CN102351709A - Preparation method for synthesis of dibutyl carbonate under catalysis of alkaline ion liquid - Google Patents
Preparation method for synthesis of dibutyl carbonate under catalysis of alkaline ion liquid Download PDFInfo
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- CN102351709A CN102351709A CN2011103129561A CN201110312956A CN102351709A CN 102351709 A CN102351709 A CN 102351709A CN 2011103129561 A CN2011103129561 A CN 2011103129561A CN 201110312956 A CN201110312956 A CN 201110312956A CN 102351709 A CN102351709 A CN 102351709A
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Abstract
The invention discloses a preparation method for synthesis of dibutyl carbonate under catalysis of an alkaline ion liquid. The preparation method comprises the following steps: carrying out ester exchange reaction on n-butanol and dimethyl carbonate in the presence of an alkaline ion liquid catalyst; and then distilling under reduced pressure and collecting colorless liquid of 100-105 DEG C namely dibutyl carbonate, wherein the adopted catalyst is an environmentally-friendly and recyclable alkaline ion liquid 1-butyl-3-methyl imidazole hydroxide. In the preparation method for synthesis of dibutyl carbonate under catalysis of the alkaline ion liquid, the product dibutyl carbonate can be easily separated from the catalyst 1-butyl-3-methyl imidazole hydroxide; operation process is simple, reaction condition is mild, the purity of the product dibutyl carbonate reaches 96-98%, and the yield of the product dibutyl carbonate reaches 50-55%.
Description
Technical field
The invention relates to a kind of preparation method of alkali ion liquid catalytic synthesis of C dibutyl phthalate.
Background technology
Dibutyl carbonate is a kind of organic synthesis intermediate of growing carbochain; Because it has good lubricity, wear resistance, self-cleaning property, erosion resistance, higher thermo-oxidative stability and lower pour point, good biodegradable and has good solubility with hydrocarbon-type oil, is a kind of environment-friendly type lubricating oil base of excellence.It uses day by day extensive in high-end ucon oil market segment, have higher utility.The method of carbonate synthesis dibutylester mainly contains methods such as phosgenation, alcoholysis of urea and transesterify at present.Phosgenation exists shortcomings such as raw material severe toxicity, operational cycle length and by product severe corrosion equipment, just progressively is eliminated.Though alcoholysis of urea does not have above-mentioned shortcoming, because resonance effect, the amido alkoxy in the acid amides substitutes the very difficulty, particularly diamide of carrying out, and only under the reaction conditions of harshness, for example high temperature just can carry out.Ester-interchange method mainly is through methylcarbonate and propyl carbinol transesterify carbonate synthesis dibutylester.This method adopts environmental protection material carbon dimethyl phthalate, and by-product carbinol is the raw material of Synthesis of dimethyl carbonate, can carry out recycle.Therefore this method is considered to a kind of production process route of cleaning, and bright development prospect is arranged.In the operational path of ester-interchange method carbonate synthesis dibutylester, adopt solid basic catalysts such as sodium methylate or aluminum methylate, potassium titanate, zirconium white, Natural manganese dioxide, potassiumiodide to carry out catalysis at the existing methylcarbonate of reporting mostly.But solid catalyst preparation technology is comparatively complicated, and the selectivity of reaction is relatively poor, and very easily by shortcomings such as pollution such as Atmospheric Carbon Dioxide and water, the drawn up industrialization of dibutyl carbonate of these shortcomings is synthesized.
Summary of the invention
The objective of the invention is to provide in order to solve above-mentioned technical problem a kind of preparation method of alkali ion liquid catalytic synthesis of C dibutyl phthalate, employed catalyzer is that alkali ionic liquid is hydroxide 1-butyl-3-methylimidazole salt.This catalyzer has catalytic activity preferably, and reaction conditions is gentle, and said catalyzer is environmental protection, can reuses.
Technical scheme of the present invention
A kind of preparation method of alkali ion liquid catalytic synthesis of C dibutyl phthalate, promptly in inert gas environment, alkali ion liquid is as catalyzer, propyl carbinol and methylcarbonate are carried out transesterification reaction after, and after removing methyl alcohol and catalyzer, collect 100-105
oThe colourless liquid cut of C promptly gets dibutyl carbonate;
The mass ratio of described propyl carbinol and methylcarbonate is a propyl carbinol: methylcarbonate is 8:3～4;
Described alkali ion liquid catalyst hydroxide 1-butyl-3-methylimidazole salt;
Described alkali ion liquid catalyst consumption is that reactant is the 0.5-4% of propyl carbinol and methylcarbonate total mass, preferred 2～3%.
The preparation method of above-mentioned a kind of alkali ion liquid catalytic synthesis of C dibutyl phthalate specifically comprises the following steps:
(1), in the four-hole boiling flask that agitator, thermometer, prolong, constant pressure funnel are housed, after with the air in the inert gas replacement dereaction container, add propyl carbinol and alkali ion liquid catalyst, heat temperature raising is to 80-120
oC slowly at the uniform velocity drips methylcarbonate, carries out transesterification reaction 1-2h;
(2), water trap is inserted in step (1) device; Methyl alcohol and unreacted methylcarbonate that reaction is generated steam, and keep original temperature, proceed transesterification reaction 1-5h; Be cooled to after room temperature, control vacuum tightness 3-10mmHg carry out underpressure distillation 20～30min standing demix;
Above-mentioned transesterification reaction temperature is preferably 100～110 ℃, and the preferred time does;
(3), the supernatant liquid of gained carries out underpressure distillation again after step (2) static layering, vacuum distillation process control vacuum tightness 3-10mmHg, after the time was 30～60min, the colourless liquid cut of collecting 100-105 ℃ was the target product dibutyl carbonate;
The brown viscous liquid of lower floor is an alkali ionic liquid, and recovery can be recycled.
Useful technique effect of the present invention
The preparation method of a kind of alkali ion liquid catalytic synthesis of C dibutyl phthalate of the present invention, because the alkali ion liquid catalyst catalytic performance that adopts is good, Heat stability is good, selectivity is high; And to the basic toxicological harmless effect of environment, belong to green catalyst, product and catalyzer be separate easily relatively, and operating procedure is simple, and catalyzer can reuse repeatedly and obvious reduction does not take place catalytic performance.
In addition; The preparation method of a kind of alkali ion liquid catalytic synthesis of C dibutyl phthalate of the present invention; Through adjusting the propyl carbinol and the proportioning of methylcarbonate, usage quantity and kind, temperature of reaction and the reaction times of alkali ion liquid; Can obtain purity, the higher dibutyl carbonate of yield; The purity of product dibutyl carbonate reaches 96 ~ 99%, and the highest yield can reach 50 ~ 55%.
Description of drawings
Fig. 1 is the mass spectrum of the GC-MS of embodiment 1 dibutyl carbonate;
Fig. 2 is the infrared spectra of embodiment 1 dibutyl carbonate;
Fig. 3 is the nuclear magnetic resonance spectrum of embodiment 1 dibutyl carbonate.
Embodiment
Through embodiment the present invention is further set forth below, but do not limit the present invention.
The present invention judges that the used instrument of generation and the purity thereof of dibutyl carbonate is following:
Gas-matter coupling GC-MS is Aligent 7890A-5975c, and nitrogen is as carrier gas;
The NICOLET 6700 that the infrared appearance of Fourier is produced for THERMO scientific;
The AYANCE III that nuclear magnetic resonance analyser is produced for Bruker company, solvent is CDCl
3
The measuring method of dibutyl carbonate is used for reference document M.A.P.J. Hacking; F.van Rantwijk, R.A.Sheldon. Lipase catalyzed reactions of aliphatic and arylaliphatic carbonic acid esters. Journal of Molecular Catalysis B:Enzymatic 9 (2000) 201-208.
The various raw materials that the present invention is used all be analytical pure, manufacturer is Chemical Reagent Co., Ltd., Sinopharm Group.
A kind of preparation method of alkali ion liquid catalytic synthesis of C dibutyl phthalate specifically comprises the following steps:
Agitator is being housed; Thermometer; Prolong; In the four-hole boiling flask of constant pressure funnel; After with the air in the inert gas replacement dereaction container; The hydroxide 1-butyl-3-Methylimidazole salt catalyst that adds 24g propyl carbinol and reactant total mass 3%; Heat temperature raising to 100 ℃; Slowly at the uniform velocity drip the 9g methylcarbonate; Carrying out inserting behind the transesterification reaction 1h methyl alcohol and the unreacted methylcarbonate that water trap will react generation steams; Keep 100 ℃ and proceed transesterification reaction 3h; Be cooled to room temperature; After control vacuum tightness 3-10mmHg carries out underpressure distillation 20～30min, standing demix;
Supernatant liquid carries out underpressure distillation again, and vacuum distillation process control vacuum tightness 3-10mmHg is after the time is 30～60min; Collect 100-105 ℃ colourless liquid cut; Obtain the thick product dibutyl carbonate of 9.78g, recording purity is 98.51%, and the yield of dibutyl carbonate is 55.4%;
The brown viscous liquid of lower floor is an alkali ionic liquid, i.e. alkali ion liquid hydrogen oxidation 1-butyl-3-methylimidazole salt, and recovery can be recycled.
The mass spectrum of the GC-MS of the dibutyl carbonate of above-mentioned gained is seen Fig. 1, and as can be seen from Figure 1 fragment ion peak has 27,41,57,63,73,118,175.175 with the expection synthetic compound relative molecular weight M+1 conform to, wherein M is a relative molecular weight.Mass to charge ratio m / Z: 29 for the C2H5 +, m / Z: 41 for the C3H5 +, m / Z: 57 for the C4H9 +, m / Z: 63 to?
+3 H, m / Z: 73 is C4H9O +, m / Z: 118 to
+2 H.With the matching degree of the dibutyl carbonate of standard spectrum storehouse wiley7n.l be 95%;
The infrared spectrogram of the dibutyl carbonate of gained is seen Fig. 2, as can be seen from Figure 2 2962cm
-1Be that saturated C-H stretching vibration absorbs; 1746 cm
-1The stretching vibration that is C=O absorbs; 1468cm
-1, 1405cm
-1The flexural vibration that are C-H absorb 1257 cm
-1The stretching vibration that is C-O absorbs;
The nuclear magnetic resonance spectrum of the dibutyl carbonate of gained is seen Fig. 3, as can be seen from Figure 3
1H NMR (500 MHz, CDCl
3) δ 4.12 (t, J=6.6Hz, 4H), 1.63 (m, 4H), 1.40 (m, 4H), 0.92 (t, J=7.3Hz, 6H).
Embodiment 2
A kind of preparation method of alkali ion liquid catalytic synthesis of C dibutyl phthalate specifically comprises the following steps:
Agitator is being housed; Thermometer; Prolong; In the four-hole boiling flask of constant pressure funnel; After with the air in the inert gas replacement dereaction container; The hydroxide 1-butyl-3-Methylimidazole salt catalyst that adds 22.2g propyl carbinol and reactant total mass 2%; Heat temperature raising to 100 ℃; Slowly at the uniform velocity drip the 9g methylcarbonate; Carrying out inserting behind the transesterification reaction 1h methyl alcohol and the unreacted methylcarbonate that water trap will react generation steams; Keep 100 ℃ and proceed transesterification reaction 3h; Be cooled to room temperature; After control vacuum tightness 3-10mmHg carries out underpressure distillation 20～30min, standing demix;
Supernatant liquid carries out underpressure distillation again, and vacuum distillation process control vacuum tightness 3-10mmHg is after the time is 30～60min; Collect 100-105 ℃ colourless liquid cut; Obtain the thick product dibutyl carbonate of 9.27g, recording purity is 96.83%, and the yield of dibutyl carbonate is 52.5%;
The brown viscous liquid of lower floor is an alkali ionic liquid, i.e. alkali ion liquid hydrogen oxidation 1-butyl-3-methylimidazole salt, and recovery can be recycled.
Embodiment 3
A kind of preparation method of alkali ion liquid catalytic synthesis of C dibutyl phthalate specifically comprises the following steps:
Agitator is being housed; Thermometer; Prolong; In the four-hole boiling flask of constant pressure funnel; After with the air in the inert gas replacement dereaction container; The hydroxide 1-butyl-3-Methylimidazole salt catalyst that adds 22.2g propyl carbinol and reactant total mass 3%; Heat temperature raising to 80 ℃; Slowly at the uniform velocity drip the 9g methylcarbonate; Carrying out inserting behind the transesterification reaction 1h methyl alcohol and the unreacted methylcarbonate that water trap will react generation steams; Keep 80 ℃; Proceed transesterification reaction 3h; Be cooled to room temperature; After control vacuum tightness 3-10mmHg carries out underpressure distillation 20～30min, standing demix;
Supernatant liquid carries out underpressure distillation again, and vacuum distillation process control vacuum tightness 3-10mmHg is after the time is 30～60min; Collect 100-105 ℃ colourless liquid cut; Obtain the thick product dibutyl carbonate of 3.86g, recording purity is 97.33%, and the yield of dibutyl carbonate is 21.6%;
The brown viscous liquid of lower floor is an alkali ionic liquid, i.e. alkali ion liquid hydrogen oxidation 1-butyl-3-methylimidazole salt, and recovery can be recycled.
Embodiment 4
A kind of preparation method of alkali ion liquid catalytic synthesis of C dibutyl phthalate specifically comprises the following steps:
Agitator is being housed; Thermometer; Prolong; In the four-hole boiling flask of constant pressure funnel; After with the air in the inert gas replacement dereaction container; The hydroxide 1-butyl-3-Methylimidazole salt catalyst that adds 7.4g propyl carbinol and reactant total mass 3%; Heat temperature raising to 100 ℃; Slowly at the uniform velocity drip the 9g methylcarbonate; Carrying out inserting behind the transesterification reaction 1h methyl alcohol and the unreacted methylcarbonate that water trap will react generation steams; Keep 100 ℃ and proceed transesterification reaction 3h; Be cooled to room temperature; After control vacuum tightness 3-10mmHg carries out underpressure distillation 20～30min, standing demix;
Supernatant liquid carries out underpressure distillation again, and vacuum distillation process control vacuum tightness 3-10mmHg is after the time is 30～60min; Collect 100-105 ℃ colourless liquid cut; Obtain the thick product dibutyl carbonate of 5.55g, recording purity is 97.25%, and the yield of dibutyl carbonate is 31.0%;
The brown viscous liquid of lower floor is an alkali ionic liquid, i.e. alkali ion liquid hydrogen oxidation 1-butyl-3-methylimidazole salt, and recovery can be recycled.
Foregoing only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (6)
1. the preparation method of an alkali ion liquid catalytic synthesis of C dibutyl phthalate; It is characterized in that in inert gas environment; Alkali ion liquid is as catalyzer; After propyl carbinol and methylcarbonate carried out transesterification reaction, underpressure distillation was collected 100-105 ℃ colourless liquid cut and is promptly got dibutyl carbonate;
Described propyl carbinol and methylcarbonate mass ratio are propyl carbinol: methylcarbonate is 8:3～4;
Said catalyzer is hydroxide 1-butyl-3-methylimidazole salt for alkali ion liquid;
The consumption of said alkali ion liquid catalyst is that reactant is the 0.5-4% of propyl carbinol and methylcarbonate total mass.
2. the preparation method of a kind of alkali ion liquid catalytic synthesis of C dibutyl phthalate as claimed in claim 1 is characterized in that described rare gas element is one or more the gas mixture in nitrogen, helium, neon, argon gas, krypton gas, xenon or the radon gas.
3. the preparation method of a kind of alkali ion liquid catalytic synthesis of C dibutyl phthalate as claimed in claim 2, the consumption that it is characterized in that said alkali ion liquid catalyst is that reactant is the 2-3% of propyl carbinol and methylcarbonate total mass.
4. like the preparation method of claim 1,2 or 3 described a kind of alkali ion liquid catalytic synthesis of C dibutyl phthalates, it is characterized in that specifically comprising the following steps:
(1), in the four-hole boiling flask that agitator, thermometer, prolong, constant pressure funnel are housed, after with the air in the inert gas replacement dereaction container, add propyl carbinol and alkali ion liquid catalyst, heat temperature raising is to 80-120
oC slowly at the uniform velocity drips methylcarbonate, carries out transesterification reaction 1-2h;
(2), water trap is inserted in step (1) device, methyl alcohol and unreacted methylcarbonate that reaction is generated steam, and keep 80-120
oC proceeds transesterification reaction 1-5h, is cooled to after room temperature, control vacuum tightness 3-10mmHg carry out underpressure distillation 20～30min standing demix;
(3), the supernatant liquid of gained carries out underpressure distillation again after step (2) static layering, vacuum distillation process control vacuum tightness 3-10mmHg, after the time was 30～60min, the colourless liquid cut of collecting 100-105 ℃ was dibutyl carbonate.
5. the preparation method of a kind of alkali ion liquid catalytic synthesis of C dibutyl phthalate as claimed in claim 4 is characterized in that the brown viscous liquid of lower floor of gained is the recycling of alkali ion liquid after step (2) static layering.
6. the preparation method of a kind of alkali ion liquid catalytic synthesis of C dibutyl phthalate as claimed in claim 4 is characterized in that the temperature of the ester-exchange reaction control reaction described in step (1) and the step (2) is preferably 80-100
oC, total transesterification reaction time is preferably 4h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058873A (en) * | 2013-02-06 | 2013-04-24 | 上海应用技术学院 | Synthesis method of diisooctyl carbonate |
| CN103709032A (en) * | 2013-12-26 | 2014-04-09 | 江西师范大学 | Preparation method for catalytically synthesizing dibutyl carbonate by proline ionic liquid |
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|---|---|---|---|---|
| CN1569811A (en) * | 2004-04-22 | 2005-01-26 | 宁夏大学 | Process for synthesizing dibutyl carbonate |
| CN101531595A (en) * | 2009-04-22 | 2009-09-16 | 江苏工业学院 | Method for synthesizing Guerbet alcoholic carbonic ester |
| CN101735064A (en) * | 2009-12-11 | 2010-06-16 | 大连工业大学 | Method for catalytically synthesizing di-2-ethyhexyl carbonate by alkali ionic liquid |
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2011
- 2011-10-17 CN CN2011103129561A patent/CN102351709A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1569811A (en) * | 2004-04-22 | 2005-01-26 | 宁夏大学 | Process for synthesizing dibutyl carbonate |
| CN101531595A (en) * | 2009-04-22 | 2009-09-16 | 江苏工业学院 | Method for synthesizing Guerbet alcoholic carbonic ester |
| CN101735064A (en) * | 2009-12-11 | 2010-06-16 | 大连工业大学 | Method for catalytically synthesizing di-2-ethyhexyl carbonate by alkali ionic liquid |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058873A (en) * | 2013-02-06 | 2013-04-24 | 上海应用技术学院 | Synthesis method of diisooctyl carbonate |
| CN103709032A (en) * | 2013-12-26 | 2014-04-09 | 江西师范大学 | Preparation method for catalytically synthesizing dibutyl carbonate by proline ionic liquid |
| CN103709032B (en) * | 2013-12-26 | 2015-09-09 | 江西师范大学 | Preparation method for catalytically synthesizing dibutyl carbonate by proline ionic liquid |
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Application publication date: 20120215 |