CN100579952C - Method for synthesizing acetyl tributyl citrate by using ion type catalyst - Google Patents
Method for synthesizing acetyl tributyl citrate by using ion type catalyst Download PDFInfo
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- CN100579952C CN100579952C CN200710132445A CN200710132445A CN100579952C CN 100579952 C CN100579952 C CN 100579952C CN 200710132445 A CN200710132445 A CN 200710132445A CN 200710132445 A CN200710132445 A CN 200710132445A CN 100579952 C CN100579952 C CN 100579952C
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention relates to a method for synthesizing acetyl tributyl citrate through electrophoretic catalyst. The method comprises the steps: step one: citric acid, butanol and sodium bisulfate monohydrate are added into a reactor, and the catalyst is recycled and filtered after the cooling of the stirring reflux reaction, filtrate is neutralized by adding alkaline solution and rinsed till neutral state, then the butanol is distilled and recycled under normal pressure, and the residual water is steamed under reduced pressure to acquire crude tirbutyl citrate, and the compound decolurant of acticarbon and aluminum oxide is added into the crude tirbutyl citrat for decoloring treatment, thereby, the finished tirbutyl citrat is acquired; step two: the finished tirbutyl citrate, acetic anhydride and the sodium bisulfate monohydrate are added into the reactor, and the catalyst is filtered , cooled and recycled after 1.0-3.0 hours of stirring reaction under the temperature of 50-90 DEG C; filtrate is neutralized by adding alkaline solution and rinsed till neutral state; acetyl tributyl citrate is acquired after water phase is separated and n-butyl acetate is distilled under reduced pressure and recycled. The catalyst of the method of the invention is easily separated and recycled, the esterification process is not easily influenced by by-product, emulsification is not easy during the rinsing process and the product yield is high.
Description
Technical field
The present invention relates to a kind of synthetic method of non-toxic plasticizer, be specifically related to a kind of method of utilizing the ionized catalyst synthesizing acetyl tributyl citrate.Belong to the fine chemical technology field.
Background technology
Softening agent at present commonly used mostly is phthalic ester plasticizer, because of it may bring out carcinogenicly, abroad made laws and limited it and use, and actively searching can replace the non-toxic plasticizer of phthalate.Tributyl acetylcitrate is a kind of non-toxic plasticizer that has very much the exploitation future, and FDA (FDA) thinks that it is one of safest softening agent.Tributyl acetylcitrate winter hardiness, photostabilization and have excellent water-resistance, with polyvinyl chloride, polypropylene with various fibre resin consistency is good, plasticizing efficiency is high, nontoxic, characteristics such as volatility is little, especially have significant superiority and use widely in fields such as food product pack, medical article, toys for children.Therefore, the development of tributyl acetylcitrate has crucial meaning for the exploitation non-toxic plasticizer.
Tributyl acetylcitrate (acetyl tri-n-butyl citrate) is called for short ATBC, molecular formula C
20H
34O
8, be a kind of oily liquids of colorless and odorless, relative density (25 ℃) 1.046,343 ℃ of boiling points (0.1MPa) are dissolved in most of organic solvents, and are water insoluble.
The synthetic method of tributyl acetylcitrate is at present: esterification under various homogeneous catalyst effects gets tributyl citrate (tri-n-butyl citrate with citric acid and propyl carbinol, be called for short TBC), tributyl citrate reacts under various homogeneous catalysts with diacetyl oxide and makes tributyl acetylcitrate (acetyl tri-n-butyl citrate is called for short ATBC).The shortcoming of this method is the recovery difficulty of catalyzer, easy emulsification when dealcoholysis during tributyl citrate is synthetic, dehydration, and the purifying products time is long; When tributyl acetylcitrate synthesized, the by-product acetic acid of generation was unfavorable for the carrying out of esterification, and the output capacity of tributyl acetylcitrate is low, therefore needed constantly to remove acetate from reaction mixture, and complex operation has also increased production cost.
Summary of the invention
The objective of the invention is to overcome above-mentioned deficiency, provide the easily separated recovery of a kind of catalyzer, by product not to influence esterification and carry out, be difficult for when washing emulsification, the method for utilizing the ionized catalyst synthesizing acetyl tributyl citrate that product yield is high.
The object of the present invention is achieved like this: a kind of method of utilizing the ionized catalyst synthesizing acetyl tributyl citrate is characterized in that described method comprises following processing step:
Synthesizing of step 1, tributyl citrate
In the reactor that has agitator, condenser, thermometer, according to the 1.0mol citric acid, cooperating 3.0～8.0mol propyl carbinol and consumption is the ionized catalyst adding material of citric acid weight 0.5～5.0%, under agitation reclaims catalyzer in 2.0～5.0 hours cooled and filtered of 110～140 ℃ of back flow reaction; Adding basic solution neutralization in filtrate (remove byproduct of reaction---citric acid one butyl ester, citric acid dibutylester and unreacted citric acid, the purity of raising tributyl citrate), be washed to neutrality (removing excessive water-soluble impurities such as alkali lye) again; Propyl carbinol is reclaimed in air distillation to washing back water phase separated again, underpressure distillation is removed remaining moisture content and got the tributyl citrate crude product; The composite decoloring agent decolouring processing that adds tributyl citrate crude product weight 0.5～4.5% in the tributyl citrate crude product that makes makes the tributyl citrate finished product.The tributyl citrate finished product purity that this method makes is higher than 99.5%, and average yield is greater than 98.0%.
Synthesizing of step 2, tributyl acetylcitrate
In the reactor that has agitator, condenser, thermometer, according to 1.0mol tributyl citrate finished product, cooperation 1.0～3.5mol diacetyl oxide, 0.5～2.0mol propyl carbinol and consumption are that the ionized catalyst of tributyl citrate weight 0.5～5.0% feeds intake, and under agitation reclaim catalyzer in 1.0～3.0 hours cold filtrations of 50～90 ℃ of reactions; In filtrate, add basic solution neutralization (removing byproduct of reaction acetate), be washed to neutrality (removing excessive alkali lye and water-soluble impurity) again; Dividing anhydrates mutually gets tributyl acetylcitrate after n-butyl acetate is reclaimed in underpressure distillation.The tributyl acetylcitrate purity that this method makes is higher than 99.5%, and average yield is greater than 98.0%.
Described ionized catalyst is a sulfuric acid monohydrate hydrogen sodium.
Described composite decoloring agent is gac and alumina mixture, proportion scale is 1: 0.3～1.5, use the activated carbon decolorizing effect not too obvious separately, only too high with aluminum oxide decolouring cost, yet adopt both composite decolorations not only to reach decolorizing effect but also can reduce production costs, can not exert an influence easily separated recovery simultaneously to product.
The present invention utilizes the method for ionized catalyst synthesizing acetyl tributyl citrate, and the basic solution of described neutralization usefulness is: basic solution (being mass percent) such as 1.0～10.0% solution of potassium carbonate, 0.1～5.0% potassium hydroxide solution, 2.0～10.0% sodium carbonate solution or 0.1～5.0% sodium hydroxide.
The present invention utilizes the method for ionized catalyst synthesizing acetyl tributyl citrate, described adding basic solution neutralization, and its pH value is: 7.0～8.5.
The present invention utilizes the method for ionized catalyst synthesizing acetyl tributyl citrate, and described underpressure distillation is: vacuum tightness is 0.075～0.098MPa, and the still temperature is no more than 60 ℃.
It should be noted that in the such scheme:
1, described catalyzer is a sulfuric acid monohydrate hydrogen sodium, and its preparation is simple, cheap, excellent catalytic effect, there is not tangible equipment corrosion phenomenon, easily separated, shortening purifying time, and recyclable utilization again, reuse 6 product yields and still be higher than 96.0%, greatly reduce production cost.
2, in the water washing process of synthesizing citric acid tri-n-butyl, generally adopt first air distillation to reclaim propyl carbinol, carry out processes such as alkali cleaning, washing then, but serious emulsification can take place in this process washing, makes product and water not easily separated, and the washing time is prolonged greatly; But in the present invention, adopt and wash the method that propyl carbinol is reclaimed in underpressure distillation more earlier, so just can avoid the generation of emulsion, shortened the washing time greatly; Yet wash propyl carbinol will be run off, and therefore in reaction process, at first adopt basic solution to wash, and then wash neutrality, so just reduce the number of dropouts of propyl carbinol with a large amount of water.Adopted first alkali cleaning, washing in the water washing process of synthesizing acetyl tributyl citrate equally, decompression removes the scheme of n-butyl acetate again.
3, in the tributyl acetylcitrate building-up process, the adding of propyl carbinol, one side improves the mixedness of catalyzer and reactant as solvent; On the other hand as catalyst aid, with byproduct of reaction---acetic acidreaction, promote esterification to carry out (because of this reaction is reversible reaction to positive dirction, along with reaction is carried out, the concentration of by product---acetate constantly increases, to cause reaction to be carried out as untimely removing to the reversed reaction direction), favourable to speed of response and the raising productive rate of accelerating positive reaction.
Reaction conditions is easy among the present invention, is fit to laboratory and industrial scale production.Adopt this invention synthesizing acetyl tributyl citrate to have advantages such as yield height, purity height and color and luster are good, product purity is greater than 99.5%.The reacting middle catalyst consumption is little and can recycle and reuse in addition, the results showed that product yield still was higher than 96.0% when reclaiming catalyzer used 6 times, and production cost reduces significantly, and is convenient to the purifying of reaction mixture.
Embodiment
One, tributyl citrate is synthetic
In the 500ml four-hole boiling flask of agitator, thermometer, reflux exchanger and water-and-oil separator is housed, add the citric acid of 0.60mol, add sulfuric acid monohydrate hydrogen sodium (3.0%, the citric acid mass percent) and propyl carbinol (2.4～3.8mol); Stir, heat, dissolve, when temperature reaches 50 ℃, extract reaction solution the survey initial acid value, clock when system begins to reflux and and time-division water, 110～140 ℃ of reflux temperatures react 2～5 hours (temperature is not higher than 170 ℃), every the 30min sampling detecting acid number, change according to acid number before and after the GB GB1668-81 method assaying reaction, and be calculated as follows esterification yield:
The initial acid number of esterification yield=(react initial acid number-reaction and finish acid number)/react.
Reaction is inclined reaction solution to go out filtering recovering catalyst after finishing.Reaction solution respectively through the neutralization of the sodium carbonate solution of 5.0% weight percent, to be washed to pH value be about 7.0, first then normal pressure steams unreacted propyl carbinol, the remaining moisture content of underpressure distillation gets the tributyl citrate crude product again; 5.0% of its total amount of adding composite decoloring agent in the tributyl citrate crude product gets light yellow tributyl citrate finished product in 80～90 ℃ of 60～90min that decolour down.Through gas chromatographic detection content 〉=99.5%, acid number≤0.1mgKOH/g, esterification yield 〉=98%.Wherein composite decoloring agent is gac and alumina mixture, and proportion scale is 1: 0.3～1.5.
Two, tributyl acetylcitrate is synthetic
In the there-necked flask that has agitator, condenser, thermometer, the tributyl citrate, 1.2～2.0mol diacetyl oxide, 1.5mol propyl carbinol and the catalyzer sulfuric acid monohydrate hydrogen sodium (0.5～5.0% that add 1.0mol, the tributyl citrate mass percent), stirring reaction 60～120min under 60～90 ℃ of temperature, the crude product of tributyl acetylcitrate.Behind the crude product filtering recovering catalyst, elder generation neutralizes with 5.0% sodium carbonate solution, is washed to neutrality again, remove underpressure distillation behind the water layer, reclaim the positive butyl ester of by-product acetic acid, dewater then tributyl acetylcitrate, more than 99.5%, yield is higher than 98% with its content of gas chromatographic analysis.
Claims (4)
1, a kind of method of utilizing the ionized catalyst synthesizing acetyl tributyl citrate is characterized in that described method comprises following processing step:
Synthesizing of step 1, tributyl citrate
In the reactor that has agitator, condenser, thermometer, according to the 1.0mol citric acid, cooperating 3.0～8.0mol propyl carbinol and consumption is the ionized catalyst adding material of citric acid weight 0.5～5.0%, under agitation reclaims catalyzer in 2.0～5.0 hours cooled and filtered of 110～140 ℃ of back flow reaction; In filtrate, add the basic solution neutralization, be washed to neutrality again; Propyl carbinol is reclaimed in air distillation to washing back water phase separated again, underpressure distillation is removed remaining moisture content and got the tributyl citrate crude product; The composite decoloring agent decolouring processing that adds tributyl citrate crude product weight 0.5～4.5% in the tributyl citrate crude product that makes makes the tributyl citrate finished product,
Synthesizing of step 2, tributyl acetylcitrate
In the reactor that has agitator, condenser, thermometer, according to 1.0mol tributyl citrate finished product, cooperation 1.0～3.5mol diacetyl oxide, 0.5～2.0mol propyl carbinol and consumption are that the ionized catalyst of tributyl citrate weight 0.5～5.0% feeds intake, and under agitation reclaim catalyzer in 1.0～3.0 hours cold filtrations of 50～90 ℃ of reactions; In filtrate, add the basic solution neutralization, be washed to neutrality again; Dividing anhydrates mutually gets tributyl acetylcitrate after n-butyl acetate is reclaimed in underpressure distillation,
Described ionized catalyst is a sulfuric acid monohydrate hydrogen sodium,
Described composite decoloring agent is gac and alumina mixture, and proportion scale is 1: 0.3～1.5.
2, a kind of method of utilizing the ionized catalyst synthesizing acetyl tributyl citrate according to claim 1, it is characterized in that: the basic solution of described neutralization usefulness is: 1.0～10.0% solution of potassium carbonate, 0.1～5.0% potassium hydroxide solution, 2.0～10.0% sodium carbonate solution or 0.1～5.0% alkaline solution of sodium hydroxide.
3, a kind of method of utilizing the ionized catalyst synthesizing acetyl tributyl citrate according to claim 1 is characterized in that: described adding basic solution neutralization, its pH value is: 7.0～8.5.
4, a kind of method of utilizing the ionized catalyst synthesizing acetyl tributyl citrate according to claim 1, it is characterized in that: described underpressure distillation: vacuum tightness is 0.075～0.098MPa, the still temperature is no more than 60 ℃.
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336662A (en) * | 2010-07-14 | 2012-02-01 | 中国石油天然气股份有限公司 | Preparation method of diglycol di-2-ethylhexoate |
| CN102249916B (en) * | 2011-05-26 | 2014-07-23 | 南京化工职业技术学院 | Continuous production process for tributyl citrate |
| CN102285882B (en) * | 2011-06-17 | 2013-10-09 | 宜昌五帝机电有限公司 | Method for synthesizing acetyl tributyl citrate (ATBC) by adopting composite ionic liquid catalyst |
| CN102285883B (en) * | 2011-06-17 | 2013-07-24 | 宜昌五帝机电有限公司 | Method for synthesizing tributyl citrate (TBC) by adopting composite ionic liquid catalyst |
| CN102304044B (en) * | 2011-07-11 | 2013-07-31 | 南京工业大学 | Integrated process for catalytically synthesizing acetyl tributyl citrate by sodium bisulfate monohydrate |
| CN102304045B (en) * | 2011-07-11 | 2014-04-30 | 南京工业大学 | Integrated process for synthesizing acetyl tributyl citrate (ATBC) from active carbon solid-carried sulphuric acid catalyst |
| CN102351696B (en) * | 2011-08-26 | 2014-04-30 | 南京工业大学 | Technology for synthesizing acetyl citrate |
| CN102503824B (en) * | 2011-11-09 | 2014-12-10 | 南京工业大学 | Process for synthesizing long chain acylation citric acid ester |
| CN104945257B (en) * | 2014-06-24 | 2019-06-25 | 广东东阳光药业有限公司 | The preparation method of triethyl citrate |
| CN104650335A (en) * | 2015-02-04 | 2015-05-27 | 南京航空航天大学 | Technology for preparing long-chain acylated citric acid ester by distributed control continuous integration technique |
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| CN1557800A (en) * | 2004-02-06 | 2004-12-29 | 江南大学 | Process for preparing ethyl citrate suitable for industrialized production |
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| CN1557800A (en) * | 2004-02-06 | 2004-12-29 | 江南大学 | Process for preparing ethyl citrate suitable for industrialized production |
Non-Patent Citations (2)
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| 柠檬酸三丁酯,乙酰柠檬酸三丁酯的催化合成研究. 谢春和.浙江大学2006年硕士论文. 2006 |
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Assignee: JIANGYIN XIANGYANG TECHNOLOGY CO., LTD. Assignor: Li Xiangqing Contract record no.: 2012320000158 Denomination of invention: Method for synthesizing acetyl tributyl citrate by using ion type catalyst Granted publication date: 20100113 License type: Exclusive License Open date: 20080220 Record date: 20120302 |