CN104744247B - A kind of preparation method of alkyl carbonate - Google Patents
A kind of preparation method of alkyl carbonate Download PDFInfo
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- CN104744247B CN104744247B CN201510111698.9A CN201510111698A CN104744247B CN 104744247 B CN104744247 B CN 104744247B CN 201510111698 A CN201510111698 A CN 201510111698A CN 104744247 B CN104744247 B CN 104744247B
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- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
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Abstract
The preparation method that the invention discloses a kind of alkyl carbonate。This preparation method, comprises the steps: that (1) carbamide generates Polyethylene Glycol two (1,2-carbonic ester) glycerin ether and ammonia with Polyethylene Glycol two glycerin ether through alcoholysis reaction；(2) by Polyethylene Glycol two (1, the 2-carbonic ester) glycerin ether that obtains in step (1) with low carbon fat alcohol through ester exchange, obtain alkyl carbonate and Polyethylene Glycol two glycerin ether。The present invention prepares alkyl carbonate with carbamide and low carbon fat alcohol generation alcoholysis reaction, significantly reduces production cost；With Polyethylene Glycol two glycerin ether for medium, reduce with the energy expenditure in low carbon fat alcohol and urea synthesis process, improve production efficiency；Polyethylene Glycol two glycerin ether and catalyst are all recyclable, recycle；Productivity is high, and cost is low, and energy consumption is low, has broad application prospects。
Description
Technical field
The preparation method that the present invention relates to a kind of alkyl carbonate, is specifically related to a kind of method utilizing Polyethylene Glycol two glycerin ether promotion carbamide to prepare alkyl carbonate with low carbon fat alcohol, belongs to the field of chemical synthesis。
Background technology
Dimethyl carbonate (DMC) is a kind of green solvent nontoxic, biodegradable, may be substituted for part volatile organic matter (VOC), can be used to the precursor as Merlon, the phosgene of severe toxicity, dimethyl sulfate, methylchloroformate can be replaced as methylating and carbonylation agent (Tundo, P.&Selva, M.Thechemistryofdimethylcarbonate.Acc.Chem.Res.2002,35,706)。DMC can also be used with and is used as gasoline additive and improves its octane number, if reducing the production cost of DMC, will obtain and being widely applied in petroleum refining。
Currently, DMC can pass through the production of following several method and obtain: phosgene and methanol reaction, the oxidation carbonylation of methanol and carbon monoxide, oxygen, carbon monoxide reacts with Nitrocarbol., the ester exchange reaction of methanol and cyclic carbonate。But, there is use severe toxicity, corrosivity, explosive substance and relatively costly problem in these methods。
It is all the relatively low bulk chemical of price that carbamide and methanol generation alcoholysis reaction can obtain DMC, carbamide and methanol, therefore, adopts this method production DMC and production cost can be greatly reduced。But, this reaction is the reaction that a thermodynamics is limited, the low conversion rate of reaction。In order to improve productivity, need to constantly discharging the ammonia that reaction produces, and the volatility of methanol and DMC is all significantly high, constantly evaporates at reaction conditions in course of reaction, accordingly, it would be desirable to arrange condensing unit, the energy consumption further resulting in reaction is high。As:
CN01131680.2 discloses a kind of method that carbamide and methanol adopt heterogeneous catalysis Synthesis of dimethyl carbonate, and the method is at temperature 600～1300 DEG C, pressure 10 × 10 by alkali metal, the carbonate of alkaline-earth metal or hydroxide5～1 × 105Calcine 1～10 hour under Pa, air or oxygen atmosphere, obtain catalyst, carbamide and methanol are added in autoclave, and adds catalyst, be warming up to 120～180 DEG C when magnetic agitation, low-temp reaction time 2hr～10hr；Rise to 180～240 DEG C again, pyroreaction time 2hr～20hr；Question response temperature is down to room temperature, separates and prepares product。
CN02156481.7 discloses Synthesis of Dimethyl Carbonate from Urea metal oxide catalyst and preparation method thereof, this catalyst is made up of the 1-3 kind metal-oxide in lithium, magnesium, nickel, zinc, lead, aluminum, ferrum, molybdenum, zirconium, lanthanum, its mixed metal oxide catalyst is based on zinc oxide, and its percentage by weight is 35～95%。When this catalyst is three kinds of mixed-metal oxides, other the two kinds of metal oxide weight percentage ratios beyond zinc oxide are 1:1。Its preparation adopts thermal decomposition method, the sedimentation method and coprecipitation。This catalyst is easily prepared, separation, recovery and regeneration；To Synthesis of Dimethyl Carbonate from Urea, having higher catalysis activity, yield is 49.7%。
Application number be 201310394760.0 patent application disclose one ionic liquid and promote carbamide and methanol-fueled CLC dimethyl carbonate method。First carbamide generate cyclic carbonate ester ionic liquid with the vicinal diamines functional group reactions contained by ionic liquid；Cyclic carbonate ester ionic liquid and methanol react generation dimethyl carbonate and vicinal diamines ionic liquid。This method it makes use of the nonvolatile characteristic of ionic liquid, with in urea reaction, it is possible to remove the ammonia generated in course of reaction easily, make reaction be smoothed out。The method that this invention provides is greatly lowered with the energy expenditure in methanol and urea synthesis process, improves production efficiency and the yield of dimethyl carbonate。But the selling at exorbitant prices of ionic liquid, hinder it and apply on a large scale。
Diethyl carbonate, dipropyl carbonate have the feature of safety, low toxicity, and they are important organic synthesis intermediates, are also used as the electrolyte of solvent and lithium battery。Diethyl carbonate, dipropyl carbonate can be synthesized by the ester exchange of dimethyl carbonate with ethanol, propanol。Therefore it provides the preparation method of the alkyl carbonate of a kind of low cost, low energy consumption and high yield, significant。
Summary of the invention
The preparation method that it is an object of the invention to provide a kind of alkyl carbonate, the method adopts carbamide and low carbon fat alcohol that alkyl carbonate is synthesized, carbamide and low carbon fat alcohol are all the bulk chemical that price is relatively low, production cost can be greatly reduced, with Polyethylene Glycol two glycerin ether for medium, can reduce with the energy expenditure in course of reaction, improve productivity and the production efficiency of alkyl carbonate。
The preparation method of alkyl carbonate provided by the invention, comprises the steps:
(1) under the effect of catalyst, carbamide generates Polyethylene Glycol two (1,2-carbonic ester) glycerin ether and ammonia with Polyethylene Glycol two glycerin ether through alcoholysis reaction；
(2) Polyethylene Glycol two (1, the 2-carbonic ester) glycerin ether obtained in step (1) and low carbon fat alcohol are carried out ester exchange, obtain alkyl carbonate and Polyethylene Glycol two glycerin ether。
Above-mentioned preparation method, in step (1), the structure of described Polyethylene Glycol two glycerin ether is shown below:
In formula I, n >=2。
Above-mentioned preparation method, in step (1), described Polyethylene Glycol two glycerin ether can be prepared via a method which to obtain:
A) under the effect of tetrabutyl ammonium bromide, polyethyleneglycol diglycidylether and carbon dioxide reaction, obtain Polyethylene Glycol two (1,2-carbonic ester) glycerin ether；
The pressure of described carbon dioxide is 2MPa, and the amount of substance of described tetrabutyl ammonium bromide is the 2% of described Polyethylene Glycol two glycerin ether；
The temperature of described reaction is 120 DEG C, and the time is 48h；
B) under the effect of potassium carbonate, Polyethylene Glycol two (1, the 2-carbonic ester) glycerin ether obtained in step (1) reacts with methanol and obtains described Polyethylene Glycol two glycerin ether；
The amount of substance of described potassium carbonate is the 10% of described Polyethylene Glycol two (1,2-carbonic ester) glycerin ether, and the described amount of substance of Polyethylene Glycol two (1,2-carbonic ester) glycerin ether is 1:100 with the ratio of the amount of substance of described methanol；
The temperature of described reaction is 20 DEG C, and the time is 10h。
Above-mentioned preparation method, in step (1), described catalyst can be metal-oxide, metal chloride or metal sulfate, concretely ZnO, ZnCl2、MgO、SnCl2、CaCl2Or ZnSO4；
The mol ratio of described catalyst and described Polyethylene Glycol two glycerin ether can be 0.02～0.4:1, concretely 0.02～0.2:1,0.1～0.4:1,0.02:1,0.1:1,0.2:1 or 0.4:1。
The addition of described catalyst can improve the productivity of Polyethylene Glycol two (1,2-carbonic ester) glycerin ether, reduces the response time, improves production efficiency。
In preparation method of the present invention, owing to Polyethylene Glycol two glycerin ether is non-volatile or volatility is low, in course of reaction, the ammonia that reaction generates can be discharged reaction system, making reaction be smoothed out, be synthesized with methanol with carbamide of the prior art compared with the method for dimethyl carbonate, method provided by the invention avoids in course of reaction also takes reactant low carbon fat alcohol out of while discharging the ammonia produced, decrease the energy expenditure in condensation process, improve production efficiency and yield。
In above-mentioned preparation method, in step (1), the mol ratio of described carbamide and described Polyethylene Glycol two glycerin ether can be 0.6～3.0:1, concretely 0.6:1,1:1,1.5:1,2:1,2.4:1,2.8:1 or 3:1；
The mean molecule quantity of described Polyethylene Glycol two glycerin ether can be 254～2036, concretely 254,298,348,436,562 or 2036。
In above-mentioned preparation method, in step (1), the temperature of described alcoholysis reaction can be 120～180 DEG C, but is not 120 DEG C, concretely 135 DEG C, 140 DEG C, 145 DEG C, 165 DEG C or 180 DEG C, it is preferable that 150～180 DEG C。
The time of described alcoholysis reaction can be 1～15h, concretely 1h, 2h, 4h, 6h, 8h, 10h or 12h, when the response time in step (1) is 1h, described Polyethylene Glycol two (1, 2-carbonic ester) yield of glycerin ether is about 15%, increase along with the response time, described Polyethylene Glycol two (1, 2-carbonic ester) yield of glycerin ether constantly raises, when the response time in step (1) is 6h, described Polyethylene Glycol two (1, 2-carbonic ester) yield of glycerin ether can reach about 70%, when the response time in step (1) is 10h, described Polyethylene Glycol two (1, 2-carbonic ester) yield of glycerin ether (changes rate of charge and can make yield close to 100%) up to 75%, therefore, the response time of alcoholysis reaction described in step (1) is preferably 6～10h, it most preferably is 8～10h。
In above-mentioned preparation method, in step (1), owing to described alcoholysis reaction is the limited reaction of a thermodynamics, the low conversion rate of reaction, taken out of by carbon dioxide gas stream by described ammonia, nitrogen stream is taken out of or pumped, can be greatly enhanced the productivity of this reaction；
The flow velocity of described carbon dioxide gas stream or nitrogen stream can be 1～10mL/min, concretely 5mL/min；
The speed of exhaust of described pump is 10～100L/min, is specially 10L/min, described pump concretely water pump。
Above-mentioned preparation method, in step (2), the mol ratio of described low carbon fat alcohol and described Polyethylene Glycol two glycerin ether can be 100～10:1, concretely 100:1 or 10:1；
Described low carbon fat alcohol is carbon number can be the fatty alcohol of 1～3, concretely methanol, ethanol or normal propyl alcohol。
Above-mentioned preparation method, in step (2), described ester exchange can following 1) or 2) when carries out:
1) temperature can be 120～180 DEG C；
2) under the effect of catalyst, temperature can be 20 DEG C～80 DEG C；
Described catalyst can be potassium carbonate, cesium carbonate or sodium carbonate, and the mol ratio of described catalyst and described Polyethylene Glycol two glycerin ether can be 0.04～0.3:1, concretely 0.04～0.1:1,0.1～0.3:1,0.04:1,0.1:1 or 0.3:1；
Above-mentioned 1) and 2) catalysis process under two kinds of conditions all can improve the yield of alkyl carbonate, improves production efficiency:
Condition 1) in temperature directly can carry out under the reaction temperature in step (1), course of reaction is simple；
Condition 2) in temperature concretely 20 DEG C or 80 DEG C, the mol ratio of described catalyst and described Polyethylene Glycol two glycerin ether can be 0.04～0.3:1, when the mol ratio of described catalyst and described Polyethylene Glycol two glycerin ether is lower than 0.1:1, catalytic effect is poor, directly affect the yield of alkyl carbonate, when the mol ratio of described catalyst with described Polyethylene Glycol two glycerin ether is higher than 0.3:1, increase along with described catalyst amount, it is little that the yield of described alkyl carbonate increases change, when the mol ratio of described catalyst Yu described Polyethylene Glycol two glycerin ether is 0.1～0.3:1, while ensureing that alkyl carbonate has higher productivity, this reaction can ensure have relatively low cost and higher production efficiency。Reaction temperature under this condition is relatively low, and reaction condition is tolerant, the easily controllable operation of course of reaction, and yield is high。
Above-mentioned preparation method, in step (2), the time of described ester exchange can be 0.5～2h, concretely 0.5～1h, 1～2h, 0.5h, 1h or 2h。
Above-mentioned preparation method, in step (2), described alkyl carbonate is any one in dimethyl carbonate, diethyl carbonate and carbonic acid di-n-propyl ester。
Above-mentioned preparation method, after ester exchange described in step (2), the mixture in reaction system includes alkyl carbonate, Polyethylene Glycol two glycerin ether and the boiling point reacted between remaining low-carbon alkyl alcohol and differs greatly, specifically by the mode distilled, the mixture in reaction system can be easily separated, obtain described alkyl carbonate。In process of the present invention, owing to experimental measuring is less, the alkyl carbonate obtained after distillation cannot further be used for detecting analysis, so directly adopting carbon dioxide gas stream the alkyl carbonate prepared and the remaining low carbon fat alcohol of reaction to be taken out of, utilizing gas chromatogram to carry out detection after absorbing with absorbent and analyzing；The flow velocity of described carbon dioxide gas stream can be 1～10mL/min, concretely 5mL/min。
Above-mentioned preparation method, the catalyst in Polyethylene Glycol two glycerin ether of the functionalization generated after ester exchange described in step (2) and reaction system all can directly be reused。
With of the prior art prepare alkyl carbonate with carbamide with fatty alcohol generation alcoholysis reaction compared with, having the advantages that of the inventive method
(1) present invention prepares alkyl carbonate with carbamide and low carbon fat alcohol generation alcoholysis reaction, significantly reduces production cost。
(2) present invention is with Polyethylene Glycol two glycerin ether for medium, reduces with the energy expenditure in low carbon fat alcohol and urea synthesis process, improves production efficiency。
(3) method of the present invention improves the yield of alkyl carbonate。
(4) Polyethylene Glycol two glycerin ether and catalyst are all recyclable, recycle。
(5) the synthetic method productivity of alkyl carbonate provided by the invention is high, and cost is low, and energy consumption is low, has broad application prospects。
Accompanying drawing explanation
Fig. 1 is the nuclear magnetic resonance map of Polyethylene Glycol two glycerin ether 562 in embodiment。
Fig. 2 is the nuclear magnetic resonance map of polyethyleneglycol diglycidylether 526 in embodiment。
Fig. 3 is the nuclear magnetic resonance map of Polyethylene Glycol two (1,2-carbonic ester) glycerin ether 614 in embodiment。
Fig. 4 is the gas chromatography mass spectrometry spectrogram of dimethyl carbonate in embodiment。
Fig. 5 is the gas chromatography mass spectrometry spectrogram of diethyl carbonate in embodiment。
Fig. 6 is the gas chromatography mass spectrometry spectrogram of dipropyl carbonate in embodiment。
Detailed description of the invention
The experimental technique used in following embodiment if no special instructions, is conventional method。
Material used in following embodiment, reagent etc., if no special instructions, all commercially obtain。
Polyethylene Glycol two glycerin ether in following embodiment all can be prepared via a method which to obtain:
(1) by polyethyleneglycol diglycidylether at 120 DEG C, with the carbon dioxide reaction 48 hours of 2MPa under 2% (molal quantity is the 2% of polyethyleneglycol diglycidylether) tetrabutyl ammonium bromide catalysis, obtain Polyethylene Glycol two (1,2-carbonic ester) glycerin ether；
(2) Polyethylene Glycol two (1 obtained in step (1), 2-carbonic ester) glycerin ether and molal quantity be its methanol of 100 times, it is Polyethylene Glycol two (1 at molal quantity, 2-carbonic ester) 10% potassium carbonate catalysis under, at 20 DEG C react 10 hours, after having reacted, be filtered to remove insoluble matter, 60 DEG C of rotations are evaporated off volatile methanol and dimethyl carbonate, 120 DEG C of vacuum dryings 24 hours, obtain Polyethylene Glycol two glycerin ether, and yield is 90%。
The polyethyleneglycol diglycidylether of different molecular weight all can obtain Polyethylene Glycol two glycerin ether of corresponding molecular weight by above-mentioned preparation method。
Gained Polyethylene Glycol two glycerin ether guarantees to obtain corresponding product each through nuclear-magnetism detection, for Polyethylene Glycol two glycerin ether 562, as shown in Figure 1。By with raw material polyethyleneglycol diglycidylether and Polyethylene Glycol two (1,2-carbonic ester) glycerin ether nuclear magnetic spectrogram comparison and with Polyethylene Glycol two (1,2-carbonic ester) mutual conversion between glycerin ether, may determine that products obtained therefrom is Polyethylene Glycol two glycerin ether, the nuclear magnetic resonance map of polyethyleneglycol diglycidylether 526 (1HNMR(CDCl3, 400MHz)) as in figure 2 it is shown, intermediate product Polyethylene Glycol two (1,2-carbonic ester) glycerin ether (614):1HNMR(CDCl3, 400MHz) nuclear magnetic resonance map as it is shown on figure 3, empirical tests structure is correct。
Because the characteristic peak of Polyethylene Glycol two (1,2-carbonic ester) glycerin ether easily distinguishes than the characteristic peak of Polyethylene Glycol two glycerin ether, therefore the nuclear-magnetism modal data of corresponding Polyethylene Glycol provided herein two (1,2-carbonic ester) glycerin ether, result is as follows:
Polyethylene Glycol two (1,2-carbonic ester) glycerin ether 306 (diglycol two glycerin ether correspondence intermediate product):1HNMR(CDCl3,400MHz)δ(ppm),4.8(m,2H),4.5(m,2H),4.4(m,2H),3.6-3.9(m,12H)。
Polyethylene Glycol two (1,2-carbonic ester) glycerin ether 350 (triethylene-glycol two glycerin ether correspondence intermediate product):1HNMR(CDCl3,400MHz)δ(ppm),4.8(m,2H),4.5(m,2H),4.4(m,2H),3.6-3.9(m,16H)。
Polyethylene Glycol two (1,2-carbonic ester) glycerin ether 400:1HNMR(CDCl3, 400MHz) and δ (ppm), 4.8 (m, 2H), 4.5 (m, 2H), 4.4 (m, 2H), 3.6-3.9 (m ,～20H)。
Polyethylene Glycol two (1,2-carbonic ester) glycerin ether 488:1HNMR(CDCl3, 400MHz) and δ (ppm), 4.8 (m, 2H), 4.5 (m, 2H), 4.4 (m, 2H), 3.6-3.9 (m ,～28H)。
Polyethylene Glycol two (1,2-carbonic ester) glycerin ether 614: as shown in Figure 3。
Polyethylene Glycol two (1,2-carbonic ester) glycerin ether 2088:1HNMR(CDCl3, 400MHz) and δ (ppm), 4.8 (m, 2H), 4.5 (m, 2H), 4.4 (m, 2H), 3.6-3.9 (m ,～175H)。
The following content executing Polyethylene Glycol two (1, the 2-carbonic ester) glycerin ether prepared in example obtains each through nuclear-magnetism detection, and condition is1HNMR(CDCl3,400MHz)。
The content of the alkyl carbonate prepared in following embodiment obtains each through gas chromatographic detection, and chromatographic condition is as follows: PEG-20M chromatographic column, long 30m, internal diameter is 0.25mm, use high pure nitrogen as carrier gas, split sampling, flame ionization ditector (FID)；Temperature programming, initial temperature is 60 DEG C, keeps 2min, and 20 DEG C/min is warming up to 230 DEG C；Vaporizer, detector temperature: 265 DEG C；Sample size: 0.4 μ L。
Embodiment 1, dimethyl carbonate preparation
Prepare dimethyl carbonate as follows:
(1) in the reactor of 10 milliliters, (mean molecule quantity is 562 to be sequentially added into 0.562 gram of Polyethylene Glycol two glycerin ether 562, lower same), 0.180 gram of carbamide (mol ratio of carbamide and Polyethylene Glycol two glycerin ether is 3:1), 0.016 gram of ZnO (mol ratio of ZnO and Polyethylene Glycol two glycerin ether is 0.2:1), reactor is put in the heating furnace of 150 DEG C, stirring, CO2Air-flow (5mL/min) purges, and reacts stopping in 10 hours, cooling, obtains Polyethylene Glycol two (1,2-carbonic ester) glycerin ether 614 (mean molecule quantity is 614, lower same)。
The nuclear magnetic resonance map of Polyethylene Glycol two (1, the 2-carbonic ester) glycerin ether 614 prepared in the present embodiment step (1) is as shown in Figure 3。Detected by nuclear-magnetism, obtain the yield of Polyethylene Glycol two (1,2-carbonic ester) glycerin ether close to 100%。
(2) in above-mentioned reactant liquor, add potassium carbonate 0.014 gram (mol ratio of potassium carbonate and Polyethylene Glycol two glycerin ether is 0.1:1), methanol 3.2 grams (mol ratio of methanol and Polyethylene Glycol two glycerin ether is 100:1), stir 1 hour at 20 DEG C, obtain Polyethylene Glycol two glycerin ether 562 and dimethyl carbonate, after having reacted, use CO2Methanol and product dimethyl carbonate are taken out of by air-flow (flow velocity is 5mL/min), with cold DMF for absorbent, with ethylbenzene for interior mark, by gas chromatographic detection, utilizing conventional internal standard method to be calculated, the yield obtaining dimethyl carbonate is 83%。
Adopting low-polarity components, as shown in Figure 4, empirical tests structure is correct for the gas chromatography mass spectrometry spectrogram of dimethyl carbonate。
Reacted Polyethylene Glycol two glycerin ether 562 detects through nuclear-magnetism, and structure is not changed in。
As comparison, removing the catalyst of first step reaction in above-described embodiment, other condition is constant, and the yield obtaining dimethyl carbonate is 2%。
Embodiment 2, dimethyl carbonate preparation
Prepare dimethyl carbonate as follows:
(1) in the reactor of 10 milliliters, (mean molecule quantity is 562 to be sequentially added into 0.562 gram of Polyethylene Glycol two glycerin ether 562, lower same), 0.120 gram of carbamide (mol ratio of carbamide and Polyethylene Glycol two glycerin ether is 2:1), 0.016 gram of ZnO (mol ratio of ZnO and Polyethylene Glycol two glycerin ether is 0.2:1), reactor is put in the heating furnace of 150 DEG C, stirring, CO2Air-flow (5mL/min) purges, and reacts stopping in 2 hours, cooling, obtains Polyethylene Glycol two (1,2-carbonic ester) glycerin ether 614。
(2) in above-mentioned reactant liquor, add potassium carbonate 0.014 gram (mol ratio of potassium carbonate and Polyethylene Glycol two glycerin ether is 0.1:1), methanol 3.2 grams (mol ratio of methanol and Polyethylene Glycol two glycerin ether is 100:1), stir 1 hour at 20 DEG C, obtain Polyethylene Glycol two glycerin ether 562 and dimethyl carbonate, after having reacted, use CO2Methanol and product dimethyl carbonate are taken out of by air-flow (flow is 5mL/min), with cold DMF for absorbent, with ethylbenzene for interior mark, by gas chromatographic detection, utilizing conventional internal standard method to be calculated, the yield obtaining dimethyl carbonate is 24.9%。
Reacted Polyethylene Glycol two glycerin ether 562 detects through nuclear-magnetism, and structure is not changed in。
Embodiment 3, dimethyl carbonate preparation
Adopt and the identical reaction condition of embodiment 2 and detection method, only first step catalyst is changed into 0.034 gram of ZnSO4, all the other are with embodiment 2, and the yield obtaining dimethyl carbonate is 21.7%。
Embodiment 4, dimethyl carbonate preparation
Adopting and the identical reaction condition of embodiment 2 and detection method, first step catalyst only changes into 0.008 gram of MgO, all the other are with embodiment 2, and the yield obtaining dimethyl carbonate is 19.2%。
Embodiment 5, dimethyl carbonate preparation
Adopt and the identical reaction condition of embodiment 2 and detection method, only first step catalyst is changed into 0.026 gram of ZnCl2, all the other are with embodiment 2, and the yield obtaining dimethyl carbonate is 24.1%。
Embodiment 6, dimethyl carbonate preparation
Adopt and the identical reaction condition of embodiment 2 and detection method, only first step catalyst is changed into 0.022 gram of CaCl2, all the other are with embodiment 2, and the yield obtaining dimethyl carbonate is 19.8%。
Embodiment 7, dimethyl carbonate preparation
Adopt and the identical reaction condition of embodiment 2 and detection method, only first step catalyst is changed into 0.002 gram of ZnO (mol ratio of ZnO and Polyethylene Glycol two glycerin ether is 0.02:1), all the other are with embodiment 2, and the yield obtaining dimethyl carbonate is 2.0%。
Embodiment 8, dimethyl carbonate preparation
Adopt and the identical reaction condition of embodiment 1 and detection method, only first step catalyst is changed into 0.008 gram of ZnO (mol ratio of ZnO and Polyethylene Glycol two glycerin ether is 0.1:1), all the other are with embodiment 1, and the yield obtaining dimethyl carbonate is 10.2%。
Embodiment 9, dimethyl carbonate preparation
Adopt and the identical reaction condition of embodiment 2 and detection method, only first step catalyst is changed into 0.032 gram of ZnO (mol ratio of ZnO and Polyethylene Glycol two glycerin ether is 0.4:1), all the other are with embodiment 2, and the yield obtaining dimethyl carbonate is 22.5%。
Embodiment 10, dimethyl carbonate preparation
Adopt and the identical reaction condition of embodiment 2 and detection method, only being changed into 1 hour in the first step response time, all the other are with embodiment 2, obtain Polyethylene Glycol two (1,2-carbonic ester) yield of glycerin ether is 15%, the yield of dimethyl carbonate is 11.0%。
Embodiment 11, dimethyl carbonate preparation
Adopt and the identical reaction condition of embodiment 2 and detection method, only being changed into 4 hours in the first step response time, all the other are with embodiment 2, obtain Polyethylene Glycol two (1,2-carbonic ester) yield of glycerin ether is 60%, the yield of dimethyl carbonate is 49.8%。
Embodiment 12, dimethyl carbonate preparation
Adopt and the identical reaction condition of embodiment 2 and detection method, only being changed into 6 hours in the first step response time, all the other are with embodiment 2, obtain Polyethylene Glycol two (1,2-carbonic ester) yield of glycerin ether is 70%, the yield of dimethyl carbonate is 58.1%。
Embodiment 13, dimethyl carbonate preparation
Adopt and the identical reaction condition of embodiment 2 and detection method, only being changed into 8 hours in the first step response time, all the other are with embodiment 2, obtain Polyethylene Glycol two (1,2-carbonic ester) yield of glycerin ether is 74%, the yield obtaining dimethyl carbonate is 61.4%。
Embodiment 14, dimethyl carbonate preparation
A. adopting and the identical reaction condition of embodiment 2 and detection method, only changed into 10 hours in the first step response time, all the other are with embodiment 2, and step is as follows:
(1) in the reactor of 10 milliliters, (mean molecule quantity is 562 to be sequentially added into 0.562 gram of Polyethylene Glycol two glycerin ether 562, lower same), 0.120 gram of carbamide (mol ratio of carbamide and Polyethylene Glycol two glycerin ether is 2:1), 0.016 gram of ZnO, reactor is put in the heating furnace of 150 DEG C, stirring, CO2Air-flow (5mL/min) purges, and reacts stopping in 10 hours, cooling, obtains Polyethylene Glycol two (1,2-carbonic ester) glycerin ether 614。
Being detected by nuclear-magnetism, the yield obtaining Polyethylene Glycol two (1,2-carbonic ester) glycerin ether is 75%。
(2) in above-mentioned reactant liquor, add potassium carbonate 0.014 gram, methanol 3.2 grams, stir 1 hour at 20 DEG C, obtain Polyethylene Glycol two glycerin ether 562 and dimethyl carbonate, after having reacted, use CO2Methanol and product dimethyl carbonate are taken out of by air-flow (flow is 5mL/min), with cold DMF for absorbent, with ethylbenzene for interior mark, by gas chromatographic detection, utilizing conventional internal standard method to be calculated, the yield obtaining dimethyl carbonate is 62.3%。
Reacted Polyethylene Glycol two glycerin ether 562 detects through nuclear-magnetism, and structure is not changed in。
B. in order to verify the facilitation of Polyethylene Glycol two glycerin ether, will without Polyethylene Glycol two glycerin ether as comparison, step is as follows:
In the capping still of 10 milliliters, add 0.120 gram of carbamide, 0.016 gram of ZnO and methanol 3.2 grams, reactor is put in the heating furnace of 150 DEG C, stirring, react stopping in 10 hours, cooling, centrifugal, with ethylbenzene for interior mark, pass through gas chromatographic detection, utilizing conventional internal standard method to be calculated, the yield obtaining dimethyl carbonate is 2%。
Can being known by above-mentioned comparative experiments, when other reaction condition is identical, adopting Polyethylene Glycol two glycerin ether is after medium, drastically increases the yield of dimethyl carbonate。
Embodiment 15, dimethyl carbonate preparation
Adopting and the identical reaction condition of embodiment 2 and detection method, only changed into 12 hours in the first step response time, all the other are with embodiment 2, and the yield obtaining dimethyl carbonate is 62.3%。
Embodiment 16, dimethyl carbonate preparation
Adopting and the identical reaction condition of embodiment 2 and detection method, only change first step reaction temperature into 120 DEG C, all the other are with embodiment 2, and the yield obtaining dimethyl carbonate is 0%。
Embodiment 17, dimethyl carbonate preparation
Adopting and the identical reaction condition of embodiment 2 and detection method, only change first step reaction temperature into 135 DEG C, all the other are with embodiment 2, and the yield obtaining dimethyl carbonate is 4%。
Embodiment 18, dimethyl carbonate preparation
Adopting and the identical reaction condition of embodiment 2 and detection method, only change first step reaction temperature into 140 DEG C, all the other are with embodiment 2, and the yield obtaining dimethyl carbonate is 5.7%。
Embodiment 19, dimethyl carbonate preparation
Adopting and the identical reaction condition of embodiment 2 and detection method, only change first step reaction temperature into 145 DEG C, all the other are with embodiment 2, and the yield obtaining dimethyl carbonate is 19.1%。
Embodiment 20, dimethyl carbonate preparation
Adopting and the identical reaction condition of embodiment 2 and detection method, only change first step reaction temperature into 165 DEG C, all the other are with embodiment 2, and the yield obtaining dimethyl carbonate is 24.1%。
Embodiment 21, dimethyl carbonate preparation
Adopting and the identical reaction condition of embodiment 2 and detection method, only change first step reaction temperature into 180 DEG C, all the other are with embodiment 2, and the yield obtaining dimethyl carbonate is 23.2%。
Embodiment 22, dimethyl carbonate preparation
Adopt and the identical reaction condition of embodiment 1 and detection method, only the addition of first step carbamide is changed into 0.168g (mol ratio of carbamide and Polyethylene Glycol two glycerin ether is 2.8:1), all the other are with embodiment 1, and the yield obtaining dimethyl carbonate is 79%。
Embodiment 23, dimethyl carbonate preparation
Adopt and the identical reaction condition of embodiment 1 and detection method, only the addition of first step carbamide is changed into 0.144g (mol ratio of carbamide and Polyethylene Glycol two glycerin ether is 2.4:1), all the other are with embodiment 1, and the yield obtaining dimethyl carbonate is 72%。
Embodiment 24, dimethyl carbonate preparation
Adopt and the identical reaction condition of embodiment 1 and detection method, only the addition of first step carbamide is changed into 0.090g (mol ratio of carbamide and Polyethylene Glycol two glycerin ether is 1.5:1), all the other are with embodiment 1, and the yield obtaining dimethyl carbonate is 55%。
Embodiment 25, dimethyl carbonate preparation
Adopt and the identical reaction condition of embodiment 1 and detection method, only the addition of first step carbamide is changed into 0.060g (mol ratio of carbamide and Polyethylene Glycol two glycerin ether is 1:1), all the other are with embodiment 1, and the yield obtaining dimethyl carbonate is 32%。
Embodiment 26, dimethyl carbonate preparation
Adopt and the identical reaction condition of embodiment 1 and detection method, only the addition of second step potassium carbonate is changed into 0.006g (mol ratio of potassium carbonate and Polyethylene Glycol two glycerin ether is 0.04:1), all the other are with embodiment 1, and the yield obtaining dimethyl carbonate is 58%。
Embodiment 27, dimethyl carbonate preparation
Adopt and the identical reaction condition of embodiment 1 and detection method, only the addition of second step potassium carbonate is changed into 0.041g (mol ratio of potassium carbonate and Polyethylene Glycol two glycerin ether is 0.3:1), all the other are with embodiment 1, and the yield obtaining dimethyl carbonate is 83%。
Embodiment 28, dimethyl carbonate preparation
Adopt and the identical reaction condition of embodiment 1 and detection method, only the addition of second step potassium carbonate is changed into 0.006g (mol ratio of potassium carbonate and Polyethylene Glycol two glycerin ether is 0.04:1), simultaneous reactions system maintains 80 DEG C, all the other are with embodiment 1, and the yield obtaining dimethyl carbonate is 77%。
Embodiment 29, dimethyl carbonate preparation
Adopting and the identical reaction condition of embodiment 1 and detection method, only changed into 0.5 hour in the second step response time, all the other are with embodiment 1, and the yield obtaining dimethyl carbonate is 73%。
Embodiment 30, dimethyl carbonate preparation
Adopting and the identical reaction condition of embodiment 1 and detection method, only changed into 2 hours in the second step response time, all the other are with embodiment 1, and the yield obtaining dimethyl carbonate is 83%。
Embodiment 31, dimethyl carbonate preparation
Adopting and the identical reaction condition of embodiment 1 and detection method, the potassium carbonate of second step only changes into 0.033 gram of cesium carbonate, all the other are with embodiment 1, and the yield obtaining dimethyl carbonate is 83%。
Embodiment 32, dimethyl carbonate preparation
Adopting and the identical reaction condition of embodiment 1 and detection method, the potassium carbonate of second step only changes into 0.011 gram of sodium carbonate, all the other are with embodiment 1, and the yield obtaining dimethyl carbonate is 19%。
Embodiment 33, dimethyl carbonate preparation
Adopt and the identical reaction condition of embodiment 1 and detection method, only the addition of second step methanol is changed into 0.320g (mol ratio of methanol and Polyethylene Glycol two glycerin ether is 10:1), all the other are with embodiment 1, and the yield obtaining dimethyl carbonate is 65%。
Embodiment 34, dimethyl carbonate preparation
Adopt and the identical reaction condition of embodiment 1 and detection method, only by CO in the first step2Gas changes N into2, all the other are with embodiment 1, and the yield obtaining dimethyl carbonate is 83%。
Embodiment 35, dimethyl carbonate preparation
Adopt and the identical reaction condition of embodiment 1 and detection method, only the first step will be used CO2Gas purging changes into water pump evacuation (speed of exhaust is 10L/min), and all the other are with embodiment 1, and the yield obtaining dimethyl carbonate is 81%。
Embodiment 36, dimethyl carbonate preparation
Adopt and the identical reaction condition of embodiment 1 and detection method, only Polyethylene Glycol in the first step two glycerin ether 562 is changed into Polyethylene Glycol two glycerin ether 254 (diglycol two glycerin ether) 0.254g, carbamide 0.120g (mol ratio of carbamide and Polyethylene Glycol two glycerin ether is 2:1), all the other are with embodiment 1, and the yield obtaining dimethyl carbonate is 74%。
The structure verification result of intermediate product Polyethylene Glycol two (1, the 2-carbonic ester) glycerin ether 306 prepared in the present embodiment is as follows:1HNMR(CDCl3,400MHz)δ(ppm),4.8(m,2H),4.5(m,2H),4.4(m,2H),3.6-3.9(m,12H)。
Embodiment 37, dimethyl carbonate preparation
Adopt and the identical reaction condition of embodiment 36 and detection method, only Polyethylene Glycol in the first step two glycerin ether 254 is changed into Polyethylene Glycol two glycerin ether 298 (triethylene-glycol two glycerin ether) 0.298g, all the other are with embodiment 36, and the yield obtaining dimethyl carbonate is 71%。
The structure verification result of intermediate product Polyethylene Glycol two (1, the 2-carbonic ester) glycerin ether 350 prepared in the present embodiment is as follows:1HNMR(CDCl3,400MHz)δ(ppm),4.8(m,2H),4.5(m,2H),4.4(m,2H),3.6-3.9(m,16H)。
Embodiment 38, dimethyl carbonate preparation
Adopt and the identical reaction condition of embodiment 36 and detection method, only change Polyethylene Glycol two glycerin ether corresponding for diglycol in the first step two glycerin ether into Polyethylene Glycol two glycerin ether 348, addition is 0.348g, and all the other are with embodiment 36, and the yield obtaining dimethyl carbonate is 70%。
The structure verification result of intermediate product Polyethylene Glycol two (1, the 2-carbonic ester) glycerin ether 400 prepared in the present embodiment is as follows:1HNMR(CDCl3, 400MHz) and δ (ppm), 4.8 (m, 2H), 4.5 (m, 2H), 4.4 (m, 2H), 3.6-3.9 (m ,～20H)。
Embodiment 39, dimethyl carbonate preparation
Adopting and the identical reaction condition of embodiment 36 and detection method, only change Polyethylene Glycol in the first step two glycerin ether 254 into Polyethylene Glycol two glycerin ether 436, addition is 0.436g, and all the other are with embodiment 36, and the yield obtaining dimethyl carbonate is 66%。
The structure verification result of intermediate product Polyethylene Glycol two (1, the 2-carbonic ester) glycerin ether 488 prepared in the present embodiment is as follows:1HNMR(CDCl3, 400MHz) and δ (ppm), 4.8 (m, 2H), 4.5 (m, 2H), 4.4 (m, 2H), 3.6-3.9 (m ,～28H)。
Embodiment 40, dimethyl carbonate preparation
Adopting and the identical reaction condition of embodiment 36 and detection method, only change Polyethylene Glycol in the first step two glycerin ether 254 into Polyethylene Glycol two glycerin ether 2036, addition is 2.036g, and all the other are with embodiment 36, and the yield obtaining dimethyl carbonate is 48%。
Intermediate product Polyethylene Glycol two (1, the 2-carbonic ester) glycerin ether 2088 that the present embodiment prepares:1HNMR(CDCl3, 400MHz) and δ (ppm), 4.8 (m, 2H), 4.5 (m, 2H), 4.4 (m, 2H), 3.6-3.9 (m ,～175H)。
Embodiment 41, diethyl carbonate preparation
Adopting and the identical reaction condition of embodiment 1 and detection method, methanol in second step only changes into ethanol 4.6g, the second step response time is 2 hours, and all the other are with embodiment 1, and the yield obtaining diethyl carbonate is 78%。
Adopting low-polarity components, the gas chromatography mass spectrometry spectrogram of diethyl carbonate is as it is shown in figure 5, empirical tests structure is correct。
Embodiment 42, dipropyl carbonate preparation
Adopting and the identical reaction condition of embodiment 1 and detection method, methanol in second step only changes into normal propyl alcohol 6.01g, the second step response time is 3 hours, and all the other are with embodiment 1, and the yield obtaining dipropyl carbonate is 69%。
Adopting low-polarity components, as shown in Figure 6, empirical tests structure is correct for the gas chromatography mass spectrometry spectrogram of dipropyl carbonate。
Embodiment 43, dimethyl carbonate preparation
Prepare dimethyl carbonate as follows:
(1) in the reactor of 10 milliliters, (mean molecule quantity is 562 to be sequentially added into 0.562 gram of Polyethylene Glycol two glycerin ether 562, lower same), 0.180 gram of carbamide (mol ratio of carbamide and Polyethylene Glycol two glycerin ether is 3:1), 0.016 gram of ZnO, reactor is put in the heating furnace of 150 DEG C, stirring, CO2Air-flow (5mL/min) purges, and reacts stopping in 10 hours, cooling, obtains Polyethylene Glycol two (1,2-carbonic ester) glycerin ether 614。
(2) adding 3.2 grams of methanol in above-mentioned reactant liquor, controlling temperature is 150 DEG C, reacts 2 hours, obtains Polyethylene Glycol two glycerin ether 562 and dimethyl carbonate。After having reacted, use CO2Methanol and product dimethyl carbonate are taken out of by air-flow (flow is 5mL/min), do absorbent with cold DMF, with ethylbenzene for interior mark, by gas chromatographic detection, utilizing conventional internal standard method to be calculated, the yield obtaining dimethyl carbonate is 79%。
Adding 0.180 gram of carbamide in Polyethylene Glycol two glycerin ethers after separation/zinc oxide system, repeat above step twice, the dimethyl carbonate yield of twice is all 77%。
The impact on the yield on alkyl carbonate of each reaction condition is compared for by embodiment 1-42, finally draw: when the mol ratio of carbamide Yu Polyethylene Glycol two glycerin ether is 1-3:1, the response time of step (1) is 4-12h, when reaction temperature is 145-180 DEG C, the yield of alkyl carbonate can reach more than 25%；When the mol ratio of carbamide Yu Polyethylene Glycol two glycerin ether is 2-3:1, the response time of step (1) is 6-12h, when reaction temperature is 150-180 DEG C, the yield of dimethyl carbonate can reach 58%-83%, and the yield of dimethyl carbonate is about 20% in prior art, therefore, the method for the present invention has very high yield。
Claims (10)
1. a preparation method for alkyl carbonate, comprises the steps:
(1) under the effect of catalyst, carbamide generates Polyethylene Glycol two (1,2-carbonic ester) glycerin ether and ammonia with Polyethylene Glycol two glycerin ether through alcoholysis reaction；
Described catalyst is metal-oxide, metal chloride or metal sulfate；
The temperature of described alcoholysis reaction is 120～180 DEG C, but is not 120 DEG C；
(2) Polyethylene Glycol two (1, the 2-carbonic ester) glycerin ether obtained in step (1) and low carbon fat alcohol are carried out ester exchange, obtain alkyl carbonate and Polyethylene Glycol two glycerin ether；
Described low carbon fat alcohol is carbon number is the fatty alcohol of 1～3。
2. preparation method according to claim 1, it is characterised in that: in step (1), the structure of described Polyethylene Glycol two glycerin ether is as follows:
In formula I, n >=2。
3. preparation method according to claim 1 and 2, it is characterised in that: in step (1), the mol ratio of described catalyst and described Polyethylene Glycol two glycerin ether is 0.02～0.4:1；
The mol ratio of described carbamide and described Polyethylene Glycol two glycerin ether is 0.6～3.0:1；
The mean molecule quantity of described Polyethylene Glycol two glycerin ether is 254～2036。
4. preparation method according to claim 1 and 2, it is characterised in that: in step (1), the time of described alcoholysis reaction is 1～15h。
5. preparation method according to claim 1 and 2, it is characterised in that: in step (1), described ammonia is taken out of by carbon dioxide gas stream, nitrogen stream is taken out of or uses pumped；
The flow velocity of described carbon dioxide gas stream or nitrogen stream is 1～10mL/min；
The speed of exhaust of described pump is 10～100L/min。
6. preparation method according to claim 1 and 2, it is characterised in that: in step (2), the mol ratio of described low carbon fat alcohol and described Polyethylene Glycol two glycerin ether is 100～10:1。
7. preparation method according to claim 1 and 2, it is characterised in that: in step (2), described ester exchange is following 1) or 2) when carries out:
1) temperature is 120～180 DEG C；
2) under the effect of catalyst, temperature is 20 DEG C～80 DEG C；
Described catalyst is potassium carbonate, cesium carbonate or sodium carbonate, and the mol ratio of described catalyst and described Polyethylene Glycol two glycerin ether is 0.04～0.3:1。
8. preparation method according to claim 1 and 2, it is characterised in that: in step (2), the time of described ester exchange is 0.5～2h。
9. preparation method according to claim 1 and 2, it is characterised in that: after step (2), obtain described alkyl carbonate by separated。
10. preparation method according to claim 1 and 2, it is characterised in that: described alkyl carbonate is any one in dimethyl carbonate, diethyl carbonate and carbonic acid two normal propyl alcohol ester。
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