CN108911984A - A kind of method of microwave cooperating 5A type Zeolite synthesis plasticizer tri-n-butyl citrate - Google Patents
A kind of method of microwave cooperating 5A type Zeolite synthesis plasticizer tri-n-butyl citrate Download PDFInfo
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- CN108911984A CN108911984A CN201810754721.XA CN201810754721A CN108911984A CN 108911984 A CN108911984 A CN 108911984A CN 201810754721 A CN201810754721 A CN 201810754721A CN 108911984 A CN108911984 A CN 108911984A
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- 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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Abstract
The invention belongs to plasticizer synthesis technical fields, and in particular to a kind of method of microwave cooperating 5A type Zeolite synthesis plasticizer tri-n-butyl citrate.It the described method comprises the following steps：First by 5A molecular sieve activation, reaction vessel then is added in 5A molecular sieve, anhydrous citric acid and the n-butanol after activation, esterification obtains tri-n-butyl citrate under the conditions of microwave irradiation；Wherein microwave irradiation power is 100~500W, and microwave irradiation time is 3~7min, and microwave irradiation temperature is 100~140 DEG C.The present invention has merged the advantages of both molecular sieve and microwave heating technique, have the characteristics that quickly, easy, yield is high, easy purification and pollution-free.
Description
Technical field
The invention belongs to plasticizer synthesis technical fields, and in particular to a kind of microwave cooperating 5A type Zeolite synthesis plasticizer
The method of tri-n-butyl citrate.
Background technique
In recent years, China has been increasingly becoming Asia plasticizer production amount and the most country of consumption figure, with state foreign minister
Than China's plasticizer kind is slightly single, and product structure is also unreasonable, its synthesis unit is more in addition, yield is not high, soda acid
The exhaust emission of the three wastes is serious, forces domestic many plasticizer enterprise underproduction or halt production.In addition, having in recent years more and more
Research and report make a declaration of the negative effect of dioctyl phthalate DOP and other adjacent benzene class plasticizer.Since China lacks
The raw material sources such as few isononyl alcohol, decyl alcohol cause China and the production and marketing structure of American-European countries plasticizer to differ greatly.With state foreign minister
Than the domestic plastic additive examination criteria in fields such as food, medical treatment seriously lags, and at home and abroad standard is forced down, and future increases
Modeling agent will develop to the direction of safety, green and profession, and environmentally friendly machine includes citric acid ester type, polyesters, biodegradable class
Deng.
Tri-n-butyl citrate plasticizer is obtained by citric acid and alcohols esterification, and synthetic route is not multiple
Miscellaneous, synthetic technology superiority and inferiority depends primarily on the difference of selected catalyst.Traditional esterification generally uses sulfuric acid as catalysis
Agent, although the method catalyst is cheap, catalytic activity is high, and there are equipment seriously corroded, side reaction is more, waste reaction solution difficulty
The disadvantages of reason, high production cost.Sieve peg-raking catalyst is widely used, and molecular sieve has regular and uniform transgranular duct,
And pore size keeps the catalytic performance of molecular sieve intermediate with reactant molecule, product molecule or reaction close to molecular dimension
The variation of the geometric dimension of object and significant changes.However due to the particularity of tributyl citrate, molecular sieve catalytic is synthesized at present
Tri-n-butyl citrate yield is lower, and the reaction time is longer.
Summary of the invention
To solve the shortcomings and deficiencies of the prior art, the purpose of the present invention is to provide a kind of microwave cooperating 5A types point
The method of son sieve synthesis plasticizer tri-n-butyl citrate.
Microwave-assisted synthesis is environment amenable green synthesis techniques developed in recent years, has yield height, speed
The advantages that degree is fast, with high purity, energy saving, efficient and environmentally friendly, has been widely used for the field of chemical synthesis.Molecular sieve-microwave synthesis
Method, the advantages of having merged both molecular sieve and microwave heating technique, have quickly, easy, yield is high, easy purification and pollution-free etc.
Feature.
The object of the invention is achieved through the following technical solutions：
A kind of method of microwave cooperating 5A type Zeolite synthesis plasticizer tri-n-butyl citrate, includes the following steps：First
By 5A molecular sieve activation, reaction vessel then is added in 5A molecular sieve, anhydrous citric acid and the n-butanol after activation, in microwave spoke
Esterification obtains tri-n-butyl citrate according under the conditions of；Wherein microwave irradiation power is 100~500W, and microwave irradiation time is
3~7min, microwave irradiation temperature are 100~140 DEG C；The dosage of the 5A molecular sieve be anhydrous citric acid quality 1%~
5%.
Preferably, the 5A molecular sieve after the 5A molecular sieve is activated for dry 2 hours in 300 DEG C.
Preferably, the molar ratio of the anhydrous citric acid and n-butanol is 1:4~1:8, more preferably 1:7.
Preferably, the dosage of the 5A molecular sieve is the 4% of anhydrous citric acid quality.
Preferably, the microwave irradiation power is 400W, and microwave irradiation time 3min, microwave irradiation temperature is 130
℃。
Compared with prior art, the present invention has the following advantages and beneficial effects：
(1) time-consuming is short, yield is high；On the basis of microwave catalysis, molecular sieve provides suitable aperture catalysis, improves microwave
Absorptivity shortens the reaction time, increases reaction rate and yield；
(2) pollution is small, has a wide range of application, and molecular sieve is recyclable；Molecular sieve is the silicate or aluminosilicate of a kind of crystalline state
Salt, good thermal stability in pyroreaction system, component are not involved in reaction, can repeatedly recycle use, expand microwave method in height
The application in warm liquid-phase catalysis synthesis field；
(3) easy to operate, safe, cost is relatively low, reaction condition is easy to accomplish, at the same reduce high temperature high pressure reverse reply set
Standby requirement and potential risk.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Material used by following embodiment is：
Anhydrous citric acid (99.5%, analyze pure), the upper smooth Science and Technology Co., Ltd. of Haitai；99% n-butanol (upper Haitai
Smooth Science and Technology Co., Ltd. analyzes pure)；5A molecular sieve (Catalyst Factory, Nankai Univ)；
Instrument used by following embodiment is：
Six magnetic stirring apparatus of HJ-6B (White Tower Xin Bao instrument plant of Jintan City)；WF-4000 normal pressure microwave quick-reaction system
(the towering like a mountain peak Yao's instrument in Shanghai analyzes Co., Ltd).
Embodiment 1
Esterification, which is carried out, according to 15 groups of difference microwave irradiation conditions of table 1-3 setting respectively in the present embodiment prepares lemon
Sour tri-n-butyl studies influence of the different microwave irradiation conditions to esterification yield.
Tri-n-butyl citrate synthesis step is as follows：5A molecular sieve is first made it in 2 hours in 300 DEG C of dryings of air dry oven
Then digestion bottle is added in 5A molecular sieve, anhydrous citric acid and n-butanol after activation by activation, anhydrous citric acid and n-butanol
Molar ratio is 1:6, the amount of catalyst 5A molecular sieve is the 3% of anhydrous citric acid quality；Respectively according to the microwave irradiation item of table 1-3
Part is tested.After product is cooling, citrate, shadow of the different microwave irradiation conditions to esterification yield are detected with gas chromatography
Sound the results are shown in Table 1-3：
Influence of 1 microwave power of table to esterification yield
| Number | 1-1 | 1-2 | 1-3 | 1-4 | 1-5 |
| Microwave power/W | 100 | 200 | 300 | 400 | 500 |
| The microwave time/min | 5 | 5 | 5 | 5 | 5 |
| Microwave temperature/DEG C | 120 | 120 | 120 | 120 | 120 |
| Esterification yield/% | 17.43 | 38.49 | 45.42 | 42.75 | 31.23 |
Influence of the 2 microwave time of table to esterification yield
Influence of 3 microwave temperature of table to esterification yield
| Number | 1-11 | 1-12 | 1-13 | 1-14 | 1-15 |
| Microwave power/W | 200 | 200 | 200 | 200 | 200 |
| The microwave time/min | 2 | 3 | 4 | 5 | 6 |
| Microwave temperature/DEG C | 120 | 120 | 120 | 120 | 120 |
| Esterification yield/% | 30.40 | 50.78 | 37.60 | 38.49 | 30.86 |
Embodiment 2
Esterification is carried out according to ratio shown in table 4 and table 5 respectively in the present embodiment and prepares tri-n-butyl citrate, is ground
Study carefully acid alcohol molar ratio, catalyst charge influences esterification yield.
Tri-n-butyl citrate synthesis step is as follows：5A molecular sieve is first made it in 2 hours in 300 DEG C of dryings of air dry oven
Then digestion bottle (acid alcohol molar ratio, 5A molecular sieve is added in 5A molecular sieve, anhydrous citric acid and n-butanol after activation by activation
Additional amount is shown in Table 4 and 5)；Esterification under the conditions of microwave power 200W, time 5min, the microwave irradiation that temperature is 120 DEG C
Prepare tri-n-butyl citrate.After product is cooling, citrate, different acid alcohol molar ratios, catalysis are detected with gas chromatography
Agent additional amount the results are shown in Table 4-5 to esterification yield influence：
The influence of the comparison esterification yield of the amount of 4 acid alcohol substance of table
| Number | 2-1 | 2-2 | 2-3 | 2-4 |
| Anhydrous citric acid and n-butanol molar ratio | 1：5 | 1：6 | 1：7 | 1：8 |
| 5A molecular sieve and anhydrous citric acid mass ratio/% | 3 | 3 | 3 | 3 |
| Esterification yield/% | 20.49 | 38.49 | 69.97 | 63.84 |
Influence of the amount of 5 catalyst of table to esterification yield
| Number | 2-1 | 2-2 | 2-3 | 2-4 | 2-5 |
| Anhydrous citric acid and n-butanol molar ratio | 1：6 | 1：6 | 1：6 | 1：6 | 1：6 |
| 5A molecular sieve and anhydrous citric acid mass ratio/% | 1 | 2 | 3 | 4 | 5 |
| Esterification yield/% | 1.44 | 11.20 | 38.49 | 45.19 | 44.68 |
Embodiment 3
The present embodiment provides a kind of methods of microwave cooperating 5A type Zeolite synthesis tri-n-butyl citrate, and steps are as follows：
5A molecular sieve is first made into its activation in 2 hours in 300 DEG C of dryings of air dry oven, then by 5A molecular sieve, the anhydrous lemon after activation
Lemon acid and n-butanol, which are added, digests bottle, and the molar ratio of anhydrous citric acid and n-butanol is 1:7, the amount of catalyst 5A molecular sieve is nothing
The 4% of water citric acid quality；It is esterified under the conditions of microwave power 400W, time 3min, the microwave irradiation that temperature is 130 DEG C anti-
Tri-n-butyl citrate should be prepared.After product is cooling, citrate, esterification yield 70.3% are detected with gas chromatography.
Embodiment 4
After the completion of the esterification of embodiment 3,5A molecular sieve is recycled by filtering, it is real to carry out recycling for 150 DEG C of drying
It tests：Then reaction is added in 5A molecular sieve, anhydrous citric acid and n-butanol after activation by the 5A molecular sieve activation that recycling is obtained
Container, esterification obtains tri-n-butyl citrate, experimental procedure and technological parameter and 3 phase of embodiment under the conditions of microwave irradiation
Together.
After product is cooling, citrate is detected with gas chromatography.Through detecting, the 5A molecular sieve once recycled is most suitable
It is 69.22% that (the technological parameter condition of embodiment 3) catalysis, which prepares the esterification yied of tri-n-butyl citrate, under the conditions of preferably, secondary
(the technological parameter condition of the embodiment 3) catalysis under optimum of the molecular sieve of recycling prepares the esterification of tri-n-butyl citrate
Yield is 65.47%.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (7)
1. a kind of method of microwave cooperating 5A type Zeolite synthesis plasticizer tri-n-butyl citrate, which is characterized in that including with
Lower step：First by 5A molecular sieve activation, reaction then is added in 5A molecular sieve, anhydrous citric acid and the n-butanol after activation and is held
Device, esterification obtains tri-n-butyl citrate under the conditions of microwave irradiation；Wherein microwave irradiation power is 100~500W, micro-
Wave irradiation time is 3~7min, and microwave irradiation temperature is 100~140 DEG C.
2. a kind of side of microwave cooperating 5A type Zeolite synthesis plasticizer tri-n-butyl citrate according to claim 1
Method, which is characterized in that the dosage of the 5A molecular sieve is the 1%~5% of anhydrous citric acid quality.
3. a kind of side of microwave cooperating 5A type Zeolite synthesis plasticizer tri-n-butyl citrate according to claim 2
Method, which is characterized in that the dosage of the 5A molecular sieve is the 4% of anhydrous citric acid quality.
4. a kind of side of microwave cooperating 5A type Zeolite synthesis plasticizer tri-n-butyl citrate according to claim 1
Method, which is characterized in that the molar ratio of the anhydrous citric acid and n-butanol is 1:4~1:8.
5. a kind of side of microwave cooperating 5A type Zeolite synthesis plasticizer tri-n-butyl citrate according to claim 4
Method, which is characterized in that the molar ratio of the anhydrous citric acid and n-butanol is 1:7.
6. a kind of side of microwave cooperating 5A type Zeolite synthesis plasticizer tri-n-butyl citrate according to claim 1
Method, which is characterized in that the microwave irradiation power is 400W, and microwave irradiation time 3min, microwave irradiation temperature is 130
℃。
7. a kind of side of microwave cooperating 5A type Zeolite synthesis plasticizer tri-n-butyl citrate according to claim 1
Method, which is characterized in that 5A molecular sieve of the 5A molecular sieve after 300 DEG C of dryings are activated for 2 hours.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117105778A (en) * | 2023-10-23 | 2023-11-24 | 深圳尚诺生物科技有限公司 | Preparation process of triethyl citrate |
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| CN1762969A (en) * | 2005-09-28 | 2006-04-26 | 华东师范大学 | Method for preparing tributyl citrate using mesoporous molecular sieve as catalyst |
| CN101973873A (en) * | 2010-10-09 | 2011-02-16 | 东北石油大学 | Method for synthesizing carboxylic ester by microwave radiation catalysis |
| CN104262156A (en) * | 2014-09-06 | 2015-01-07 | 中国农业科学院油料作物研究所 | Method for microwave-assisted fast and efficient preparation of phenethyl caffeate |
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| CN1762969A (en) * | 2005-09-28 | 2006-04-26 | 华东师范大学 | Method for preparing tributyl citrate using mesoporous molecular sieve as catalyst |
| CN101973873A (en) * | 2010-10-09 | 2011-02-16 | 东北石油大学 | Method for synthesizing carboxylic ester by microwave radiation catalysis |
| CN104262156A (en) * | 2014-09-06 | 2015-01-07 | 中国农业科学院油料作物研究所 | Method for microwave-assisted fast and efficient preparation of phenethyl caffeate |
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| CN117105778A (en) * | 2023-10-23 | 2023-11-24 | 深圳尚诺生物科技有限公司 | Preparation process of triethyl citrate |
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Application publication date: 20181130 |