CN1762969A - Method for preparing tributyl citrate using mesoporous molecular sieve as catalyst - Google Patents
Method for preparing tributyl citrate using mesoporous molecular sieve as catalyst Download PDFInfo
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- CN1762969A CN1762969A CN 200510030100 CN200510030100A CN1762969A CN 1762969 A CN1762969 A CN 1762969A CN 200510030100 CN200510030100 CN 200510030100 CN 200510030100 A CN200510030100 A CN 200510030100A CN 1762969 A CN1762969 A CN 1762969A
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- molecular sieve
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- tributyl citrate
- mesopore molecular
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Abstract
The tributyl citrate preparing process features using mesoporous molecular sieve as catalyst for the synthesis of tributyl citrate, filtering out the catalyst from the reacted product after reaction for reuse, and treating the filtrate through distillation, water washing, alkali washing, and re-distillation to obtain tributyl citrate. The catalyst has relatively high catalytic activity on the esterification of citric acid and n-butanol. The present invention has the advantages of high yield, cheap catalyst, small catalyst consumptlion, mild reaction condition, short reaction period, reusability of the catalyst, no environmental pollution, direct use of non-toxic reactant n-butanol as water entrainer, etc.
Description
Technical field
The present invention relates to the organic chemistry synthesis technical field, specifically a kind of is the method for Preparation of Catalyst tributyl citrate with the mesopore molecular sieve.
Background technology
Tributyl citrate is nonpoisonous and tasteless " green " environment-friendly plasticizer, be widely used in food and medical instrumentation package, makeup, daily necessities, toy, military supplies etc., have that consistency is good, plasticizing efficiency is high, nontoxic, easily by advantage such as biological degradation and volatility be little, winter hardiness, photostabilization and have excellent water-resistance, and mould resistance is arranged in resin, do not grow mould.The shared goods hardness that improves of tributyl citrate and other non-toxic plasticizers, especially more suitable to soft fiber ether.Simultaneously, have the nitrocotton of improvement anti-uv-ray, and be the solvent of multiple spices, also can be used for the defoamer of protein-based solution.Therefore, tributyl citrate becomes present conventional plasticizers phthalate " green " substitute.The traditional method of synthesizing citric acid tri-n-butyl is to do catalyzer [Song Qihuang chief editor with the vitriol oil, fine chemistry industry technology, Beijing: Chemical Industry Press, 1995:95], this catalyzer exists side reaction many, refining difficulty, equipment corrosion is serious, and the aftertreatment complexity produces industry " three wastes ", shortcomings such as contaminate environment, its application have been subjected to very big restriction.Some catalyzer that grew up afterwards as tosic acid [Xie Wenlei etc., Speciality Petrochemicals, 1998, (4): 7-9], all have catalytic activity preferably to this reaction, but catalyzer costs an arm and a leg, and can not recirculation use.
Summary of the invention
The object of the present invention is to provide a kind of eco-friendly, economic heterogeneous catalysis to prepare the method for tributyl citrate, is that catalyzer solves the existing problem of background technology with the mesopore molecular sieve.
The present invention solves this technical problem by the following technical programs:
Be catalyzer with the HAl-MCM-41 mesopore molecular sieve in the ester building-up process, reaction filters out catalyzer after finishing from reaction mixture, and filtrate is through distillation, washing, alkali cleaning, redistillation, tributyl citrate.The catalyzer that reaction end after-filtration goes out is reusable, and activity remains unchanged substantially, and reaction yield reaches more than 98%.
Reaction expression of the present invention is as follows:
Now describe technical scheme of the present invention in detail:
A kind of method with mesopore molecular sieve catalysis synthesizing citric acid tri-n-butyl is characterized in adopting nontoxic, free from corrosion, the HAl-MCM-41 mesopore molecular sieve that can be recycled as catalyzer, the concrete operations step:
The preparation of the 1st step HAl-MCM-41 mesopore molecular sieve
The Al-MCM-41 mesopore molecular sieve that makes with prior art is through the NH of 4mol/L
4NO
3Aqueous solution exchange, 550 ℃ of roastings three times, the HAl-MCM-41 mesopore molecular sieve;
The second step esterification
Having induction stirring, thermometer, reflux condensing tube, add 0.1～0.15mol citric acid in the 100mL three-necked bottle of water trap, 0.4～0.6mol propyl carbinol carries out heated and stirred, treat citric acid complete molten after, the sampling and measuring acid number adds the HAl-MCM-41 molecular sieve of 0.1～0.5g then, carrying out reflux stirs, the water that reaction is produced is told from water trap, and reaction is reacted about 4h to anhydrous, sampling and measuring acid number, the mensuration of acid number are pressed GB/T1668-1995 and are measured;
The separation of the 3rd step catalyzer and the purifying of product
Reaction mixture in the three-necked bottle is filtered, and the catalyzer that leaches can be directly used in down secondary response, and filtrate is used air distillation, to reclaim excessive propyl carbinol, is cooled to room temperature then, and the adding massfraction is 5～10% NaHCO
3Solution 10～100ml washing is removed unreacted citric acid to neutral, tells upper organic phase with separating funnel then, with anhydrous MgSO
4Drying removes by filter siccative, underpressure distillation, and the cut of 178～180 ℃/400Pa of collection obtains nearly water white product and is tributyl citrate.
Compare with background technology, advantage of the present invention is: (1) productive rate height is 97.5～99.6%; (2) catalyzer is cheap, and catalyst levels is little, accounts for 0.37～1.85% of reaction raw materials gross weight; (3) reaction conditions gentleness, the reaction times is short; (4) catalyzer is reused; (5) there is not environmental pollution; (6) directly make the band aqua, avoided using deleterious toluene etc. with the reactant propyl carbinol.
Embodiment
Below will the present invention is further elaborated by specific embodiment:
Embodiment 1
The preparation of the 1st step catalyzer HAl-MCM-41 mesopore molecular sieve
The Al-MCM-41 mesopore molecular sieve that makes with prior art is through the NH of 4mol/L
4NO
3Aqueous solution exchange, 550 ℃ of roastings (three times) can get the HAl-MCM-41 mesopore molecular sieve;
The 2nd step esterification
Having induction stirring, thermometer, reflux condensing tube adds the 0.1mol citric acid in the 100mL three-necked bottle of water trap and the 0.45mol propyl carbinol carries out heated and stirred, treats the complete molten back of citric acid sampling and measuring acid number, the HAl-MCM-41 molecular sieve that adds 0.3g then, carry out reflux and stir, the water that reaction is produced is told from water trap, and reaction is to anhydrous (about 4h), sampling and measuring acid number, the mensuration of acid number are pressed GB/T1668-1995 and are measured;
The separation of the 3rd step catalyzer and the purifying of product
Reaction mixture in the three-necked bottle is filtered, and the catalyzer that leaches can be directly used in down secondary response, and filtrate is used air distillation, to reclaim excessive propyl carbinol, is cooled to room temperature then, adds 5% NaHCO
3Solution 30ml washing is told upper organic phase with separating funnel, with anhydrous MgSO to neutral
4Drying removes by filter siccative, underpressure distillation, and the cut of 178～180 ℃/400Pa of collection can obtain nearly water white product and be tributyl citrate, and productive rate is 99.2%.
Embodiment 2-4
Except for the following differences, all the other are identical with embodiment 1, are 0.3g at HAl-MCM-41 molecular sieve consumption, and the citric acid consumption is 0.1mol, and propyl carbinol reacts 4h in the ratio consumption of table 1.
Table 1
| Embodiment | Acid alcohol is than (mole) | Productive rate/% |
| 2 3 4 | 1∶4.0 1∶5.0 1∶6.0 | 99.5 98.9 97.5 |
Embodiment 5-7
Except for the following differences, all the other are identical with embodiment 1, and the HAl-MCM-41 molecular sieve is pressed the consumption of table 2 respectively.
Table 2
| Embodiment | Catalyst levels/g | Productive rate/% |
| 5 6 7 | 0.1 0.3 0.5 | 98.8 99.2 99.6 |
Embodiment 8-12
Except for the following differences, all the other are identical with embodiment 1, and the catalyzer recirculation uses the influence to reaction to the results are shown in Table 3.
Table 3
| Embodiment | Catalyzer reuse number of times | Productive rate/% |
| 8 9 10 11 12 | 0 1 2 3 4 | 99.2 98.9 99.0 98.7 98.7 |
Claims (4)
1, a kind of is the method for Preparation of Catalyst tributyl citrate with the mesopore molecular sieve, it is characterized in that: in the tributyl citrate building-up process, make catalyzer with mesopore molecular sieve, after reaction finishes, catalyzer is filtered out also reusable from reaction mixture, filtrate makes tributyl citrate through distillation, washing, alkali cleaning, redistillation.
2, according to claim 1 is the method for Preparation of Catalyst tributyl citrate with the mesopore molecular sieve, it is characterized in that: described catalyzer is the HAl-MCM-41 mesopore molecular sieve.
3, according to claim 1 is the method for Preparation of Catalyst tributyl citrate with the mesopore molecular sieve, it is characterized in that the concrete operations step:
The preparation of the 1st step HAl-MCM-41 mesopore molecular sieve
The Al-MCM-41 mesopore molecular sieve that makes with prior art is through the NH of 4mol/L
4NO
3Aqueous solution exchange, 550 ℃ of roastings three times, the HAl-MCM-41 mesopore molecular sieve;
The 2nd step esterification
In having the 100mL three-necked bottle of induction stirring, thermometer, reflux condensing tube, water trap, add 0.1～0.15mol citric acid, 0.4～0.6mol propyl carbinol carries out heated and stirred, after treating that citric acid is molten entirely, the HAl-MCM-41 mesopore molecular sieve that adds 0.1～0.5g, carrying out reflux stirs, the water that reaction is produced is told from water trap, and reaction is to anhydrous;
The separation of the 3rd step catalyzer and the purifying of product
Reaction mixture in the three-necked bottle is filtered, leach catalyzer HAl-MCM-41 mesopore molecular sieve, filtrate is used air distillation, reclaims excessive propyl carbinol, is cooled to room temperature then, and the adding massfraction is 5～10% NaHCO
3Solution 10～100ml washing is removed unreacted citric acid to neutral, tells upper organic phase with separating funnel then, with anhydrous MgSO
4Drying removes by filter siccative, and underpressure distillation makes tributyl citrate.
4, according to claim 2 is the method for Preparation of Catalyst tributyl citrate with the mesopore molecular sieve, it is characterized in that: catalyst levels accounts for 0.37～1.85% of reaction raw materials total amount.
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| CNB200510030100XA CN100349849C (en) | 2005-09-28 | 2005-09-28 | Method for preparing tributyl citrate using mesoporous molecular sieve as catalyst |
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| CNB200510030100XA CN100349849C (en) | 2005-09-28 | 2005-09-28 | Method for preparing tributyl citrate using mesoporous molecular sieve as catalyst |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102000611A (en) * | 2010-11-08 | 2011-04-06 | 江苏强林生物能源有限公司 | Catalyst for synthesizing tirbutyl citrate and preparation method thereof |
| CN101735055B (en) * | 2009-12-07 | 2013-06-12 | 无锡双象化学工业有限公司 | Method for producing plasticizer tirbutyl citrate |
| CN105418416A (en) * | 2015-11-18 | 2016-03-23 | 湖南尔康制药股份有限公司 | Method for preparing triethyl citrate through mesoporous silica-supported N,N-dicyclohexyl carbodiimide |
| CN105669443A (en) * | 2015-12-31 | 2016-06-15 | 江苏瑞佳化学有限公司 | Method of preparing tributyl citrate with nano-scale intercalated hydrotalcite catalyst |
| CN108863783A (en) * | 2018-07-11 | 2018-11-23 | 广东轻工职业技术学院 | A kind of method of microwave cooperating H-ZSM-5 type Zeolite synthesis tri-n-butyl citrate |
| CN108892613A (en) * | 2018-07-11 | 2018-11-27 | 广东轻工职业技术学院 | A kind of method of the modified H-ZMS-5 type Zeolite synthesis tri-n-butyl citrate of acid |
| CN108911984A (en) * | 2018-07-11 | 2018-11-30 | 广东轻工职业技术学院 | A kind of method of microwave cooperating 5A type Zeolite synthesis plasticizer tri-n-butyl citrate |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1088404C (en) * | 1998-12-15 | 2002-07-31 | 南京师范大学 | Molecular sieve catalyst for synthesis of dibutyl phthalate and its preparing process |
| CN1283609A (en) * | 2000-02-25 | 2001-02-14 | 中国科学院上海有机化学研究所 | Process for arylesterifying plenol |
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2005
- 2005-09-28 CN CNB200510030100XA patent/CN100349849C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735055B (en) * | 2009-12-07 | 2013-06-12 | 无锡双象化学工业有限公司 | Method for producing plasticizer tirbutyl citrate |
| CN102000611A (en) * | 2010-11-08 | 2011-04-06 | 江苏强林生物能源有限公司 | Catalyst for synthesizing tirbutyl citrate and preparation method thereof |
| CN102000611B (en) * | 2010-11-08 | 2012-09-26 | 江苏强林生物能源有限公司 | Catalyst for synthesizing tirbutyl citrate and preparation method thereof |
| CN105418416A (en) * | 2015-11-18 | 2016-03-23 | 湖南尔康制药股份有限公司 | Method for preparing triethyl citrate through mesoporous silica-supported N,N-dicyclohexyl carbodiimide |
| CN105669443A (en) * | 2015-12-31 | 2016-06-15 | 江苏瑞佳化学有限公司 | Method of preparing tributyl citrate with nano-scale intercalated hydrotalcite catalyst |
| CN108863783A (en) * | 2018-07-11 | 2018-11-23 | 广东轻工职业技术学院 | A kind of method of microwave cooperating H-ZSM-5 type Zeolite synthesis tri-n-butyl citrate |
| CN108892613A (en) * | 2018-07-11 | 2018-11-27 | 广东轻工职业技术学院 | A kind of method of the modified H-ZMS-5 type Zeolite synthesis tri-n-butyl citrate of acid |
| CN108911984A (en) * | 2018-07-11 | 2018-11-30 | 广东轻工职业技术学院 | A kind of method of microwave cooperating 5A type Zeolite synthesis plasticizer tri-n-butyl citrate |
| CN108892613B (en) * | 2018-07-11 | 2021-02-19 | 广东轻工职业技术学院 | Method for synthesizing tri-n-butyl citrate by using acid modified H-ZMS-5 type molecular sieve |
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Granted publication date: 20071121 Termination date: 20110928 |