CN104045556B

CN104045556B - The preparation method of a kind of tributyrin

Info

Publication number: CN104045556B
Application number: CN201410279666.5A
Authority: CN
Inventors: 周志刚; 赵炳超; 杨雅麟; 徐俐; 何夙旭; 张美超; 冉超; 于会民
Original assignee: Feed Research Institute of Chinese Academy of Agricultural Sciences
Current assignee: Feed Research Institute of Chinese Academy of Agricultural Sciences
Priority date: 2014-06-20
Filing date: 2014-06-20
Publication date: 2016-06-01
Anticipated expiration: 2034-06-20
Also published as: CN104045556A

Abstract

The present invention provides a kind of method preparing tributyrin, comprising: be acid binding agent taking organic bases, and glycerine and butyryl chloride are reacted, and obtains the mixture containing tributyrin. Wherein, the mol ratio of described glycerine, butyryl chloride, organic bases three kinds of materials is 1:(3-3.3): 3.3. Described method also comprises further and being extracted by the mixture water containing tributyrin, collects organic phase, and the solvent removed under reduced pressure in organic phase is removed, and obtains tributyrin. In the present invention, butyryl chloride and the mol ratio of glycerine during reaction remain on 3-3.3:1, it is not necessary to significantly excessive. In addition, after the trace butyryl chloride that reaction is remaining after terminating can be hydrolyzed to butyric acid and hydrochloric acid in water washing process subsequently, the glycerine together with remnants is taken away by aqueous phase, reaches the object being separated with target product.

Description

The preparation method of a kind of tributyrin

Technical field

The invention belongs to field of fine chemical, it is specifically related to the preparation method of a kind of tributyrin.

Background technology

Short chain fatty acid can provide energy for colon, is the energy source of intestinal cells preference, and very easily absorbs in enteric cavity. Wherein butyric acid is the main energy sources of Colon mucosa cell, accounts for the 70% of short chain fatty acid consumption oxygen institute production capacity, for animal provides the maintenance energy up to 30%. Butyric acid has the unhappy smell as strong cream, cheese, can bring a lot of inconvenience to operator in feed manufacturing process. Butyrin is the glyceryl ester compound of butyric acid, almost odorlessness, it is possible to overcome the butyric acid inconvenience that the smell is awful brings in feed manufacturing process well. Butyrin comprises only son's acid glyceride, two butyrins and tributyrin, enters and is absorbed after being decomposed into butyric acid and glycerine in animal body and utilize. Thering is provided with regard to three with regard to the quantity of butyric acid, tributyrin is best undoubtedly.

Have at present some about only son's acid glyceride synthesis document and patent report, as Liao and cyanines etc. have synthesized only son's acid glyceride by the method for butyric acid and glycerine esterification, content is 60.2% (synthesis of butyrin and the application [J] in grease microencapsulation thereof, Food science, 2009 (16): 203-205), Yu Jiqiang is also by patent reports a kind of method of synthetic butyric acid glyceryl ester, in product, the content of only son's acid glyceride is 78.4% (CN103012137A, butyrin preparation method), but still not about document and the patent report of tributyrin preparation method.

Literature search process has inquired the method for some synthesis vanays, mostly adopt the method for acetic acid and glycerine direct esterification, except needs acetic acid is excessive by a relatively large margin, also to be used catalyzer (Liu Qun etc. costly, sulphur zirconium catalyzes and synthesizes the reaction kinetics [J] of glycerine triacetate, process engineering journal, 2009 (1): 43-46; The preparation of Guo Xingcui etc., ZrBSAPO-5 and catalyze and synthesize glycerine triacetate [J], Industrial Catalysis, 2004 (8): 33-36). The synthesis of patent also not relevant at present or document report tributyrin.

Summary of the invention

The present invention provides a kind of method preparing tributyrin, and in the product obtained by the method, the content of tributyrin reaches more than 80%, and is easy to suitability for industrialized production.

The provided by the present invention method preparing tributyrin, comprises the steps: taking organic bases to be acid binding agent, and glycerine and butyryl chloride are reacted, and obtains the mixture containing tributyrin.

Wherein, described organic bases is triethylamine or pyridine; It is preferably triethylamine.

The mol ratio of described glycerine, butyryl chloride, organic bases three kinds of materials is 1:(3-3.3): 3.3.

Described reaction carries out in organic solvent, and described organic solvent specifically can be chloroform. The consumption of the described organic solvent that every mole of glycerin is corresponding is 1500-2500ml.

In described reaction, butyryl chloride adopts and drips the mode that adds and add reaction system, described be added in condition of ice bath under carry out, the described time controling added is at 1-3h. In order to ensure the homogeneity of reaction system, add and process also needs reaction system stirred dripping.

After described butyryl chloride dropwises, described reaction proceeds 0.5-1h under condition of ice bath, and then carries out 2-4h under room temperature (15-30 DEG C).

The by-product salt acid-respons that can generate with reaction due to organic bases in reaction process generates organic basis of hydrochloride (such as triethylamine hydrochloride), and organic basis of hydrochloride can precipitate out in reaction system, therefore the described mixture containing tributyrin is solidliquid mixture.

Described method also comprises separation from the described mixture containing tributyrin and obtains the step of tributyrin. Concrete grammar is as follows: is extracted by the described mixture water containing tributyrin, collects organic phase, and removed by the organic solvent in described organic phase, obtains tributyrin.

Described extraction can carry out 3-6 time, to be taken away by the organic basis of hydrochloride generated in reaction process (solid in described mixture); In addition after reaction terminates, remaining trace butyryl chloride also can be hydrolyzed to butyric acid and hydrochloric acid in extraction process, and the glycerine together with remnants is taken away by aqueous phase, reaches the object of purification of target product.

When the water consumption of extraction and reaction, the volume ratio of organic solvent used is 0.5-1.5 every time.

The method that organic solvent in described organic phase is removed specifically be can be reduction vaporization method.

Described method is also included in before being removed by the organic solvent in described organic phase further, and described organic phase siccative is dried the step of process. Described siccative is anhydrous sodium sulphate. The time of described drying treatment is 1-3h.

Described method also can comprise the aqueous phase to obtaining after extraction further and process the step reclaiming described organic bases. Concrete grammar is as follows: merged by the aqueous phase obtained after extraction, by lye pH adjustment value to 10-12, and separated free organic bases out, and use desiccant dryness. Wherein, described alkali lye is sodium hydroxide solution, and described siccative is anhydrous sodium sulphate.

The present invention adopts the method for butyryl chloride and glycerine direct esterification to prepare tributyrin. During reaction, the mol ratio of butyryl chloride and glycerine remains on 3-3.3:1, it is not necessary to significantly excessive. In addition, after the trace butyryl chloride that reaction is remaining after terminating can be hydrolyzed to butyric acid and hydrochloric acid in water washing process subsequently, the glycerine together with remnants is taken away by aqueous phase, reaches the object being separated with target product.

Accompanying drawing explanation

Fig. 1 is gas-chromatography (GC) figure of tributyrin reference substance.

Fig. 2 is gas-chromatography (GC) figure of tributyrin prepared by the embodiment of the present invention 1.

Fig. 3 is gas-chromatography (GC) figure of tributyrin prepared by the embodiment of the present invention 2.

Embodiment

Below by specific embodiment, the present invention will be described, but the present invention is not limited thereto.

The experimental technique used in following embodiment if no special instructions, is ordinary method; Reagent used in following embodiment, material etc., if no special instructions, all can obtain from commercial channels.

Embodiment 1

8.6ml glycerine, 55ml triethylamine and 250ml chloroform are put into 500ml there-necked flask, then when ice bath and magnetic agitation, 37.5ml butyryl chloride is added dropwise in reaction flask, drip that to add the time be 3h. Drip Bi Jixu and react 0.5h, then remove ice-water bath, terminate after at room temperature reacting 2.5h. Reacted solidliquid mixture water extracts five times, and each water consumption is 250ml. Aqueous phase adjusts pH to be 10 by NaOH solution after merging, and the triethylamine anhydrous sodium sulfate drying Posterior circle that dissociates uses. Organic phase after washing anhydrous sodium sulfate drying 2h, evaporation under reduced pressure removed chloroform obtains 39.9g product afterwards, and in product, the content of three tributyrins is 80.25% (GC).

Fig. 1 is gas-chromatography (GC) figure of tributyrin reference substance.

Fig. 2 is gas-chromatography (GC) figure of the tributyrin prepared.

Contrast known with Fig. 1: products obtained therefrom is really tributyrin.

Embodiment 2

5.2ml glycerine, 33ml triethylamine and 150ml chloroform are put into 500ml there-necked flask, then when ice-water bath and magnetic agitation, 24.75ml butyryl chloride is added dropwise in reaction flask, drip that to add the time be 2h. Drip Bi Jixu and react 1h, then remove ice-water bath, terminate after at room temperature reacting 3h. Reacted solidliquid mixture water extracts five times, and each water consumption is 200ml. Aqueous phase adjusts pH to be 10 by NaOH solution after merging, and the triethylamine anhydrous sodium sulfate drying Posterior circle that dissociates uses. Organic phase after washing anhydrous sodium sulfate drying 2h, evaporation under reduced pressure removed chloroform obtains 24.4g product afterwards, and in product, the content of three tributyrins is 83.76% (GC).

Fig. 3 is gas-chromatography (GC) figure of the tributyrin prepared.

Contrast known with Fig. 1: products obtained therefrom is really tributyrin.

Claims

1. prepare a method for tributyrin, comprise the steps: taking organic bases to be acid binding agent, glycerine and butyryl chloride are reacted, obtain the mixture containing tributyrin;

Described organic bases is triethylamine;

The mol ratio of described glycerine, butyryl chloride, organic bases three kinds of materials is 1:3-3.3:3.3;

In described reaction, butyryl chloride adopts and drips the mode that adds and add reaction system, described be added in condition of ice bath under carry out, the described time controling added is at 1-3h; After described butyryl chloride dropwises, described reaction proceeds 0.5-1h under condition of ice bath, then carries out 2-4h at 15-30 DEG C.

2. method according to claim 1, it is characterised in that: described reaction carries out in organic solvent, and described organic solvent is chloroform;

The consumption of the described organic solvent that every mole of glycerin is corresponding is 1500-2500mL.

3. method according to claim 1, it is characterised in that: add in process at described and also reaction system is stirred.

4. method according to claim 1, it is characterised in that: described method also comprises separation from the described mixture containing tributyrin and obtains the step of tributyrin;

Concrete grammar is as follows: is extracted by the described mixture water containing tributyrin, collects organic phase, and removed by the organic solvent in described organic phase, obtains tributyrin.

5. method according to claim 4, it is characterised in that: described extraction carries out 3-6 time; When the water consumption of extraction and reaction, the volume ratio of organic solvent used is 0.5-1.5 every time.

6. method according to claim 4, it is characterised in that: the method removed by the organic solvent in described organic phase is reduction vaporization method.

7. method according to claim 4, it is characterised in that: described method is also included in before being removed by the organic solvent in described organic phase further, and described organic phase siccative is dried the step of process; Described siccative is anhydrous sodium sulphate; The time of described drying treatment is 1-3h.

8. method according to claim 4, it is characterised in that: described method also comprises the aqueous phase to obtaining after extraction further and processes the step reclaiming described organic bases;

Concrete grammar is as follows: merged by the aqueous phase obtained after extraction, by lye pH adjustment value to 10-12, and separated free organic bases out, and use desiccant dryness.