CN102659589A - Method for catalytically synthesizing acetyl tributyl citrate by using caprolactam acidic ionic liquid - Google Patents
Method for catalytically synthesizing acetyl tributyl citrate by using caprolactam acidic ionic liquid Download PDFInfo
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- CN102659589A CN102659589A CN2012101351152A CN201210135115A CN102659589A CN 102659589 A CN102659589 A CN 102659589A CN 2012101351152 A CN2012101351152 A CN 2012101351152A CN 201210135115 A CN201210135115 A CN 201210135115A CN 102659589 A CN102659589 A CN 102659589A
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- tributyl citrate
- water
- ionic liquid
- hexanolactam
- acetyl tributyl
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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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a method for catalytically synthesizing acetyl tributyl citrate by using caprolactam acidic ionic liquid. The method is characterized by comprising the following steps: taking ionic liquid as a catalyst for catalyzing the reaction of acetic anhydride and tributyl citrate for generating acetyl tributyl citrate; after ending the reaction, performing reduced pressure distillation and recycling unreacted acetic anhydride and generated byproduct acetic acid; adding less water in a crude product of acetyl citrate; performing reduced pressure distillation on water phase and recycling the catalyst; performing alkali cleaning on oil-phase liquid and rinsing till the liquid is neutral; and decolorizing by utilizing active carbon, and then performing reduced pressure distillation and removing water, thereby obtaining the qualified product of acetyl tributyl citrate. According to the method, the catalyst is repeatedly recycled; the dosage of the acetic anhydride is less; and the yield of the acetyl tributyl citrate product is higher.
Description
Technical field
The invention belongs to the chemical preparation technical field, relate to a kind of method with hexanolactam presence of acidic ionic liquid catalyst synthesizing acetyl tributyl citrate.
Background technology
Along with the exposure of Taiwan fluidizer (being softening agent) scandal, the safety-problems of conventional plasticizers has received the extensive concern of all circles.Present most popular phthalic ester plasticizer comes to light and has certain pathogenicly, and possibly bring out cancer, and the multinational strictness in west forbids that it is used for food product pack, fields such as medical apparatus and toy for children.And characteristics such as tributyl acetylcitrate (Acetyl Tri-n-butyl Citrate) has nontoxicity, is prone to degraded, environmental friendliness, plasticization effect are good are considered to one of secure replacement article of phthalic ester plasticizer.In addition, China's Hydrocerol A excess production capacity, this also provides raw material guarantee for development tributyl acetylcitrate class softening agent.
In the compound method of tributyl acetylcitrate, selection of catalysts is very crucial.Adopt the vitriol oil or tosic acid as catalyzer in the present production technique mostly, and adopt the production technique of this type of catalyzer to exist the problem that equipment corrosion is serious, by product is many, the spent acid quantity discharged is big; Solid acid also is one type of more catalyzer of research in addition, this type catalyzer or activity is lower, and reusability is relatively poor, or the preparation difficulty, costs an arm and a leg, and all not too is fit to promote.These synthesizing acetyl tributyl citrate methods all remain further to be improved.
Summary of the invention
The objective of the invention is the deficiency to prior art, a kind of method with hexanolactam presence of acidic ionic liquid catalyst synthesizing acetyl tributyl citrate is provided, the present device corrosion is little, product yield is high, the catalyzer reusability is good, production cost is low.
The objective of the invention is to realize like this: a kind of with hexanolactam presence of acidic ionic liquid catalyst synthesizing acetyl tributyl citrate method, comprise following several steps:
(1) adopting tributyl citrate and diacetyl oxide is raw material; Sulfuric acid hexanolactam ionic liquid is a catalyzer; The mol ratio of tributyl citrate and diacetyl oxide is 1:1.0-3.0; The ion liquid consumption of sulfuric acid hexanolactam is the 0.1-8.0% of tributyl citrate quality; Temperature of reaction is between 40-100
; Stir 15min-120min, make the tributyl acetylcitrate bullion.Described reactant can be disposable reinforced, also can be the continuously feeding in 0-15min of any one reactant;
(2) with behind above-mentioned tributyl acetylcitrate bullion underpressure distillation recovery diacetyl oxide and the acetate, add water, the mol ratio of water and tributyl citrate is 1-20:1, and standing demix gets oil phase and water;
(3) water is through underpressure distillation reclaim(ed) sulfuric acid hexanolactam ionic liquid;
(4) oil phase uses the alkali liquid washing of mass concentration as 2%-20% after using water washing again, washes then to water to be neutral, and oil phase adds activated carbon decolorizing, suction filtration, and filtrate decompression dephlegmate branch obtains the tributyl acetylcitrate product.
The invention has the beneficial effects as follows: (1) yield is high, is 98%-99%; (2) equipment corrosion is little, and the spent acid discharging is few; (3) the recyclable repeated use of catalyzer, and catalytic activity is constant basically; (4) raw acetic acid acid anhydride consumption is less, and economy is good.
Embodiment
The present invention utilizes ionic liquid as the catalyzer synthesizing acetyl tributyl citrate, comprises following several steps:
1, adopting tributyl citrate and diacetyl oxide is raw material; Sulfuric acid hexanolactam ionic liquid is a catalyzer; The mol ratio of tributyl citrate and diacetyl oxide is 1:1.0-3.0; The ion liquid consumption of sulfuric acid hexanolactam is the 0.1-8.0% of tributyl citrate quality; Temperature of reaction stirs 15min-120min between 40-100
, make the tributyl acetylcitrate bullion.Described reactant can be disposable reinforced, also can be the continuously feeding in 0-15min of any one reactant.
2, with behind above-mentioned tributyl acetylcitrate bullion underpressure distillation recovery diacetyl oxide and the acetate, add water, the mol ratio of water and tributyl citrate is 1-20:1, and standing demix gets oil phase and water.
3, water is through underpressure distillation reclaim(ed) sulfuric acid hexanolactam ionic liquid.
4, oil phase uses the alkali liquid washing of mass concentration as 2%-20% after using water washing again, washes then to water to be neutral, and oil phase adds activated carbon decolorizing, suction filtration, and filtrate decompression dephlegmate branch obtains the tributyl acetylcitrate product.
Catalyzer described in the present invention is [NH (CH
2)
5CO] HSO
4Ionic liquid, structural formula is following:
The used alkali lye of washing oil phase can be aqueous sodium carbonate, sodium bicarbonate aqueous solution, salt of wormwood or potassium bicarbonate aqueous solution.
Catalyst recovery used among the present invention later on can be not treated, directly is used for secondary response down, after repeatedly using, still has good catalytic effect.
Acylation reaction formula among the present invention is following:
The relevant nature of the product tributyl acetylcitrate among the present invention is following: the oily liquids of colorless and odorless; Water insoluble; The height hydrolysis; Be dissolved in most organic solvents. specific density is 1.046 (20
); Boiling point 343
(0.1MPa); 173
(133pa); Flash-point (opening cup) 204
; Viscosity 0.0427Pa.s (25
); Security is good, and is nontoxic.
For further setting forth summary of the invention, below in conjunction with the content of specific embodiment explanation invention, content of the present invention comprises following examples, but is not limited to embodiment.
Embodiment 1
With 12.24g (0.12mol) diacetyl oxide; 36.04g (0.1mol) tributyl citrate and 0.72g ionic liquid join in the there-necked flask; 60
lower magnetic force stirs, stops to stir behind the reaction 50min.The gained bullion is after acetate and diacetyl oxide are reclaimed in underpressure distillation; Add certain water gaging, layering after the magnetic agitation, catalyzer is reclaimed in the water underpressure distillation; Oil phase washs to neutrality with 5% sodium carbonate solution and water successively; Moisture is removed in underpressure distillation, uses activated carbon decolorizing again, can make the tributyl acetylcitrate finished product.Product yield is 98.26%.
Embodiment 2
With 15.30g (0.15mol) diacetyl oxide; 36.04g (0.1mol) tributyl citrate and 1.8g ionic liquid join in the there-necked flask; 80
lower magnetic force stirs, stops to stir behind the reaction 50min.The gained bullion is after acetate and diacetyl oxide are reclaimed in underpressure distillation; Add certain water gaging, layering after the magnetic agitation, catalyzer is reclaimed in the water underpressure distillation; Oil phase washs to neutrality with 5% solution of potassium carbonate and water successively; Moisture is removed in underpressure distillation, uses activated carbon decolorizing again, can make the tributyl acetylcitrate finished product.Product yield is 98.52%.
Embodiment 3
With 18.36g (0.18mol) diacetyl oxide; 36.04g (0.1mol) tributyl citrate and 0.72g ionic liquid join in the there-necked flask; 80
lower magnetic force stirs, stops to stir behind the reaction 70min.The gained bullion is after acetate and diacetyl oxide are reclaimed in underpressure distillation; Add certain water gaging, layering after the magnetic agitation, catalyzer is reclaimed in the water underpressure distillation; Oil phase washs to neutrality with 5% sodium hydrogen carbonate solution and water successively; Moisture is removed in underpressure distillation, uses activated carbon decolorizing again, can make the tributyl acetylcitrate finished product.Product yield is 99.10%.
Embodiment 4
With 12.24g (0.12mol) diacetyl oxide; 36.04g (0.1mol) tributyl citrate and 0.54g ionic liquid join in the there-necked flask; 60
lower magnetic force stirs, stops to stir behind the reaction 45min.The gained bullion is after acetate and diacetyl oxide are reclaimed in underpressure distillation; Add certain water gaging, layering after the magnetic agitation, catalyzer is reclaimed in the water underpressure distillation; Oil phase washs to neutrality with 5% sodium carbonate solution and water successively; Moisture is removed in underpressure distillation, uses activated carbon decolorizing again, can make the tributyl acetylcitrate finished product.Product yield is 98.70%.
The foregoing description is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change to the present invention makes all fall into protection scope of the present invention.
Claims (2)
1. one kind with hexanolactam presence of acidic ionic liquid catalyst synthesizing acetyl tributyl citrate method, it is characterized in that, comprises following several steps:
(1) adopting tributyl citrate and diacetyl oxide is raw material; Sulfuric acid hexanolactam ionic liquid is a catalyzer; The mol ratio of tributyl citrate and diacetyl oxide is about 1:1.0-3.0; The ion liquid consumption of sulfuric acid hexanolactam is the 0.1-8.0% of tributyl citrate quality; Temperature of reaction is between 40-100
; Stir 15-120min, make the tributyl acetylcitrate bullion;
(2) with behind above-mentioned tributyl acetylcitrate bullion underpressure distillation recovery diacetyl oxide and the acetate, add water, the mol ratio of water and tributyl citrate is 1-20:1, and standing demix gets oil phase and water;
(3) water is through underpressure distillation reclaim(ed) sulfuric acid hexanolactam ionic liquid;
(4) oil phase uses the alkali liquid washing of mass concentration as 2%-20% after using water washing again, washes then to water to be neutral, and oil phase adds activated carbon decolorizing, suction filtration, and filtrate decompression dephlegmate branch obtains the tributyl acetylcitrate product.
2. said with hexanolactam presence of acidic ionic liquid catalyst synthesizing acetyl tributyl citrate method according to claim 1; It is characterized in that; In the said step (4), the used alkali lye of said washing oil phase can be aqueous sodium carbonate, sodium bicarbonate aqueous solution, salt of wormwood or potassium bicarbonate aqueous solution.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1709854A (en) * | 2005-06-24 | 2005-12-21 | 浙江大学 | Catylatic synthesizing method of acetyl tri-in-butyl citrate |
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2012
- 2012-05-04 CN CN2012101351152A patent/CN102659589A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1709854A (en) * | 2005-06-24 | 2005-12-21 | 浙江大学 | Catylatic synthesizing method of acetyl tri-in-butyl citrate |
Non-Patent Citations (3)
| Title |
|---|
| WENJUAN WANG,ET.AL,: "[TMBSA][HSO4] Ionic Liquid as Novel Catalyst for the Rapid Acetylation of Alcohols, Hydroxyesters and Phenols under Solvent-free Conditions", 《CATAL LETT》 * |
| 王有菲: "环保增塑剂柠檬酸酯合成的研究", 《中国优秀硕士学位论文全文数据库（电子期刊）工程科技I辑》 * |
| 钱德胜等，: ""内酰胺酸性离子液体催化合成阿司匹林"", 《池州学院学报》 * |
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Application publication date: 20120912 |