CN102372635A - Method for preparing diamyl carbonate by catalyzing and synthesizing alkaline ionized liquid - Google Patents
Method for preparing diamyl carbonate by catalyzing and synthesizing alkaline ionized liquid Download PDFInfo
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- CN102372635A CN102372635A CN2011103510252A CN201110351025A CN102372635A CN 102372635 A CN102372635 A CN 102372635A CN 2011103510252 A CN2011103510252 A CN 2011103510252A CN 201110351025 A CN201110351025 A CN 201110351025A CN 102372635 A CN102372635 A CN 102372635A
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Abstract
The invention discloses a method for preparing diamyl carbonate by catalyzing and synthesizing alkaline ionized liquid, which is characterized in that: in an inert gas environment, the alkaline ionized liquid is used as a catalyst, n-amyl alcohol and methyl carbonate have an ester exchange reaction under the temperature of 90 to 130 DEG C so as to remove the methanol and the catalyst, and the colorless liquid of the temperature of 120 to 125 DEG C is collected to be distilled to obtain the diamyl carbonate. The adopted catalyst is the environment-friendly and recyclable alkaline ionized liquid which is 1-butyl-3-methylimidazolium hydroxide. The product and the catalyst of the method are easy to separate, the operation process is simple, the catalyst is environment-friendly and repeatable to use, the reaction condition is moderate, the purity of the product diamyl carbonate reaches 95 to 99 percent, and the yield of the product diamyl carbonate can reach 70 to 75 percent.
Description
Technical field
The invention relates to a kind of preparation method of alkali ion liquid catalytic synthesis of C acid diamyl ester.
Background technology
Diamyl 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 diamyl ester 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 Pentyl alcohol transesterify carbonate synthesis diamyl ester.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.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method of alkali ion liquid catalytic synthesis of C acid diamyl ester, employed catalyzer is hydroxide 1-butyl-3-methylimidazole salt for alkali ion liquid.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 acid diamyl ester; Promptly in inert gas environment, alkali ion liquid is as catalyzer, with Pentyl alcohol and methylcarbonate controlled temperature be 90 ~ 130 ℃ carry out transesterification reaction after; Remove methyl alcohol and catalyzer, collect 120-125
oThe colourless liquid cut of C promptly gets diamyl carbonate;
The mass ratio of described Pentyl alcohol and methylcarbonate is a Pentyl alcohol: methylcarbonate is 8:1～4;
Described alkali ion liquid catalyst is hydroxide 1-butyl-3-methylimidazole salt;
Described alkali ion liquid catalyst consumption is that reactant is the 0.5-4% of Pentyl alcohol and methylcarbonate total mass, preferred 2～3%.
The preparation method of above-mentioned a kind of alkali ion liquid catalytic synthesis of C acid diamyl ester specifically comprises the following steps:
(1), in the four-hole boiling flask that whisking appliance, TM, prolong, constant pressure funnel are housed, after with the air in the inert gas replacement dereaction container, add Pentyl alcohol and alkali ion liquid catalyst, heat temperature raising is to 90-130
oC, the control drop rate is 0.5 ~ 1g/min, is preferably 1g/min and slowly drips methylcarbonate;
(2), treat that step (1) methylcarbonate drips after, water trap is inserted on the four-hole boiling flask of step (1), methyl alcohol and unreacted methylcarbonate that reaction is generated steam, and keep 90-130
oC, reaction 1-4h is cooled to room temperature, control vacuum tightness 3-20mmHg, after being preferably 20mmHg and carrying out underpressure distillation 20～30min, standing demix;
(3), the supernatant liquid after step (2) static layering is carried out underpressure distillation again, vacuum distillation process control vacuum tightness 3-10mmHg is preferably 10mmHg, and the time is collected 120-125 after being 40～60min
oThe colourless liquid cut of C is the title product diamyl carbonate;
The brown viscous liquid of lower floor after step (2) static layering 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 acid diamyl ester of the present invention; Through adjusting the Pentyl alcohol 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 diamyl carbonate of yield; The purity of product diamyl carbonate reaches 96 ~ 99%, and yield reaches 70 ~ 75%.
In addition, the preparation method of a kind of alkali ion liquid catalytic synthesis of C acid diamyl ester 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.
Description of drawings
Fig. 1 is the mass spectrum of the GC-MS of embodiment 1 diamyl carbonate;
Fig. 2 is the ir spectra of embodiment 1 diamyl carbonate;
Fig. 3 is the nuclear magnetic resonance spectrum of embodiment 1 diamyl 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 diamyl 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 NMR is produced for Bruker company, solvent is a deuterochloroform.
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 acid diamyl ester specifically comprises the following steps:
(1), in the 250mL four-hole boiling flask of whisking appliance, TM, prolong, constant pressure funnel is housed; The hydroxide 1-butyl-3-Methylimidazole salt catalyst that adds 35.2g Pentyl alcohol and reactant total mass 2%; Heat temperature raising to 110 ℃, the control drop rate is that 1g/min slowly drips the 9g methylcarbonate;
(2), treat that step (1) methylcarbonate drips after; Water trap is inserted on the four-hole boiling flask of step (1), keep 110 ℃ to steam the methyl alcohol that removes the reaction generation, 3h is after be cooled to room temperature in reaction; After control vacuum tightness 20mmHg carries out underpressure distillation 20min, standing demix;
(3), the supernatant liquid of gained carries out underpressure distillation again after step (2) static layering; Vacuum distillation process control vacuum tightness 10mmHg; After time was 60min, the colourless liquid cut when collecting 120-125 ℃ obtained the thick product diamyl carbonate of 15.62g; Recording purity is 97%, and the yield of diamyl carbonate is 75%;
The brown viscous liquid of lower floor reclaims the catalyzer that obtains can be recycled, i.e. alkali ion liquid hydrogen oxidation 1-butyl-3-methylimidazole salt.
The mass spectrum of the GC-MS of the diamyl carbonate of above-mentioned gained is seen Fig. 1, and as can be seen from Figure 1 fragment ion peak has 29,41,63,71,203.203 conform to the relative molecular weight M+1 of expection synthetic compound diamyl carbonate, and wherein M is a relative molecular weight.Mass-to-charge ratio m/Z:29 is C2H5
+, m/Z:41 is C3H5
+, m/Z:63 does
+ 3H, m/Z:71 are C5H11
+
The infrared spectrogram of the diamyl carbonate of gained is seen Fig. 2, as can be seen from Figure 2 2962cm
-1It is saturated C-H stretching vibration; 1746 cm
-1It is the stretching vibration of C=O; 1473cm
-1, 1400cm
-1The flexural vibration that are C-H absorb 1262 cm
-1The stretching vibration that is C-O absorbs;
The nuclear magnetic resonance spectrum of the diamyl carbonate of gained is seen Fig. 3, as can be seen from Figure 3
1H NMR (500 MHz, CDCl
3) δ=4.10 (t, J=6.7,4H), 1.64 (dd, J=13.5,6.7,4H), 1.33 (dd, J=8.7,5.4,8H), 0.88 (t, J=6.7,6H).
A kind of preparation method of alkali ion liquid catalytic synthesis of C acid diamyl ester specifically comprises the following steps:
(1), in the 250mL four-hole boiling flask of whisking appliance, TM, prolong, constant pressure funnel is housed; The hydroxide 1-butyl-3-Methylimidazole salt catalyst that adds 8.8g Pentyl alcohol and reactant total mass 2%; Heat temperature raising to 110 ℃, the control drop rate is that 1g/min slowly drips the 9g methylcarbonate;
(2), treat that step (1) methylcarbonate drips after; Water trap is inserted on the four-hole boiling flask of step (1), keep 110 ℃ to steam the methyl alcohol that removes the reaction generation, 1h is after be cooled to room temperature in reaction; After control vacuum tightness 20mmHg carries out underpressure distillation 20min, standing demix;
(3), the supernatant liquid of gained carries out underpressure distillation again after step (2) static layering; Vacuum distillation process control vacuum tightness 10mmHg; After time was 60min, the colourless liquid cut when collecting 120-125 ℃ obtained the thick product diamyl carbonate of 7.84g; Recording purity is 97%, and the yield of diamyl carbonate is 40%.
The brown viscous liquid of lower floor reclaims, and the catalyzer that obtains can be recycled is alkali ion liquid hydrogen oxidation 1-butyl-3-methylimidazole salt.
A kind of preparation method of alkali ion liquid catalytic synthesis of C acid diamyl ester specifically comprises the following steps:
(1), in the 250mL four-hole boiling flask of whisking appliance, TM, prolong, constant pressure funnel is housed; The hydroxide 1-butyl-3-Methylimidazole salt catalyst that adds 35.2g Pentyl alcohol and reactant total mass 0.5%; Heat temperature raising to 110 ℃, the control drop rate is that 1g/min slowly drips the 9g methylcarbonate;
(2), treat that step (1) methylcarbonate drips after; Water trap is inserted on the four-hole boiling flask of step (1); Keep 110 ℃ steam removing the methyl alcohol that reaction generates, reaction 1h is after be cooled to after room temperature, control vacuum tightness 20mmHg carry out underpressure distillation 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 10mmHg; After time was 40min, the colourless liquid cut when collecting 120-125 ℃ obtained the thick product diamyl carbonate of 8.0g; Recording purity is 96%, and the yield of diamyl carbonate is 38%;
The brown viscous liquid of lower floor reclaims the catalyzer that obtains can be recycled, i.e. alkali ion liquid hydrogen oxidation 1-butyl-3-methylimidazole salt.
Embodiment 4
A kind of preparation method of alkali ion liquid catalytic synthesis of C acid diamyl ester specifically comprises the following steps:
(1), in the 250mL four-hole boiling flask of whisking appliance, TM, prolong, constant pressure funnel is housed; 1-butyl-3-Methylimidazole the carbonate catalyst that adds 35.2g Pentyl alcohol and reactant total mass 0.5%; Heat temperature raising to 90 ℃, the control drop rate is that 1g/min slowly drips the 9g methylcarbonate;
(2), treat that step (1) methylcarbonate drips after; Water trap is inserted on the four-hole boiling flask of step (1), keep 90 ℃ to steam the methyl alcohol that removes the reaction generation, 4h is after be cooled to room temperature in reaction; After control vacuum tightness 20mmHg carries out underpressure distillation 20min, standing demix;
(3), the supernatant liquid of gained carries out underpressure distillation again after step (2) static layering; Vacuum distillation process control vacuum tightness 10mmHg; After time was 60min, the colourless liquid cut when collecting 120-125 ℃ obtained the thick product diamyl carbonate of 8.54g; Recording purity is 97%, and the yield of diamyl carbonate is 41%;
The brown viscous liquid of lower floor reclaims the catalyzer that obtains can be recycled, i.e. alkali ion liquid 1-butyl-3-Methylimidazole carbonate.
Foregoing is merely 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 (9)
1. the preparation method of alkali ion liquid catalytic synthesis of C acid diamyl ester; It is characterized in that in inert gas environment alkali ion liquid is as catalyzer, with Pentyl alcohol and methylcarbonate controlled temperature be 90 ~ 130 ℃ carry out transesterification reaction after; Remove methyl alcohol and catalyzer, collect 120-125
oThe colourless liquid cut of C promptly gets diamyl carbonate;
Described Pentyl alcohol and methylcarbonate mass ratio are Pentyl alcohol: methylcarbonate is 8:1～4;
Said alkali ion liquid catalyst is hydroxide 1-butyl-3-methylimidazole salt;
The consumption of said alkali ion liquid catalyst is that reactant is the 0.5-4% of Pentyl alcohol and methylcarbonate total mass.
2. the preparation method of a kind of alkali ion liquid catalytic synthesis of C acid diamyl ester 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 acid diamyl ester 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 Pentyl alcohol 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 acid diamyl esters, it is characterized in that specifically comprising the following steps:
(1), in the four-hole boiling flask that whisking appliance, TM, prolong, constant pressure funnel are housed, after with the air in the inert gas replacement dereaction container, add Pentyl alcohol and alkali ion liquid catalyst, heat temperature raising is to 90-130
oC, the control drop rate is that 0.5-1g/min slowly drips methylcarbonate;
(2), treat that step (1) methylcarbonate drips after, water trap is inserted on the four-hole boiling flask of step (1), methyl alcohol and unreacted methylcarbonate that reaction is generated steam, and keep 90-130
oC proceeds transesterification reaction 1-4h, is cooled to after room temperature, control vacuum tightness 3-20mmHg carry out underpressure distillation 20～30min standing demix;
(3), the supernatant liquid after step (2) static layering is carried out underpressure distillation again, vacuum distillation process control vacuum tightness 3-10mmHg, the time is collected 120-125 after being 30～60min
oThe colourless liquid of C is diamyl carbonate.
5. the preparation method of a kind of alkali ion liquid catalytic synthesis of C acid diamyl ester as claimed in claim 4 is characterized in that the methylcarbonate drop rate described in the step (1) preferably is controlled to be 1g/min.
6. the preparation method of a kind of alkali ion liquid catalytic synthesis of C acid diamyl ester as claimed in claim 5 is characterized in that preferably keeping 90 ~ 110 ℃ in the step (2) carries out transesterification reaction.
7. the preparation method of a kind of alkali ion liquid catalytic synthesis of C acid diamyl ester as claimed in claim 6 is characterized in that preferred heat temperature raising to 110 in the step (1)
oC.
8. the preparation method of a kind of alkali ion liquid catalytic synthesis of C acid diamyl ester as claimed in claim 7 is characterized in that the vacuum tightness of underpressure distillation in the step (2) preferably is controlled at 20mmHg.
9. the preparation method of a kind of alkali ion liquid catalytic synthesis of C acid diamyl ester as claimed in claim 8 is characterized in that the vacuum tightness of underpressure distillation in the step (3) preferably is controlled at 10mmHg.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058822A (en) * | 2013-01-16 | 2013-04-24 | 福州大学 | Method for using ionic liquid as catalyst to prepare sec-butyl alcohol |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992018458A1 (en) * | 1991-04-12 | 1992-10-29 | Davy Research And Development Limited | Continuous production process of diarylcarbonates |
| CN101007766A (en) * | 2006-12-29 | 2007-08-01 | 江苏工业学院 | Method for catalytic synthesis of diamyl carbonate and methyl amyl 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 |
-
2011
- 2011-11-09 CN CN2011103510252A patent/CN102372635A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992018458A1 (en) * | 1991-04-12 | 1992-10-29 | Davy Research And Development Limited | Continuous production process of diarylcarbonates |
| CN101007766A (en) * | 2006-12-29 | 2007-08-01 | 江苏工业学院 | Method for catalytic synthesis of diamyl carbonate and methyl amyl 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 |
Non-Patent Citations (1)
| Title |
|---|
| 潘素娟等: "碱性[Bmim]Im 离子液体催化合成DEHC", 《大连工业大学学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058822A (en) * | 2013-01-16 | 2013-04-24 | 福州大学 | Method for using ionic liquid as catalyst to prepare sec-butyl alcohol |
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