CN101255114A - Method for preparing oleoyl tributyl citrate plasticizer - Google Patents
Method for preparing oleoyl tributyl citrate plasticizer Download PDFInfo
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- CN101255114A CN101255114A CNA2007100186922A CN200710018692A CN101255114A CN 101255114 A CN101255114 A CN 101255114A CN A2007100186922 A CNA2007100186922 A CN A2007100186922A CN 200710018692 A CN200710018692 A CN 200710018692A CN 101255114 A CN101255114 A CN 101255114A
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- tributyl citrate
- oleoyl
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Abstract
The invention provides a method for preparing oleoyl tributyl citrate plasticizer, comprises: adding citric acid, n-butanol, water-carrying agent and catalytic agent into a reactor, stirring and heating up, controlling the temperature for reaction at 96 degree C until no water is generated again, and obtaining tributyl citrate; adding oleate into the reactor, stirring and heating up, dropping phosphorus trichloride into the reactor, reacting for 3h at 60 degree C, cooling to room temperature, standing for 2h, and separating to obtain; and a step 3, synthesizing oleoyl tributyl citrate; adding tributyl citrate and a catalytic agent into the reactor, stirring and heating up to 70 degree C, dropping oleoyl chloride, absorbing the generated hydrogen chloride by introducing the drier into base, stopping the reaction until the pH value of base has no change, and obtaining oleoyl tributyl citrate by neutralizing with sodium carbonate solution, water washing, and vacuum filtrating.
Description
Technical field
The present invention relates to the preparation method of plastic plasticizer.
Background technology
The plasticizer phthalic acid ester class that is used for macromolecular materials such as food product pack, toy for children can be brought out carcinogenic, has abroad made laws and has limited the non-toxic plasticizer that it uses and actively searching can replace phthalate.Citric acid ester plasticizer is the rising non-toxic plasticizer of a class, has vast potential for future development.At present, the product development of citric acid ester type both at home and abroad mainly contains triethyl citrate (TEC), acetyl triethyl citrate (ATEC), tri-n-butyl citrate (TBC), ATBC (ATBC), trioctyl lemon acid (TOC), acetyl tributyl citrate three monooctyl esters (ATOC), citric acid tri-n-hexyl ester (THC), the just own ester of acetyl tributyl citrate three (ATHC), butyryl citric acid tri-n-hexyl ester nine aspects such as (BTHC), but these citrate series products are the ubiquity poor heat stability in actual use, the plastipaste stability of viscidity is low, the low temperature flexibility deficiency, the not good defective of the bad and anti-transport property of the extractable of anti-the solvent, the product use range of the existing citric acid ester type that the deficiency on these performances makes is limited to.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of oleoyl tributyl citrate plasticizer.
The present invention is the preparation method of oleoyl tributyl citrate plasticizer, and its synthetic route is as follows:
Step 1: tributyl citrate synthetic
Step 2: oleoyl chloride synthetic
3CH
3(CH
2)
7CH＝CH(CH
2)
7COOH+PCl
3→3CH
3(CH
2)
7CH＝CH(CH
2)
7COCl+H
3PO
3
Step 3: oleoyl tributyl citrate synthetic
Its concrete synthesis step is as follows:
Step 1: tributyl citrate synthetic.In the reactor that electronic stirring, the heating of electric heating cap, oily water separation, reflux exchanger and temp measuring system are housed, add citric acid, propyl carbinol, band aqua, catalyzer, open and stir and intensification, controlled temperature in 96 ℃ be reacted to anhydrous generation till, obtain tributyl citrate;
Step 2: oleoyl chloride synthetic.In the reactor that electronic stirring, heating in water bath, dropping funnel, reflux exchanger, temp measuring system are housed, add oleic acid, stirring heats up also drips phosphorus trichloride, and in 60 ℃ of insulation reaction 3 hours, cool to room temperature static 2 hours, separated obtaining oleoyl chloride;
Step 3: oleoyl tributyl citrate synthetic.In the reactor that electronic stirring, heating in water bath, dropping funnel, reflux exchanger, temp measuring system are housed, add tributyl citrate and catalyzer, stirring also is warmed up to 70 ℃, drip oleoyl chloride, the hydrogenchloride that generates feeds in the buck through moisture eliminator and absorbs, the PH no change of observation buck, stopped reaction, product neutralizes through sodium carbonate solution, washing is oleoyl tributyl citrate behind the decompress filter.
The existing citric acid ester plasticizer insufficient major cause of ubiquity in actual applications is: due to the ratio of less, fatty carbon of the molecular weight of product and polar group is improper.Adopt citric acid and propyl carbinol to generate tributyl citrate by esterification; With oleic acid is that the reaction of raw material and phosphorus trichloride generates oleoyl chloride; Tributyl citrate and oleoyl chloride generate oleoyl tributyl citrate by acylation reaction; introduce long fatty carbon chain in the tributyl citrate molecular structure; its molecular weight is increased be 625g/mol, fatty carbon is 8 (identical with DOP) with the ratio of polar group.Determined that thus the oleoyl tributyl citrate volatility is little, stability is high, resisted migration, anti-extraction, low-temperature flexibility, non-toxic and safe, and be better than DOP in over-all properties.
Embodiment
The present invention is the preparation method of oleoyl tributyl citrate plasticizer, and its synthetic route is as follows:
Step 1: tributyl citrate synthetic
Step 2: oleoyl chloride synthetic
3CH
3(CH
2)
7CH＝CH(CH
2)
7COOH+PCl
3→3CH
3(CH
2)
7CH＝CH(CH
2)
7COCl+H
3PO
3
Step 3: oleoyl tributyl citrate synthetic
Its concrete synthesis step is as follows:
Step 1: tributyl citrate synthetic.In the reactor that electronic stirring, the heating of electric heating cap, oily water separation, reflux exchanger and temp measuring system are housed, add citric acid, propyl carbinol, band aqua, catalyzer, open and stir and intensification, controlled temperature in 96 ℃ be reacted to anhydrous generation till, obtain tributyl citrate;
Step 2: oleoyl chloride synthetic.In the reactor that electronic stirring, heating in water bath, dropping funnel, reflux exchanger, temp measuring system are housed, add oleic acid, stirring heats up also drips phosphorus trichloride, and in 60 ℃ of insulation reaction 3 hours, cool to room temperature static 2 hours, separated obtaining oleoyl chloride;
Step 3: oleoyl tributyl citrate synthetic.In the reactor that electronic stirring, heating in water bath, dropping funnel, reflux exchanger, temp measuring system are housed, add tributyl citrate and catalyzer, stirring also is warmed up to 70 ℃, drip oleoyl chloride, the hydrogenchloride that generates feeds in the buck through moisture eliminator and absorbs, the PH no change of observation buck, stopped reaction, product neutralizes through sodium carbonate solution, washing is oleoyl tributyl citrate behind the decompress filter.
In tributyl citrate synthetic, propyl carbinol and citric acid are reaction mass, and the mol ratio of propyl carbinol and citric acid is 4.5: 1; The band aqua is a dimethylbenzene, and its consumption is 50% of a butanols quality; Catalyzer is that its consumption of tosic acid is 0.2%～0.5% of a reaction mass.
Oleic acid and phosphorus trichloride are reaction mass in oleoyl chloride synthetic, and the mol ratio of oleic acid and phosphorus trichloride is 3: 1.2.
In oleoyl tributyl citrate synthetic, tributyl citrate and oleoyl chloride are reaction mass, and the mol ratio of tributyl citrate and oleoyl chloride is 1: 1; Catalyzer is a pyridine, and consumption is 0.1%～0.2% of a reaction mass.
The molecular weight of oleoyl tributyl citrate is 625g/mol, and the ratio of fatty carbon and polar group is 8.
Be embodiment more specifically below:
(1) tributyl citrate is synthetic:
Accurately take by weighing the 192g citric acid, the 333g propyl carbinol, the 7g tosic acid, 166.5g dimethylbenzene, throw in the 1000ml four-hole reaction flask that electronic stirring, condenser, water-and-oil separator, thermometer, the heating of electric heating cap are housed, heating also is interrupted and stirs, treat material melt after continuously stirring again, each throwing amount is too much unsuitable, in order to avoid citric acid melts slowly, 96 ℃ of temperature of reaction, 5 hours reaction times, open vacuum system, propyl carbinol, dimethylbenzene and water are deviate from underpressure distillation, cooling discharge when distillating component to nothing promptly gets tributyl citrate.
(2) oleoyl chloride is synthetic
Accurately take by weighing 282g oleic acid, add and be equipped with in the 500ml four-hole reaction flask of electronic stirring, condenser, thermometer, dropping funnel, heating in water bath, stir and heat up and dropping 164.4g phosphorus trichloride in system, in 60 ℃ of insulation reaction 3 hours, underpressure distillation goes out unreacted phosphorus trichloride, cooling also static 2 hours separates obtaining oleoyl chloride.
(3) oleoyl tributyl citrate is synthetic
Accurately take by weighing the 360g tributyl citrate, 7.2g pyridine, add and be equipped with in the 1000ml four-hole bottle of electronic stirring, dropping funnel, thermometer, chlorine hydride absorption system, heating in water bath and good seal, open stirring and be warming up to 70 ℃, stir and in system, drip the 300g oleoyl chloride down, 1h dropwises, continue reaction, the hydrogenchloride that generates feeds in the buck through moisture eliminator and absorbs, the PH no change stopped reaction of observation buck, leave standstill cooling, neutralize, wash with sodium carbonate solution, underpressure distillation promptly gets oleoyl tributyl citrate.
Claims (6)
1, the preparation method of oleoyl tributyl citrate plasticizer is characterized in that synthetic route is as follows:
Step 1: tributyl citrate synthetic
Step 2: oleoyl chloride synthetic
3CH
3(CH
2)
7CH＝CH(CH
2)
7COOH+PCl
3→3CH
3(CH
2)
7CH＝CH(CH
2)
7COCl+H
3PO
3
Step 3: oleoyl tributyl citrate synthetic
2, the preparation method of oleoyl tributyl citrate plasticizer according to claim 1, its concrete synthesis step is as follows:
Step 1: tributyl citrate synthetic.In the reactor that electronic stirring, the heating of electric heating cap, oily water separation, reflux exchanger and temp measuring system are housed, add citric acid, propyl carbinol, band aqua, catalyzer, open and stir and intensification, controlled temperature in 96 ℃ be reacted to anhydrous generation till, obtain tributyl citrate;
Step 2: oleoyl chloride synthetic.In the reactor that electronic stirring, heating in water bath, dropping funnel, reflux exchanger, temp measuring system are housed, add oleic acid, stir and heat up and the dropping phosphorus trichloride, in 60 ℃ of insulation reaction 3h, cool to room temperature, static 2h separates obtaining oleoyl chloride;
Step 3: oleoyl tributyl citrate synthetic.In the reactor that electronic stirring, heating in water bath, dropping funnel, reflux exchanger, temp measuring system are housed, add tributyl citrate and catalyzer, stirring also is warmed up to 70 ℃, drip oleoyl chloride, the hydrogenchloride that generates feeds in the buck through moisture eliminator and absorbs, the PH no change of observation buck, stopped reaction, product neutralizes through sodium carbonate solution, washing is oleoyl tributyl citrate behind the decompress filter.
3, the preparation method of oleoyl tributyl citrate plasticizer according to claim 1 is characterized in that propyl carbinol and citric acid are reaction mass in tributyl citrate synthetic, and the mol ratio of propyl carbinol and citric acid is 4.5: 1; The band aqua is a dimethylbenzene, and its consumption is 50% of a butanols quality; Catalyzer is that its consumption of tosic acid is 0.2%～0.5% of a reaction mass.
4, the preparation method of oleoyl tributyl citrate plasticizer according to claim 1 is characterized in that oleic acid and phosphorus trichloride are reaction mass in oleoyl chloride synthetic, and the mol ratio of oleic acid and phosphorus trichloride is 3: 1.2.
5, the preparation method of oleoyl tributyl citrate plasticizer according to claim 1 is characterized in that tributyl citrate and oleoyl chloride are reaction mass in oleoyl tributyl citrate synthetic, and the mol ratio of tributyl citrate and oleoyl chloride is 1: 1; Catalyzer is a pyridine, and consumption is 0.1%～0.2% of a reaction mass.
6, the preparation method of oleoyl tributyl citrate plasticizer according to claim 1, the molecular weight that it is characterized in that oleoyl tributyl citrate is 625g/mol, the ratio of fatty carbon and polar group is 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100186922A CN101255114A (en) | 2007-09-06 | 2007-09-06 | Method for preparing oleoyl tributyl citrate plasticizer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100186922A CN101255114A (en) | 2007-09-06 | 2007-09-06 | Method for preparing oleoyl tributyl citrate plasticizer |
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| Publication Number | Publication Date |
|---|---|
| CN101255114A true CN101255114A (en) | 2008-09-03 |
Family
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781213A (en) * | 2010-03-29 | 2010-07-21 | 西安交通大学 | Maleic acid tributyl citrate diester compound and preparation method thereof |
| CN102249916A (en) * | 2011-05-26 | 2011-11-23 | 南京化工职业技术学院 | Continuous production process for tributyl citrate |
| CN102503823A (en) * | 2011-11-14 | 2012-06-20 | 浙江传化华洋化工有限公司 | Synthesis process for fatty acyl citrate compound |
| CN103172514A (en) * | 2013-03-07 | 2013-06-26 | 华东理工大学 | Aliphatic acid citrate preparation method |
| CN103450014A (en) * | 2013-09-09 | 2013-12-18 | 上海知研新材料科技有限公司 | Method for synthesizing acetyl diacetin dibutyl citrate |
| CN106753809A (en) * | 2016-11-24 | 2017-05-31 | 常州大学 | A kind of utilization vegetable oil esters and citrate synthetic macromolecule amount, the preparation method of hyper-branched citrate ester derivatives |
| CN110372501A (en) * | 2019-07-19 | 2019-10-25 | 中国科学院兰州化学物理研究所 | A kind of preparation method of fatty acyl citrate type lubricating oil additive |
| CN114634527A (en) * | 2022-05-17 | 2022-06-17 | 江苏恒力化纤股份有限公司 | Preparation method of phosphorus-containing multifunctional finishing agent and finishing method of polyester fiber product |
-
2007
- 2007-09-06 CN CNA2007100186922A patent/CN101255114A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781213A (en) * | 2010-03-29 | 2010-07-21 | 西安交通大学 | Maleic acid tributyl citrate diester compound and preparation method thereof |
| CN101781213B (en) * | 2010-03-29 | 2013-04-24 | 西安交通大学 | Maleic acid tributyl citrate diester compound and preparation method thereof |
| CN102249916A (en) * | 2011-05-26 | 2011-11-23 | 南京化工职业技术学院 | Continuous production process for tributyl citrate |
| CN102249916B (en) * | 2011-05-26 | 2014-07-23 | 南京化工职业技术学院 | Continuous production process for tributyl citrate |
| CN102503823A (en) * | 2011-11-14 | 2012-06-20 | 浙江传化华洋化工有限公司 | Synthesis process for fatty acyl citrate compound |
| CN102503823B (en) * | 2011-11-14 | 2013-10-23 | 浙江传化华洋化工有限公司 | Synthesis process for fatty acyl citrate compound |
| CN103172514A (en) * | 2013-03-07 | 2013-06-26 | 华东理工大学 | Aliphatic acid citrate preparation method |
| CN103450014A (en) * | 2013-09-09 | 2013-12-18 | 上海知研新材料科技有限公司 | Method for synthesizing acetyl diacetin dibutyl citrate |
| CN103450014B (en) * | 2013-09-09 | 2018-04-06 | 上海知研新材料科技有限公司 | A kind of method of the acetoglyceride dibutyl ester of synthesis of acetyl citric acid two |
| CN106753809A (en) * | 2016-11-24 | 2017-05-31 | 常州大学 | A kind of utilization vegetable oil esters and citrate synthetic macromolecule amount, the preparation method of hyper-branched citrate ester derivatives |
| CN110372501A (en) * | 2019-07-19 | 2019-10-25 | 中国科学院兰州化学物理研究所 | A kind of preparation method of fatty acyl citrate type lubricating oil additive |
| CN114634527A (en) * | 2022-05-17 | 2022-06-17 | 江苏恒力化纤股份有限公司 | Preparation method of phosphorus-containing multifunctional finishing agent and finishing method of polyester fiber product |
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Open date: 20080903 |