CN1903824A - Clean esterification method for producing bialkyl ortho phthalate - Google Patents
Clean esterification method for producing bialkyl ortho phthalate Download PDFInfo
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- CN1903824A CN1903824A CN 200610069862 CN200610069862A CN1903824A CN 1903824 A CN1903824 A CN 1903824A CN 200610069862 CN200610069862 CN 200610069862 CN 200610069862 A CN200610069862 A CN 200610069862A CN 1903824 A CN1903824 A CN 1903824A
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Abstract
The present invention relates to a clean esterification method for producing dialkyl phthalate. It is characterized by that it adopts the ionic liquid formed from sulfonic acid group functionalized alkyl pyridine cation or sulfonic acid group functionalized 1,3-dialkyl iminazol cation or 2-oxopyrrolidine cation and organic or inorganic anion X as catalyst of reaction and reaction medium; at normal pressure its reaction temperature is 90-130deg.C and reaction time is 1-2hr, it can catalyze the esterification reaction of phthalic anhydride and isooctanol or n-octanol so as to obtain the invented dialkyl phthalate.
Description
Technical field
The present invention relates to the esterification process of the production bialkyl ortho phthalate of a kind of methodology of organic synthesis, particularly a kind of cleaning.
Technical background
Bialkyl ortho phthalate class softening agent is a most popular class softening agent in the present plastic working, have that volatility is little, plasticizing efficiency is high,, electrical property low with the mutual solubility of water well, flexibility and good advantages such as comprehensive process performance preferably, thereby become the common plasticizer of the maximum class of production and consumption amount.Wherein, be most widely used again with dioctyl phthalate (DOP) (hereinafter to be referred as DOP) over-all properties the best.The synthetic method of bialkyl ortho phthalate class is an example with DOP, and liquid phase acid catalyzed esterification method, non-acid catalyzed process, catalyst-free method and solid superacid as catalyst method etc. are arranged.Use in the acid catalysis technology in traditional industry, sulfuric acid has active high and use temperature is low, advantages such as easy operation; But selectivity is low, poor product quality, to equipment corrosion and contaminate environment.And be the more non-acid catalysis technology (JP 1985-54945, EP 405332) of industrial application of representative with the titanate ester, wastewater flow rate is few, and product postprocessing is simple, good product quality, but catalyzer price height, difficult separation and recycling, energy consumption height.As for the catalyst-free technology of German BASF AG, side reaction is few, do not wash with water, but facility investment is big, and quality product is relatively poor.
Ionic liquid at room temperature (being called for short RTIL) is meant by organic cation and the salt compounds that is in a liquid state under room temperature or nearly room temperature inorganic or that organic anion constitutes, as a kind of eco-friendly solvent and catalyzer, can regulate physical and chemical performance with it, be subjected to each field scholar's extensive concern.And functionalized ion liquid (functionalized ionic liquids) has become the focus in the research in recent years.The called function ionic liquid is promptly introduced the functional group with catalytic activity on general ion liquid positively charged ion or negatively charged ion, ionic liquid is had than the stronger catalytic activity of general neutral ion liquid; And have better stability than the neutral ion liquid of compound mineral acid, also be easier to simultaneously and the separating of product ester.
Summary of the invention
The objective of the invention is to replace the synthetic method of traditional acid catalysis bialkyl ortho phthalate, a kind of efficient and eco-friendly reaction medium and catalyzer are provided, under the reaction conditions of gentleness, catalysis Tetra hydro Phthalic anhydride and isooctyl alcohol or n-Octanol esterification generate the novel method of bialkyl ortho phthalate.
Method of the present invention, it is characterized in that adopting 1 of sulfonic functional alkyl pyridine positively charged ion or sulfonic functional, the ionic liquid that 3-dialkylimidazolium positively charged ion or 2-oxo-pyrrolidine positively charged ion and organic or inorganic negatively charged ion X constitute is as catalyst for reaction and reaction medium; Under normal pressure, 90～130 ℃ of temperature of reaction, 1 to 2 hour reaction times catalysis Tetra hydro Phthalic anhydride and isooctyl alcohol or n-Octanol esterification generate bialkyl ortho phthalate.
1 of the described sulfonic functional alkyl pyridine of method of the present invention positively charged ion (1) or sulfonic functional, the general structure of 3-dialkylimidazolium positively charged ion (2) or 2-oxo-pyrrolidine positively charged ion (3) is as follows: wherein, and n=1～6, R is C
1～C
6
Wherein: n=1～6, R is C
1～C
6
The described organic or inorganic negatively charged ion of method of the present invention X is fluoroboric acid root, bisulfate ion, tosic acid root, trifluoromethanesulfonic acid root.
Method of the present invention, employed raw material are Tetra hydro Phthalic anhydride, isooctyl alcohol or n-Octanol.
Method of the present invention, when reacting, the mol ratio of Tetra hydro Phthalic anhydride and isooctyl alcohol or n-Octanol is 1: 2 to 1: 10, ionic liquid quality and reactant total mass ratio are 1: 20 to 20: 1.
Method of the present invention realizes as follows:
1. ion liquid typical production is: drip the vitriol oil in ice bath-5 ℃ under 1-methyl-3-(propyl group-3-sulfonic group) imidazole salts magnetic agitation, slowly rise to normal-temperature reaction after dripping off two days later through vacuum-drying 2 hours, the light yellow viscous liquid of gained is 1-methyl-3-(propyl group-3-sulfonic group) imidazole bisulfate ionic liquid.This ion liquid detailed synthetic method see document (Cole A C, Jensen J L, et al.J.Am.Chem.Soc., 2002,124 (21), 5962-5963.).
2. the typical production of bialkyl ortho phthalate (is example with DOP) is: in the there-necked flask of being furnished with magnetic agitation, thermometer, water trap, reflux exchanger, the Tetra hydro Phthalic anhydride, isooctyl alcohol, ionic liquid and the band aqua that add certain proportioning, wherein, Tetra hydro Phthalic anhydride and isooctyl alcohol mol ratio are 1: 2 to 1: 10, and ionic liquid quality and reactant total mass ratio are 1: 20 to 20: 1.Stirring is warming up to temperature of reaction and begins to react timing, and esterification temperature keeps stable in the back flow reaction process, stopped reaction after 1 to 2 hour reaction times, and the ester layer that reaction solution cooling standing demix is told gets product DOP through washing behind the underpressure distillation purifying.
3. the ionic liquid that method of the present invention is used is reusable, ionic liquid multiple canonical process be with last time esterification reaction solution cooling leave standstill, because of thickness very under the ionic liquid low temperature, be bonded on the wall of container, can directly incline very easily the upper strata reaction solution, and lower floor's ionic liquid need not any processing and promptly can be used for next esterification, when the ionic liquid consumption accounts for reaction solution total mass 30%, reuse eight times, transformation efficiency and selectivity are not seen obvious decline.
The present invention compares with traditional acid catalyzed process, is characterized in:
1, have higher esterification ability, and temperature of reaction is low, the time is short, less energy consumption.
2, product bialkyl ortho phthalate and ionic liquid AUTOMATIC ZONING make sepn process more easy.
3, the ionic liquid that reacted promptly can be used for reaction next time without any processing.
Embodiment
Below in conjunction with embodiment method of the present invention being described further, is not limitation of the invention.
Embodiment 1
6g ionic liquid 1-methyl-3-(propyl group-3-sulfonic group) imidazoles fluoroborate, 5.7g Tetra hydro Phthalic anhydride, 10g isooctyl alcohol and an amount of band aqua are put into reaction flask, stir, heating, esterification temperature is 110-125 ℃, reacts 1.5 hours, behind the reaction solution standing demix, incline and the upper strata reaction solution, distillation purifying, Tetra hydro Phthalic anhydride transformation efficiency 98.1%, selectivity 98.6%.
Embodiment 2
2g ionic liquid 1-methyl-3-(propyl group-3-sulfonic group) imidazole bisulfate, 5.7g Tetra hydro Phthalic anhydride, 12.5g n-Octanol and an amount of band aqua are put into reaction flask, stir, heating, esterification temperature is 110-130 ℃, reacts 2 hours, behind the reaction solution standing demix, incline and the upper strata reaction solution, distillation purifying, Tetra hydro Phthalic anhydride transformation efficiency 97.2%, selectivity 98.5%.
Embodiment 3
20g ionic liquid 1-methyl-3-(propyl group-3-sulfonic group) imidazoles tosilate, 5.7g Tetra hydro Phthalic anhydride, 15g isooctyl alcohol and an amount of band aqua are put into reaction flask, stir, heating, esterification temperature is 100-125 ℃, reacts 2 hours, behind the reaction solution standing demix, incline and the upper strata reaction solution, distillation purifying, Tetra hydro Phthalic anhydride transformation efficiency 98.2%, selectivity 99.1%.
Embodiment 4
6g ionic liquid 1-methyl-3-(propyl group-3-sulfonic group) imidazoles fluoroform sulphonate, 5.7g Tetra hydro Phthalic anhydride, 25g n-Octanol and an amount of band aqua are put into reaction flask, stir, heating, esterification temperature is 100-125 ℃, reacts 1 hour, behind the reaction solution standing demix, incline and the upper strata reaction solution, distillation purifying, Tetra hydro Phthalic anhydride transformation efficiency 98.6%, selectivity 99.2%.
Embodiment 5
20g ionic liquid N-(propyl group-3-sulfonic group) pyridine tosilate, 5.7g Tetra hydro Phthalic anhydride, 15g isooctyl alcohol and an amount of band aqua are put into reaction flask, stir, heating, esterification temperature is 110-125 ℃, reacts 1.5 hours, behind the reaction solution standing demix, incline and the upper strata reaction solution, distillation purifying, Tetra hydro Phthalic anhydride transformation efficiency 98.4%, selectivity 98.6%.
Embodiment 6
5g ionic liquid N-(propyl group-3-sulfonic group) pyridine hydrosulfate, 5.7g Tetra hydro Phthalic anhydride, 10g n-Octanol and an amount of band aqua are put into reaction flask, stir, heating, esterification temperature is 110-125 ℃, reacts 1.5 hours, behind the reaction solution standing demix, incline and the upper strata reaction solution, distillation purifying, Tetra hydro Phthalic anhydride transformation efficiency 97.5%, selectivity 97.5%.
Embodiment 7
12g ionic liquid 2-oxo-pyrrolidine tosilate, 5.7g Tetra hydro Phthalic anhydride, 15g isooctyl alcohol and an amount of band aqua are put into reaction flask, stir, heating, esterification temperature is 90-110 ℃, reacts 2 hours, behind the reaction solution standing demix, incline and the upper strata reaction solution, distillation purifying, Tetra hydro Phthalic anhydride transformation efficiency 97.9%, selectivity 98.5%.
Embodiment 8
6g ionic liquid 2-oxo-pyrrolidine hydrosulfate, 5.7g Tetra hydro Phthalic anhydride, 10g n-Octanol and an amount of band aqua are put into reaction flask, stir, heating, esterification temperature is 90-115 ℃, reacts 2 hours, behind the reaction solution standing demix, incline and the upper strata reaction solution, distillation purifying, Tetra hydro Phthalic anhydride transformation efficiency 98.2%, selectivity 98.6%.
Embodiment 9
12g ionic liquid 2-oxo-pyrrolidine fluoroborate, 5.7g Tetra hydro Phthalic anhydride, 15g isooctyl alcohol and an amount of band aqua are put into reaction flask, stir, heating, esterification temperature is 90-110 ℃, reacts 2 hours, behind the reaction solution standing demix, incline and the upper strata reaction solution, distillation purifying, Tetra hydro Phthalic anhydride transformation efficiency 98.5%, selectivity 98.8%.
Claims (5)
1, a kind of esterification process of bialkyl ortho phthalate, the ionic liquid that it is characterized in that constituting with 1,3 dialkylimidazolium positively charged ion of the alkyl pyridine positively charged ion of sulfonic functional or sulfonic functional or 2-oxo-pyrrolidine positively charged ion and organic or inorganic negatively charged ion is as catalyst for reaction and reaction medium; Reaction conditions is normal pressure, temperature of reaction 90-130 ℃, reaction times 1-2h, and catalysis Tetra hydro Phthalic anhydride and isooctyl alcohol or n-Octanol esterification generate bialkyl ortho phthalate.
2, the esterification process of bialkyl ortho phthalate as claimed in claim 1, it is characterized in that described sulfonic functional alkyl pyridine positively charged ion (1), sulfonic functional 1, the general structure of 3-dialkylimidazolium positively charged ion (2), 2 oxo-pyrrolidine positively charged ions (3) is as follows:
Wherein, n=1～6, R is C
1～C
6
3. the esterification process of bialkyl ortho phthalate as claimed in claim 1 is characterized in that described inorganic or organic anion X is fluoroboric acid root, bisulfate ion, tosic acid root, trifluoromethanesulfonic acid root.
4. the esterification process of bialkyl ortho phthalate as claimed in claim 1 is characterized in that described Tetra hydro Phthalic anhydride and isooctyl alcohol or n-Octanol mol ratio are 1: 2 to 1: 10.
5. the esterification process of bialkyl ortho phthalate as claimed in claim 1 is characterized in that described ionic liquid quality and reactant total mass ratio are 1: 20 to 20: 1.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100513394C (en) * | 2007-03-23 | 2009-07-15 | 广东工业大学 | Ketopyrrolidine sulfurate in liquid and its prpearing method |
| CN101823966A (en) * | 2010-05-25 | 2010-09-08 | 江南大学 | Method for synthesizing cyclohexane 1, 2-dibutyl carboxylic acid by using ionic liquid catalysis |
| CN101024613B (en) * | 2007-03-16 | 2010-11-17 | 广东工业大学 | Method for catalyzing alochol acid esterization by sulfonic-acid-radical functionized ion liquid |
| CN101024612B (en) * | 2007-03-16 | 2010-11-17 | 广东工业大学 | Method for catalyzing alcohol acid esterization by acidic ion liquid |
| CN101985423A (en) * | 2009-12-18 | 2011-03-16 | 镇江高鹏药业有限公司 | Method for catalytic synthesis of salicylate alkyl ester by using ionic liquid under microwave promotion |
| CN101348432B (en) * | 2008-08-28 | 2012-03-21 | 四川大学 | Method for preparing halogenated carboxylic ester by catalysis of ion liquid |
| CN102773118A (en) * | 2012-08-14 | 2012-11-14 | 南京大学 | Ion-like liquid composition catalyst and application thereof in organic acid esterification process for reaction-extraction coupling |
| CN103752340A (en) * | 2013-12-30 | 2014-04-30 | 浙江工业大学 | Applications of acidic functionalized ion liquid in esterification reaction |
| CN104084234A (en) * | 2014-07-16 | 2014-10-08 | 沈阳工业大学 | Crosslinked polyethylene pyrrolidone based catalyst and preparation method thereof |
| CN106800669A (en) * | 2017-01-09 | 2017-06-06 | 青州市瑞鑫再生资源科技有限公司 | A kind of method that plasticizer is prepared with PTA residues |
| CN110330428A (en) * | 2019-07-31 | 2019-10-15 | 浙江建业化工股份有限公司 | The method for preparing diisobutyl phthalate |
| CN111302936A (en) * | 2020-03-31 | 2020-06-19 | 辽宁石化职业技术学院 | Preparation method of dibutyl phthalate |
-
2006
- 2006-08-03 CN CN 200610069862 patent/CN1903824A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101024613B (en) * | 2007-03-16 | 2010-11-17 | 广东工业大学 | Method for catalyzing alochol acid esterization by sulfonic-acid-radical functionized ion liquid |
| CN101024612B (en) * | 2007-03-16 | 2010-11-17 | 广东工业大学 | Method for catalyzing alcohol acid esterization by acidic ion liquid |
| CN100513394C (en) * | 2007-03-23 | 2009-07-15 | 广东工业大学 | Ketopyrrolidine sulfurate in liquid and its prpearing method |
| CN101348432B (en) * | 2008-08-28 | 2012-03-21 | 四川大学 | Method for preparing halogenated carboxylic ester by catalysis of ion liquid |
| CN101985423A (en) * | 2009-12-18 | 2011-03-16 | 镇江高鹏药业有限公司 | Method for catalytic synthesis of salicylate alkyl ester by using ionic liquid under microwave promotion |
| CN101823966A (en) * | 2010-05-25 | 2010-09-08 | 江南大学 | Method for synthesizing cyclohexane 1, 2-dibutyl carboxylic acid by using ionic liquid catalysis |
| CN102773118A (en) * | 2012-08-14 | 2012-11-14 | 南京大学 | Ion-like liquid composition catalyst and application thereof in organic acid esterification process for reaction-extraction coupling |
| CN102773118B (en) * | 2012-08-14 | 2015-06-10 | 南京大学 | Ion-like liquid composition catalyst and application thereof in organic acid esterification process for reaction-extraction coupling |
| CN103752340A (en) * | 2013-12-30 | 2014-04-30 | 浙江工业大学 | Applications of acidic functionalized ion liquid in esterification reaction |
| CN104084234A (en) * | 2014-07-16 | 2014-10-08 | 沈阳工业大学 | Crosslinked polyethylene pyrrolidone based catalyst and preparation method thereof |
| CN106800669A (en) * | 2017-01-09 | 2017-06-06 | 青州市瑞鑫再生资源科技有限公司 | A kind of method that plasticizer is prepared with PTA residues |
| CN110330428A (en) * | 2019-07-31 | 2019-10-15 | 浙江建业化工股份有限公司 | The method for preparing diisobutyl phthalate |
| CN110330428B (en) * | 2019-07-31 | 2022-05-03 | 浙江建业化工股份有限公司 | Method for preparing diisobutyl phthalate |
| CN111302936A (en) * | 2020-03-31 | 2020-06-19 | 辽宁石化职业技术学院 | Preparation method of dibutyl phthalate |
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