaction kettle in the step 2.
5. a kind of catalytic preparation 2 as claimed in claim 1,5-dihydric para-phthalic acid's method is characterized in that: the mass percentage concentration of sodium sulfite anhy 96 is 0.1% in the step 3.
6. a kind of catalytic preparation 2 as claimed in claim 1,5-dihydric para-phthalic acid's method is characterized in that: said 2,5-dihydric para-phthalic acid's yield＞70%, purity＞99%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100302157A CN101508642B (en) | 2009-03-17 | 2009-03-17 | Method for preparing 2,5-dihydroxy p-benzene dicarboxylic acid |
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|---|---|---|---|
| CN2009100302157A CN101508642B (en) | 2009-03-17 | 2009-03-17 | Method for preparing 2,5-dihydroxy p-benzene dicarboxylic acid |
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| CN101508642B true CN101508642B (en) | 2012-06-20 |
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| CN104829449B (en) * | 2015-05-12 | 2020-06-02 | 云南大学 | Method for synthesizing 2,5-dihydroxy terephthalic acid |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1202147A (en) * | 1995-11-10 | 1998-12-16 | 阿克佐诺贝尔公司 | Process for dicarboxylating dihydric phenols |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1202147A (en) * | 1995-11-10 | 1998-12-16 | 阿克佐诺贝尔公司 | Process for dicarboxylating dihydric phenols |
Non-Patent Citations (2)
| Title |
|---|
| 漆琳 等.2,5-二羟基对苯二甲酸的合成及表征.《精细石油化工》.2007,第24卷(第1期),23-25. * |
| 漆琳等.2 5-二羟基对苯二甲酸的合成及表征.《精细石油化工》.2007 |
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