CN105237395B - A kind of synthetic method of the different monooctyl ester of low color citric acid three - Google Patents
A kind of synthetic method of the different monooctyl ester of low color citric acid three Download PDFInfo
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- CN105237395B CN105237395B CN201510679899.9A CN201510679899A CN105237395B CN 105237395 B CN105237395 B CN 105237395B CN 201510679899 A CN201510679899 A CN 201510679899A CN 105237395 B CN105237395 B CN 105237395B
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- citric acid
- monooctyl ester
- different monooctyl
- isooctanol
- synthetic method
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of synthetic method of the different monooctyl ester of low color citric acid three, this method is citric acid and different monooctyl ester is initiation material, then using aluminium salt as catalyst, alkane is water entrainer, citric acid and different monooctyl ester is carried out esterification under in catalyst and water entrainer；After reaction terminates, steam water entrainer and applied mechanically with isooctanol, be filtered under diminished pressure out catalyst, product is washed through washing, weak base, the different monooctyl ester of low color citric acid three that color number is less than No. 30 is obtained after steam distillation.The synthetic method craft is simple and environmentally-friendly, can good citric acid three different monooctyl ester of the secondary colour number less than 30.
Description
Technical field
The present invention relates to the preparation field of the different monooctyl ester of citric acid three of fine chemistry industry, more particularly to a kind of low color lemon
The synthetic method of sour three different monooctyl esters.
Background technology
Citric acid ester type compound is using citric acid as primary raw material, with nontoxic, biological degradability is good, volatility is small, anti-
The advantages of bacterium, be a kind of environmentally friendly material.The widest purposes of citrate is the plasticizer of plastics, due to its nothing
Poison, plasticization effect is good, is food packaging PVC film, medicine medicine instrument, the main plasticizer of toy product.
Citrate can be obtained by citric acid and alcohols esterification, and its synthetic route is simultaneously uncomplicated.But current conjunction
Into technique, the problem of existing be using it is traditional have to the esterification good catalytic activity such as sulfuric acid, sulphonic acids, solid
The color number for the product that the catalyst such as super acids, heteropoly acid, inorganic salts, acidic cationic resin and titanate esters synthesize is too high, most
Small also can only achieve 50.United States Patent (USP) USP 4931583 makees catalyst using organic titanate, and its product color number is 50-60,
Current method exist can not secondary colour number be less than 30 low three different monooctyl ester of color citric acid the problem of.
The content of the invention
The invention aims to overcome above-mentioned the deficiencies in the prior art and to provide a kind of low color citric acid three different pungent
The synthetic method of ester, can synthesize the different monooctyl ester of low color citric acid three for obtaining that color number is less than 30 with relatively simple process, its
It is simple to operate.Side reaction is few and high income.
In order to solve the above technical problems, the present invention provides a kind of synthetic method of the different monooctyl ester of low color citric acid three, including：
Using aluminium salt as catalyst, alkane is water entrainer, and citric acid is entered with isooctanol under catalyst and water entrainer effect
Row esterification；
After reaction terminates, steam water entrainer and apply mechanically, then depressurize and steam most of remaining isooctanol and apply mechanically, be filtered under diminished pressure out and urge
Agent, by the obtained different monooctyl ester of product citric acid three through washing, after weak base is washed, residual isooctanol is removed using steam distillation,
Decolorization, obtains the different monooctyl ester of low color citric acid three that color number is less than No. 30 after being filtered under diminished pressure.
Beneficial effects of the present invention are：The aluminium salt not being usually used in citric acid and alcohols esterification is used for catalysis
In agent, course of reaction, the water of esterification generation makes aluminium salt be hydrolyzed into the aluminium hydroxide with suction-operated, so as to effectively suction
The coloring matter aconitic acid produced during reaction enclosure, makes the product color number of synthesis be less than 30；And it is used as by adding alkane
Band water so that the reaction temperature of esterification is low, reaction condition is gentle, and energy consumption is low, simultaneously effective reduces containing for aconitic acid
Amount, high income, ester yield is up to more than 98%.The synthetic method is easy to operate, and catalyst cost of material is low, convenient sources, after
Processing is convenient, realizes that high-quality and efficient, corrosivity is small, be easily isolated, the mode that cost is low synthesizes the low citric acid three of low color number
Different monooctyl ester.
Embodiment
The technical scheme in the embodiment of the present invention is clearly and completely described below, it is clear that described embodiment
Only a part of embodiment of the invention, rather than whole embodiments.Based on embodiments of the invention, ordinary skill
The every other embodiment that personnel are obtained under the premise of creative work is not made, belongs to protection scope of the present invention.
The embodiment of the present invention provides a kind of synthetic method of the different monooctyl ester of low color citric acid three, and energy secondary colour number is less than 30
The different monooctyl ester of citric acid three, this method includes：
Using aluminium salt as catalyst, alkane is water entrainer, using citric acid and isooctanol as initiation material, by citric acid with it is different pungent
Alcohol carries out esterification under catalyst and water entrainer effect；
After reaction terminates, steam water entrainer and apply mechanically, then depressurize and steam most of remaining isooctanol and apply mechanically, be filtered under diminished pressure out and urge
Agent, by the obtained different monooctyl ester of product citric acid three through washing, after weak base is washed, residual isooctanol is removed using steam distillation,
Decolorization, obtains the different monooctyl ester of low color citric acid three that color number is less than No. 30 after being filtered under diminished pressure.
In above-mentioned synthetic method, the mol ratio of citric acid and isooctanol is 1:3.5-4.0, esterification reaction temperature is 90-140
DEG C, reaction time of esterification is 2-6h；It is preferred that, the reaction time is 2-3h.
As the aluminium salt of catalyst using any of aluminum sulfate, alchlor or their mixture.It is preferred that, urge
Agent uses the aluminum sulfate of 18 crystallizations water；Catalyst loading is citric acid and the 1-5% of isooctanol gross mass.
As water entrainer alkane use petroleum ether, hexamethylene, normal heptane, benzene,toluene,xylene in it is any in；Band
Aqua is preferred to use nontoxic material, it is preferred to use boiling point is 90-120 DEG C of petroleum ether；The addition of water entrainer is citric acid
With the 15-25% of isooctanol gross mass.
In above-mentioned synthetic method, decolorization uses activated carbon decolorizing, or directly uses anhydrous magnesium sulfate drying process.
The synthetic method of the present invention is described further with reference to specific embodiment.
Embodiment 1
The present embodiment provides a kind of synthetic method of the different monooctyl ester of low color citric acid three, comprises the following steps：
Citric Acid Mono 84.1g, isooctanol 182.3g are weighed, 18 water aluminum sulfate 2.7g, boiling point is 100-110 DEG C of oil
Ether 66.6g, heating tape water, 98-120 DEG C of reaction temperature, reaction 2h10min terminates；Normal pressure steams petroleum ether to solution temperature
128-130 DEG C, the water aluminum sulfate of solid catalyst 18 is filtered under diminished pressure, product is removed through washing → alkali cleaning → washing, steam distillation
Isooctanol, obtains product 208.2g, yield 98.4%, purity 98.97%, and product color number is 25.
Embodiment 2
The present embodiment provides a kind of synthetic method of the different monooctyl ester of low color citric acid three, comprises the following steps：
Citric Acid Mono 84.1g, isooctanol 182.3g are weighed, 18 water aluminum sulfate 13.3g, boiling point is 100-110 DEG C of oil
Ether 68.4g, heating tape water, 98-121 DEG C of reaction temperature, reaction 2h15min terminates；Normal pressure steams petroleum ether to solution temperature
128-130 DEG C, solid catalyst is filtered under diminished pressure, product removes isooctanol, obtained through washing → alkali cleaning → washing, steam distillation
Product 209.1g, yield 98.9%, purity 99.10%, product color number is 25.
Embodiment 3
The present embodiment provides a kind of synthetic method of the different monooctyl ester of low color citric acid three, comprises the following steps：
Citric Acid Mono 168.1g, isooctanol 364.4g are weighed, 18 water aluminum sulfate 16.0g, boiling point is 100-110 DEG C of stone
Oily ether 106.6g, heating tape water, 97-122 DEG C of reaction temperature, reaction 2h5min terminates；Normal pressure steams petroleum ether to solution temperature
128-130 DEG C, solid catalyst is filtered under diminished pressure, product removes isooctanol, obtained through washing → alkali cleaning → washing, steam distillation
Product 420.0g, yield 99.3%, purity 99.15%, product color number is 25.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art is in the technical scope of present disclosure, the change or replacement that can be readily occurred in,
It should all be included within the scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Enclose and be defined.
Claims (4)
1. a kind of synthetic method of the different monooctyl ester of low color citric acid three, it is characterised in that including：
Using aluminium salt as catalyst, alkane is water entrainer, and boiling point is used for 90-120 DEG C of petroleum ether as the alkane of water entrainer, will
Citric acid carries out esterification with isooctanol under catalyst and water entrainer effect；The mol ratio of the citric acid and isooctanol is
1:3.5-4.0, esterification reaction temperature is 90-140 DEG C, and reaction time of esterification is 2-6h；The aluminium salt of the catalyst uses 18
The aluminum sulfate of the crystallization water；
After reaction terminates, steam water entrainer and apply mechanically, then depressurize and steam most of remaining isooctanol and apply mechanically, be filtered under diminished pressure out catalysis
Agent, by the obtained different monooctyl ester of product citric acid three through washing, after weak base is washed, removes residual isooctanol using steam distillation, takes off
Color processing, obtains the different monooctyl ester of low color citric acid three that color number is less than No. 30 after being filtered under diminished pressure.
2. the synthetic method of the different monooctyl ester of a kind of low color citric acid three according to claim 1, it is characterised in that described to urge
Agent addition is citric acid and the 1-5% of isooctanol gross mass.
3. a kind of synthetic method of the different monooctyl ester of low color citric acid three according to claim 1, it is characterised in that the band
The addition of aqua is citric acid and the 15-25% of isooctanol gross mass.
4. the synthetic method of the different monooctyl ester of a kind of low color citric acid three according to claim 1, it is characterised in that described de-
Color processing uses activated carbon decolorizing, or directly uses anhydrous magnesium sulfate drying process.
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| CN201510679899.9A CN105237395B (en) | 2015-10-19 | 2015-10-19 | A kind of synthetic method of the different monooctyl ester of low color citric acid three |
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| CN105237395B true CN105237395B (en) | 2017-10-24 |
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| CN112209824A (en) * | 2020-10-20 | 2021-01-12 | 山东朗晖石油化学股份有限公司 | Production method of citric acid mixed ester |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4710532A (en) * | 1985-03-13 | 1987-12-01 | Morflex Chemical Company, Inc. | Medical article and method |
| CN101830803A (en) * | 2010-01-25 | 2010-09-15 | 西北师范大学 | Method for synthesizing citric acid ester type compound |
| CN102417452A (en) * | 2011-12-16 | 2012-04-18 | 中粮生物化学（安徽）股份有限公司 | Preparation method of citrate |
-
2015
- 2015-10-19 CN CN201510679899.9A patent/CN105237395B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4710532A (en) * | 1985-03-13 | 1987-12-01 | Morflex Chemical Company, Inc. | Medical article and method |
| CN101830803A (en) * | 2010-01-25 | 2010-09-15 | 西北师范大学 | Method for synthesizing citric acid ester type compound |
| CN102417452A (en) * | 2011-12-16 | 2012-04-18 | 中粮生物化学（安徽）股份有限公司 | Preparation method of citrate |
Non-Patent Citations (2)
| Title |
|---|
| 合成柠檬酸三丁酯的催化体系;侯小娟等;《当代化工》;20070430;第36卷(第2期);第164-167页 * |
| 无水三氯化铝催化合成柠檬酸三正丁酯;蒋月秀等;《广西大学学报(自然科学版)》;19970630;第22卷(第2期);全文 * |
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