CN102627550B - Preparation methods of butanetetracarboxylic acid and butanetetracarboxyl dianhydride - Google Patents
Preparation methods of butanetetracarboxylic acid and butanetetracarboxyl dianhydride Download PDFInfo
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- CN102627550B CN102627550B CN201110193138.4A CN201110193138A CN102627550B CN 102627550 B CN102627550 B CN 102627550B CN 201110193138 A CN201110193138 A CN 201110193138A CN 102627550 B CN102627550 B CN 102627550B
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Abstract
The invention discloses a preparation method of butanetetracarboxylic acid and belongs to the field of chemical preparation method. The preparation method of butanetetracarboxylic acid comprises the following steps of: dissolving tetrahydrophthalic anhydride and a catalyst in water by heating while dropwisely adding hydrogen peroxide, continuously producing water during the reaction process, and finally heating to 110-130 DEG C for oxidation so as to prepare butanetetracarboxylic acid. Further, the invention also discloses a method for preparing butanetetracarboxyl dianhydride, comprising the following steps of: dissolving a butanetetracarboxylic acid crude product in a solvent, adding excess 5-25% of acid anhydrides, and performing a dehydration reaction at the temperature of 25-60 DEG C to prepare butanetetracarboxyl dianhydride. The preparation method of butanetetracarboxylic acid is an oxidation reaction/water evaporation coupling technology. The preparation method requires no substep to finish, avoids complex technologies of stepwise reactions of hydrolysis and reoxidation and prevents dangerous technology of hydrogen peroxide concentration. By the adoption of the preparation method of butanetetracarboxyl dianhydride, its purity and conversion rate can be raised.
Description
Technical field
The invention belongs to chemical preparation method field, relate in particular to the preparation method of BTCA and butane tetracarboxylic acid dianhydride.
Background technology
BTCA (BTCA) is a kind of important Chemicals, is used as non formaldehyde durable press finishing agent in textile industry.Practical application shows, the fabric arranging through BTCA has higher dry self-balancing, crease resistance, dimensional stability, is difficult for yellowing, formaldehydeless arrangement, hypotoxicity and the premium properties such as restorative again.It is generally acknowledged that it is the major cause that hinders its application that the expensive and BTCA of BTCA arranges catalyzer cost height.
At present, the method for synthetic BTCA is more, has chemical oxidization method, Radiation Synthesis Method, electrochemical synthesis etc., and wherein chemical oxidization method is the unique method of current industrial production BCTA.According to the oxygenant difference adopting, be mainly nitric acid oxidation method and hydrogen peroxide oxidation method.Nitric acid oxidation method is the traditional method of preparation BTCA, but this technological process is very strong to equipment corrosion, and reaction preference is low, produce spent acid, strong heat release, process is easily blasted, and controls stricter to reaction, tail gas needs the inherent defects such as cyclic processing device, makes BTCA production cost high.Hydrogen peroxide oxidation method is the chemical synthesis process of a kind of " clean, green ", in synthetic BTCA, is subject to extensive concern, as patent CN 00112301.7, and the synthetic method that patent CN02113193.7 is openly correlated with.In general, these technological processs are: first tetrahydrophthalic anhydride is heated up and is hydrolyzed into tetrahydrochysene phthalic acid, then tetrahydrochysene phthalic acid substep heats up to be oxidized and obtains BTCA, as first become 1 by hydrogen peroxide oxidation, 2-dicarboxylic acid-4,5-dihydroxyl tetrahydrochysene benzene, then make BTCA by hydrogen peroxide and catalyst oxidation.
There are hydrolysis and oxidation two steps in these techniques, and the hydrogen peroxide concentration using is all 50%.And domestic hydrogen peroxide is generally 30% left and right even lower (decomposing in storage process), thereby necessary supporting hydrogen peroxide concentration technology, thereby exist unsafe factor.Oxidase complex technique and the hydrogen peroxide that utilizes lower concentration are the invention solves.
Based on BTCA and the butane tetracarboxylic acid dianhydride (BTCD) further obtaining is one of monomer of synthesizing polyamides material.Polyimide is the aromatic heterocycle polymer material of developing at the beginning of the 60's of 20th century, be the aromatic heterocycle superpolymer being obtained through polycondensation by aromatic series or alicyclic tetracarboxylic dianhydride and diamine, its hydrolysis and salt fog are good, splendid organic solvent-resistant, fuel oil and oil, and resistance to strong acid, high-low temperature resistant.Polyimide is also the heat-resisting electrically insulating material of excellent property, there is excellent especially resistance to atomic radiation (electronics and neutron) property, can be used for preparing sqtructural adhesive, Bonding Metal, as aluminium, stainless steel and titanium alloy etc., meets Aeronautics and Astronautics industry, microelectronics industry as the splicing requirement of flexible printed circuit board.Polyimide also has the good high-permeability to gas and selectivity, and the film becoming is applicable to the mixed gas such as CO2/CH4, CO2/N2 and separates very much, can think solubleness selective membrane, is therefore regarded as the very promising material of a class of gas separation membrane.Polyimide is for electrical insulating coating, photo sensitive polymeric materials, medical macromolecular materials, photostabilizer, high molecular functional mould material etc., and recent domestic market presents a rapidly rising trend to its demand.But the dicarboxylic anhydride class monomer reagent of domestic supply is too single and need a large amount of imports, and the development of this material is under some influence.
Summary of the invention
The technical problem to be solved in the present invention is: propose a kind of novel method of preparing BTCA, it completes without substep, and the complicated technology of the stepwise reaction that avoid hydrolysis, reoxidizes is avoided the concentrated dangerous technique of hydrogen peroxide; The present invention has also further proposed a kind of novel method of preparing butane tetracarboxylic acid dianhydride, improves its purity and transformation efficiency.
The object of the invention realizes by following technical proposals:
The preparation method of BTCA: by tetrahydrophthalic anhydride and the water-soluble hydrogen peroxide that drips of catalyzer temperature-elevating simultaneously, in reaction process, continuous recovered water, is finally warming up to 110 DEG C～130 DEG C oxidations and makes BTCA.
As optimal way, described hydrogen peroxide quality percentage composition concentration is 20%～30%.
As optimal way, described hydrogen peroxide rate of addition be 0.3～0.7g hydrogen peroxide/g tetrahydrophthalic anhydride/minute.
As optimal way, described catalyzer is tungstic oxide, wolframic acid or its salt.
As optimal way, described tungstate is sodium wolframate or phospho-wolframic acid.
As optimal way, the water of described dissolving tetrahydrophthalic anhydride be deionized water or make BTCA after the mother liquor that filters.
On a kind of preparation method's in aforementioned BTCA basis, further prepare the method for butane tetracarboxylic acid dianhydride: will in thick the BTCA making product solvent, dissolve, add excessive 5～25% acid anhydrides to carry out dehydration reaction at 25 DEG C～60 DEG C, make butane tetracarboxylic acid dianhydride.
As optimal way, described acid anhydrides is acetic anhydride or propionic anhydride.
As optimal way, described solvent is single solvent or the mixed solvent of tetrahydrofuran (THF), diglyme or dioxane.
Beneficial effect of the present invention: propose a kind of novel method of preparing BTCA, i.e. the coupling technique of oxidation/water evaporation:
1. single stage method is prepared BTCA, has greatly simplified processing step, is easy at industrializing implementation;
2. adopt the hydrogen peroxide of lower concentration, reduced production cost and simplified production technique, and having reduced danger;
3. select suitable solvent, control suitably excessive mode of acid anhydrides, improve transformation efficiency, improved the purity of butane tetracarboxylic acid dianhydride.
Brief description of the drawings
Fig. 1 is the schematic diagram of apparatus of the present invention;
Wherein 1 is that heating jacket, 2 is that reactor, 3 is rectifying tower.
Embodiment
Object of the present invention is realized by following technology implementation, and wherein said content, except specified otherwise, is quality percentage composition.
1. BTCA preparation
Tetrahydrophthalic anhydride is placed in container, add again the mother liquor of appropriate deionized water or last test-filtration and appropriate catalyzer, stir on limit, add concentration as 20%～30% hydrogen peroxide taking 0.3～0.7g hydrogen peroxide/g tetrahydrophthalic anhydride/minute speed, limit is warmed up to 75 DEG C～110 DEG C, and in reaction process, part hydromining goes out (device signal as shown in Figure 1), hydrogen peroxide drips, be warmed up to again 110 DEG C～130 DEG C, react after 3～6 hours, cooling.Separate out precipitation, be the BTCA containing partial crystallization water, after vacuum-drying, be the thick product of BTCA.
2. butane tetracarboxylic acid dianhydride preparation
By the cymogene tetracarboxylic acid of preparation, be dissolved in suitable solvent, then add the acetic anhydride amount of substances such as stoichiometric ratio or excessive 5～25%, stir, control 25 DEG C～60 DEG C of temperature of reaction, in reaction process, partly precipitated is slowly separated out, and reacts after 4～8 hours, filter, obtain butane tetracarboxylic acid dianhydride.
Below by embodiment, the present invention is specifically described, is necessary to be pointed out here that embodiment is herein only applicable to the present invention to be further described, can not be considered as limiting the scope of the invention.Preparing in butane tetracarboxylic acid dianhydride process, the thick inadequate part of product BTCA, the product being obtained by many experiments supplements.
embodiment 1
Take 400g tetrahydrophthalic anhydride, 0.4g sodium wolframate, 100g water, Hybrid Heating to 90 DEG C dissolving in the there-necked flask stirring at band, then add concentration as 25% hydrogen peroxide taking 0.3g hydrogen peroxide/g tetrahydrophthalic anhydride/minute speed, be warmed up to gradually 100 DEG C simultaneously, continuous extraction part water in oxidising process, drip after hydrogen peroxide, then be warmed up to 130 DEG C and react again 3 hours, then after extraction part moisture, cooling, separate out a large amount of butane tetracarboxylic Acid precipitation, the mother liquor after filtration, adds in reaction system as water solvent next time.The thick product of BTCA of 120 DEG C of dry filters 4 hours, thick further recrystallizing and refining of product, BTCA yield 78%.
Dried cymogene tetracarboxylic acid product, directly adds 450g acetic anhydride, and at 45 DEG C, stirring reaction 5 hours, generates white precipitate in reaction process, filters and obtain butane tetracarboxylic acid dianhydride, yield 65%.
The catalyzer using in above-described embodiment can also be tungstic oxide, wolframic acid or its other salt; The acid anhydrides using can be also propionic anhydride.Reaction conditions can be selected arbitrarily within the scope of aforementioned claim.
embodiment 2
BTCA is prepared with embodiment 1.
Get dried cymogene tetracarboxylic acid product 400g, be dissolved in the tetrahydrofuran (THF) of 1000g, then add 450g propionic anhydride, at 35 DEG C, stir 6 hours, in reaction process, slowly Precipitation of butane tetracarboxylic acid dianhydride, filter and obtain butane tetracarboxylic acid dianhydride, yield 80%.
The solvent using in above-described embodiment can also be the suitable solvent such as diglyme, dioxane; The catalyzer, solvent, anhydrides using is like in example 1; Reaction conditions can be selected arbitrarily within the scope of aforementioned claim.
embodiment 3
Take 400g tetrahydrophthalic anhydride, 0.4g sodium wolframate, add the mother liquor after filtration in embodiment 2, Hybrid Heating to 90 DEG C dissolving in the there-necked flask stirring at band, then add concentration as 25% hydrogen peroxide taking 0.6g hydrogen peroxide/g tetrahydrophthalic anhydride/minute speed, be warmed up to gradually 110 DEG C simultaneously, in oxidising process, continuous extraction part water, drips after hydrogen peroxide, then is warmed up to 130 DEG C, react again 4 hours, after the moisture of extraction part again, cooling, separate out a large amount of butane tetracarboxylic Acid precipitation, mother liquor after filtration, adds in reaction system as water solvent next time.The thick product of the BTCA of dry filter 4 hours under 120 DEG C of conditions, thick further recrystallizing and refining of product, BTCA yield 80%.
Get dried cymogene tetracarboxylic acid product 400g, be dissolved in the tetrahydrofuran (THF) of 1000g, then chemical requirement add 350g acetic anhydride, at 35 DEG C, stir 6 hours, in reaction process, slowly Precipitation of butane tetracarboxylic acid dianhydride, filter and obtain butane tetracarboxylic acid dianhydride, yield 60%.
The solvent using in above-described embodiment can also be the suitable solvent such as diglyme, dioxane or mixed solvent; The catalyzer, solvent, anhydrides using is like in example 1; Reaction conditions can be selected arbitrarily within the scope of aforementioned claim.
embodiment 4
Take 400g tetrahydrophthalic anhydride, 0.4g sodium wolframate, 80g water, Hybrid Heating to 80 DEG C dissolving in the there-necked flask stirring at band, then add concentration as 30% hydrogen peroxide taking 0.3g hydrogen peroxide/g tetrahydrophthalic anhydride/minute speed, be warmed up to gradually 100 DEG C simultaneously, in oxidising process, continuous extraction part water, drips after hydrogen peroxide, then is warmed up to 110 DEG C, react again 5 hours, after the moisture of extraction part again, cooling, separate out a large amount of butane tetracarboxylic Acid precipitation, mother liquor after filtration, adds in reaction system as water solvent next time.The thick product of the BTCA of dry filter 4 hours under 120 DEG C of conditions, thick further recrystallizing and refining of product, BTCA yield 84%.
Get dried cymogene tetracarboxylic acid product 400g, be dissolved in the diglyme of 1000g, then add 400g acetic anhydride, at 45 DEG C, stir 4 hours, in reaction process, slowly Precipitation of butane tetracarboxylic acid dianhydride, filter and obtain butane tetracarboxylic acid dianhydride, yield 70%.
The solvent using in above-described embodiment can also be the suitable solvent such as tetrahydrofuran (THF), dioxane or mixed solvent; The catalyzer, solvent, anhydrides using is like in example 1; Reaction conditions can be selected arbitrarily within the scope of aforementioned claim.
embodiment 5
Take 400g tetrahydrophthalic anhydride, 0.4g tungstic oxide, add 70g distilled water, Hybrid Heating to 90 DEG C dissolving in the there-necked flask stirring at band, then add concentration as 20% hydrogen peroxide taking 0.7g hydrogen peroxide/g tetrahydrophthalic anhydride/minute speed, be warmed up to gradually 100 DEG C simultaneously, in oxidising process, continuous extraction part water, drips after hydrogen peroxide, then is warmed up to 130 DEG C, react again 6 hours, after the moisture of extraction part again, cooling, separate out a large amount of butane tetracarboxylic Acid precipitation, mother liquor after filtration, adds in reaction system as water solvent next time.The thick product of the BTCA of dry filter 4 hours under 120 DEG C of conditions, thick further recrystallizing and refining of product, BTCA yield 70%.
Get dried cymogene tetracarboxylic acid product 400g, be dissolved in the tetrahydrofuran (THF) of 1000g, then add 450g acetic anhydride, at 45 DEG C, stir 4 hours, in reaction process, slowly Precipitation of butane tetracarboxylic acid dianhydride, filter and obtain butane tetracarboxylic acid dianhydride, yield 80%.
The solvent using in above-described embodiment can also be the suitable solvent such as diglyme, dioxane or mixed solvent; The catalyzer, solvent, anhydrides using is like in example 1; Reaction conditions can be selected arbitrarily within the scope of aforementioned claim.
embodiment 6
Take 400g tetrahydrophthalic anhydride, 0.4g phospho-wolframic acid, add the mother liquor after filtration, Hybrid Heating to 90 DEG C dissolving in the there-necked flask stirring at band, then add concentration as 27% hydrogen peroxide taking 0.6g hydrogen peroxide/g tetrahydrophthalic anhydride/minute speed, be warmed up to gradually 100 DEG C simultaneously, in oxidising process, continuous extraction part water, drips after hydrogen peroxide, then is warmed up to 130 DEG C, react again 6 hours, after the moisture of extraction part again, cooling, separate out a large amount of butane tetracarboxylic Acid precipitation, mother liquor after filtration, adds in reaction system as water solvent next time.The thick product of the BTCA of dry filter 4 hours under 120 DEG C of conditions, thick further recrystallizing and refining of product, BTCA yield 76%.
Get dried cymogene tetracarboxylic acid product 400g, be dissolved in the dioxane of 1000g, then add 450g acetic anhydride, at 45 DEG C, stir 5 hours, in reaction process, slowly Precipitation of butane tetracarboxylic acid dianhydride, filter and obtain butane tetracarboxylic acid dianhydride, yield 81%.
The solvent using in above-described embodiment can also be the suitable solvent such as tetrahydrofuran (THF), diglyme or mixed solvent; The catalyzer, solvent, anhydrides using is like in example 1; Reaction conditions can be selected arbitrarily within the scope of aforementioned claim.
embodiment 7
Take 400g tetrahydrophthalic anhydride, 0.3g sodium wolframate, add the mother liquor after filtration, Hybrid Heating to 90 DEG C dissolving in the there-necked flask stirring at band, then add concentration as 27% hydrogen peroxide taking 0.5g hydrogen peroxide/g tetrahydrophthalic anhydride/minute speed, be warmed up to gradually 100 DEG C simultaneously, in oxidising process, continuous extraction part water, drips after hydrogen peroxide, then is warmed up to 120 DEG C, react again 4 hours, after the moisture of extraction part again, cooling, separate out a large amount of butane tetracarboxylic Acid precipitation, mother liquor after filtration, adds in reaction system as water solvent next time.The thick product of the BTCA of dry filter 4 hours under 120 DEG C of conditions, thick further recrystallizing and refining of product, BTCA yield 81%.
Get dried cymogene tetracarboxylic acid product 400g, be dissolved in the diglyme of 1000g, then add 400g acetic anhydride, at 45 DEG C, stir 6 hours, in reaction process, slowly Precipitation of butane tetracarboxylic acid dianhydride, filter and obtain butane tetracarboxylic acid dianhydride, yield 80%.
The solvent using in above-described embodiment can also be the suitable solvent such as tetrahydrofuran (THF), dioxane or mixed solvent; The catalyzer, solvent, anhydrides using is like in example 1; Reaction conditions can be selected arbitrarily within the scope of aforementioned claim.
Claims (4)
1. the preparation method of a BTCA, it is characterized in that: tetrahydrophthalic anhydride is placed in container, add the mother liquor of appropriate deionized water or last test-filtration and appropriate catalyzer, stir on limit, adds concentration as 20%～30% hydrogen peroxide taking 0.3～0.7g hydrogen peroxide/g tetrahydrophthalic anhydride/minute speed again, limit is warmed up to 75 DEG C～110 DEG C, in reaction process, part hydromining goes out, and hydrogen peroxide drips, then is warmed up to 110 DEG C～130 DEG C, react after 3～6 hours, cooling; Separate out precipitation, be the BTCA containing partial crystallization water, after vacuum-drying, be the thick product of BTCA; Described catalyzer is tungstic oxide, wolframic acid.
2. the preparation method of a butane tetracarboxylic acid dianhydride, it is characterized in that: the method for claim 1 is prepared BTCA, to in thick the BTCA making product solvent, dissolve, add the acid anhydrides of molar excess per-cent 5～25% to carry out dehydration reaction at 25 DEG C～60 DEG C, make butane tetracarboxylic acid dianhydride.
3. the preparation method of butane tetracarboxylic acid dianhydride as claimed in claim 2, is characterized in that: described acid anhydrides is acetic anhydride or propionic anhydride.
4. the preparation method of butane tetracarboxylic acid dianhydride as claimed in claim 2, is characterized in that: described solvent is single solvent or the mixed solvent of tetrahydrofuran (THF), diglyme or dioxane.
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Citations (1)
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| US5157152A (en) * | 1986-12-11 | 1992-10-20 | Ortec, Inc. | Process for the oxidation of a tetrahydrophthalic acid |
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| JPS54157521A (en) * | 1978-05-30 | 1979-12-12 | Mitsui Toatsu Chem Inc | Purification of 1,2,3,4-butanetetracarboxylic acid di-anhydride |
| JP4321216B2 (en) * | 2003-10-31 | 2009-08-26 | 新日本理化株式会社 | A method for producing 1,2,3,4-butanetetracarboxylic acid. |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5157152A (en) * | 1986-12-11 | 1992-10-20 | Ortec, Inc. | Process for the oxidation of a tetrahydrophthalic acid |
Non-Patent Citations (5)
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| JP特开2005-132789A 2005.05.26 * |
| 三氧化钨直接催化氧化四氢苯酐合成丁烷四羧酸;阎松等;《中国钨业》;20080630;第23卷(第3期);31-33 * |
| 张俊彦等.1,2,3 ,4-丁烷四羧酸二酐的制备.《化学试剂》.1995,第17卷(第2期),106、118. * |
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