WO2006054833A1 - Method for preparing asymmetric linear carbonate - Google Patents
Method for preparing asymmetric linear carbonate Download PDFInfo
- Publication number
- WO2006054833A1 WO2006054833A1 PCT/KR2005/003490 KR2005003490W WO2006054833A1 WO 2006054833 A1 WO2006054833 A1 WO 2006054833A1 KR 2005003490 W KR2005003490 W KR 2005003490W WO 2006054833 A1 WO2006054833 A1 WO 2006054833A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- carbonate
- linear carbonate
- linear
- reaction
- asymmetric linear
- Prior art date
Links
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 27
- -1 ester compound Chemical class 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 9
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 8
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 7
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- 230000002829 reductive effect Effects 0.000 claims description 5
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 claims description 3
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 claims description 3
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 claims description 3
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 claims description 3
- 230000000269 nucleophilic effect Effects 0.000 claims description 3
- 229940093499 ethyl acetate Drugs 0.000 claims description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 2
- 229940011051 isopropyl acetate Drugs 0.000 claims description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 229910052744 lithium Inorganic materials 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 28
- 239000007795 chemical reaction product Substances 0.000 description 20
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 19
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 9
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 8
- 238000009835 boiling Methods 0.000 description 5
- 125000005910 alkyl carbonate group Chemical group 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 125000006165 cyclic alkyl group Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000010923 batch production Methods 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000005323 carbonate salts Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- ODCCJTMPMUFERV-UHFFFAOYSA-N ditert-butyl carbonate Chemical compound CC(C)(C)OC(=O)OC(C)(C)C ODCCJTMPMUFERV-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/08—Purification; Separation; Stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/96—Esters of carbonic or haloformic acids
Definitions
- This invention relates to a method for preparing asymmetric linear carbonate, and more specifically to a method for preparing asymmetric linear carbonate useful as a solvent for lithium secondary battery, etc.
- Asymmetric linear carbonate such as ethyl methyl carbonate (EMC) has been generally used as a solvent (electrolyte) for lithium secondary battery, and the lithium secondary battery using the asymmetric linear carbonate as an electrolyte has improved characteristics including increased energy density, increased discharge capacity, longer life cycle and higher safety performance in comparison with the battery using a con ⁇ ventional electrolyte. Accordingly, the asymmetric linear carbonate is mainly used as an electrolyte for lithium secondary battery.
- a conventional method of preparing the asymmetric linear carbonate is an esterification of alkyl chloroformate with alcohol in the presence of a basic catalyst, but the method has problems in that the esterification reaction is very reactive and requires highly toxic starting materials such as phosgene and bisphenol A.
- a method for preparing asymmetric linear carbonate is disclosed in Japanese Laid - Open patent Publication No. H6- 166660. The method uses a transesterification of symmetric linear carbonate with alkyl alcohol in the presence of a basic catalyst such as metal carbonate salt.
- a method for preparing the asymmetric linear carbonate disclosed in U.S. patent No. 5,962,720 uses a transes ⁇ terification of two different symmetric carbonates in the presence of a basic catalyst such as a Group IA or Group 2 A metal alkoxide salt or a Group IA or Group 2 A metal amide salt which is a nucleophilic or reductive catalyst.
- a basic catalyst such as a Group IA or Group 2 A metal alkoxide salt or a Group IA or Group 2 A metal amide salt which is a nucleophilic or reductive catalyst.
- the method has advantages in that the reaction yield is high, and alcohol is not necessary for the transesterification, but the method has disadvantages in that the basic catalyst should be separated from the reaction product with an Alumina or Silica Gel column, and the trace of water or alcohol in the reactants should be eliminated out before the transesterification reaction to prevent the deterioration of a catalyst activity due to water or alcohol in the reactants.
- a method disclosed in Japanese Laid-Out Patent publication Nos. 2000-344715 and 2000-344718 produces the asymmetric linear carbonate in the presence of water or alcohol, by using the oxides of rare earth metals of a Group 3B.
- the method has the problems in that the reaction is carried out at high pressure of 5 to 10 atm, and for long time interval of 200 hours or more. Disclosure of Invention
- the present invention provides the method for preparing asymmetric linear carbonate, which comprises the steps of: carrying out a transesterification of symmetric linear carbonate with linear ester compound in the presence of a basic catalyst; and separating the asymmetric linear carbonate from the transesterification product.
- the preferable ester compound includes acetate compound
- the preferable basic catalyst includes lithium methoxide, lithium ethoxide, sodium methoxide, lithium amide, calcium hydride and the mixtures thereof.
- R , R , and R can be independently a linear alkyl group, a branched alkyl group, or a cyclic alkyl group.
- R and R are different from each other and independently a Cl-ClO linear alkyl group, a C3-C10 branched alkyl group, or a C5-C10 cyclic alkyl group, and R is preferably a methyl group or an ethyl group.
- Cl-ClO represents the number of carbon atoms is 1 to 10.
- the symmetric linear carbonate can be a linear alkyl carbonate, a branched alkyl carbonate, or a cyclic alkyl carbonate, and preferably can be a Cl-ClO linear alkyl carbonate, a C3-C10 branched alkyl carbonate, or a C5-C10 cyclic alkyl carbonate.
- the symmetric linear carbonate may include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, di-n-butyl carbonate, and di-t-butyl carbonate having C1-C4 linear alkyl groups.
- the linear ester compound can be represented by formula RCOOR , wherein R and R are independently an organic group such as a linear alkyl group, a branched alkyl group, or a cyclic alkyl group.
- R is a methyl group or an ethyl group
- R is a Cl-ClO linear alkyl group, a C3-C10 branched alkyl group, or a C5-C10 cyclic alkyl group.
- the preferable linear ester compound is acetate compound
- the exemplary acetate compound includes methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, n-butyl acetate, t-butyl acetate, the mixtures thereof, and so on.
- the symmetric linear carbonate and the linear ester compound are used in the molar ratio of 1: 10 to 10: 1, and more preferably in the molar ratio of 1: 9 to 9: 1, and most preferably in the molar ratio of 1: 1.5 to 1: 4 to maximize the reaction yield. If the amounts of the symmetric linear carbonate and the linear ester compound are beyond the above mentioned range, the reaction yield of the final product, namely asymmetric linear carbonate decreases.
- the basic catalyst for the transesterification reaction may include nucleophilic or reductive metal salt.
- the preferable basic catalyst includes alkoxide salt of a group IA or a group 2A metal, amide salt of a group IA or a group 2A metal, metal hydride, more preferably hydride of a group IA or a group 2A metal, and the mixtures thereof.
- Examples of the basic catalyst include lithium methoxide(LiOCH ), lithium ethoxide(LiOC H ), sodium methoxide(NaOCH ), lithium amide(LiNH ), calcium hydride(CaH ) and so on.
- the preferable amount of the catalyst in the present invention is 0.01 to 10 weight% with respect to the total amount of the symmetric linear carbonate and the linear ester compound, and more preferably 0.1 to 5 weight%. If the amount of the catalyst is less than 0.01 weight% with respect to the total amount of the symmetric linear carbonate and the linear ester compound, the reaction rate decreases. If the amount of the catalyst is more than 10 weight% with respect to the total amount of the symmetric linear carbonate and the linear ester compound, it is eco ⁇ nomically unfavorable without additional advantages.
- the transesterification reaction can be carried out in a conventional reactor by a conventional batch process or continuous process.
- the preferable transesterification reaction temperature is 50 0 C to 250 0 C.
- the preferable reaction temperature is 70 0 C to 120 0 C. If the reaction temperature is less than 50 0 C, the productivity of the reaction decreases because of the slowdown of reaction rate. If the reaction temperature is more than 250 0 C, the reactants may be decomposed, and various byproducts can be produced.
- the pressure of the transesterification reaction can be widely varied without limitation, but the transesterification reaction can be preferably carried out in atmospheric pressure.
- the reaction time of the transesterification reaction can also be widely varied without limitation.
- the transesterification reaction can be carried out for 0.1 hour to 10 hour, and more preferably for 0.5 hour to 4 hour.
- the transesterification reaction can be carried out until the composition of reaction product is not changed.
- the variation in the composition of reaction product can be determined by sampling the reaction product periodically during the reaction, and by analyzing the sampled reaction product with a gas chromatography.
- the asymmetric linear carbonate is separated from the transesterification product.
- the separation of the asymmetric linear carbonate can be carried out by using a conventional distillation process at atmospheric or reduced pressure.
- the reaction product is distillated at atmospheric or reduced pressure, compounds in the reaction product are successively distilled according to their boiling points.
- the reaction product is successively distilled in order of methyl acetate (boiling point: 58°C), ethyl acetate (boiling point: 77°C) dimethyl carbonate (boiling point: 90 0 C), ethyl methyl carbonate, and diethyl carbonate (boiling point: 127°C).
- methyl acetate boiling point: 58°C
- ethyl acetate 77°C
- dimethyl carbonate boiling point: 90 0 C
- ethyl methyl carbonate ethyl methyl carbonate
- diethyl carbonate diethyl carbonate
- the reaction product was analyzed with a gas chromatography.
- the gas chromatography analysis indicated that methyl acetate(MA) and ethyl methyl carbonate(EMC) were newly generated, and the molar ratio of methyl acetate(MA): ethyl acetate(EA) was determined to be 1 : 1, and the molar ratio of dimethyl carbonate(DMC): ethyl methyl carbonate(EMC): diethyl carbonate(DEC) was determined to be 1 : 2 : 1, and the reaction yield of ethyl methyl carbonate(EMC) was 50% with respect to dimethyl carbonate(DMC).
- the reaction product was distilled at atmospheric pressure in a distillation tower having the number of theoretical plates of 50 and reflux ratio of more than 5 to produce ethyl methyl carbonate
- the reaction product was distilled at atmospheric pressure in a dis ⁇ tillation tower having the number of theoretical plates of 50 and reflux ratio of more than 5 to produce ethyl methyl carbonate having the purity of 99% (Distillation yield: 81%).
- the method for preparing asymmetric linear carbonate according to the present invention can prevent the deterioration of the catalyst activity, and accordingly can produce the asymmetric linear carbonate with high yield in a short time.
- byproducts are not produced, and the asymmetric linear carbonate and a catalyst can be easily separated, which results in the production of the asymmetric linear carbonate of high purity.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A method for preparing asymmetric linear carbonate useful as an electrolyte for lithium secondary battery is disclosed. The method comprises the steps of: carrying out transesterification of symmetric linear carbonate with linear ester compound in the presence of a basic catalyst; and separating asymmetric linear carbonate from the transesterification product. Preferably, the linear ester compound is acetate compound.
Description
Description
METHOD FOR PREPARING ASYMMETRIC LINEAR
CARBONATE
Technical Field
[1] This invention relates to a method for preparing asymmetric linear carbonate, and more specifically to a method for preparing asymmetric linear carbonate useful as a solvent for lithium secondary battery, etc.
Background Art
[2] Asymmetric linear carbonate such as ethyl methyl carbonate (EMC) has been generally used as a solvent (electrolyte) for lithium secondary battery, and the lithium secondary battery using the asymmetric linear carbonate as an electrolyte has improved characteristics including increased energy density, increased discharge capacity, longer life cycle and higher safety performance in comparison with the battery using a con¬ ventional electrolyte. Accordingly, the asymmetric linear carbonate is mainly used as an electrolyte for lithium secondary battery. A conventional method of preparing the asymmetric linear carbonate is an esterification of alkyl chloroformate with alcohol in the presence of a basic catalyst, but the method has problems in that the esterification reaction is very reactive and requires highly toxic starting materials such as phosgene and bisphenol A. As a method to complement these problems, a method for preparing asymmetric linear carbonate is disclosed in Japanese Laid - Open patent Publication No. H6- 166660. The method uses a transesterification of symmetric linear carbonate with alkyl alcohol in the presence of a basic catalyst such as metal carbonate salt. However, the method has problems in that the catalyst activity and the reaction yield are low, and the method requires separation and purification process of the final target compound, for example, ethyl methyl carbonate from the reaction product including three linear carbonate compounds and two alcohol compounds. A method for preparing the asymmetric linear carbonate disclosed in U.S. patent No. 5,962,720 uses a transes¬ terification of two different symmetric carbonates in the presence of a basic catalyst such as a Group IA or Group 2 A metal alkoxide salt or a Group IA or Group 2 A metal amide salt which is a nucleophilic or reductive catalyst. The method has advantages in that the reaction yield is high, and alcohol is not necessary for the transesterification, but the method has disadvantages in that the basic catalyst should be separated from the reaction product with an Alumina or Silica Gel column, and the trace of water or alcohol in the reactants should be eliminated out before the transesterification reaction to prevent the deterioration of a catalyst activity due to water or alcohol in the reactants. A method disclosed in Japanese Laid-Out Patent publication Nos.
2000-344715 and 2000-344718 produces the asymmetric linear carbonate in the presence of water or alcohol, by using the oxides of rare earth metals of a Group 3B. However, the method has the problems in that the reaction is carried out at high pressure of 5 to 10 atm, and for long time interval of 200 hours or more. Disclosure of Invention
Technical Problem
[3] Therefore, it is an object of the present invention to provide a method for preparing asymmetric linear carbonate, in which a catalyst activity is not deteriorated, and ac¬ cordingly the asymmetric linear carbonate can be produced with high yield in a short time.
[4] It is other object of the present invention to provide a method for preparing asymmetric linear carbonate of high purity, in which byproducts are not produced, and the asymmetric linear carbonate and a catalyst can be easily separated. Technical Solution
[5] To accomplish these and other objects, the present invention provides the method for preparing asymmetric linear carbonate, which comprises the steps of: carrying out a transesterification of symmetric linear carbonate with linear ester compound in the presence of a basic catalyst; and separating the asymmetric linear carbonate from the transesterification product. Wherein, the preferable ester compound includes acetate compound, and the preferable basic catalyst includes lithium methoxide, lithium ethoxide, sodium methoxide, lithium amide, calcium hydride and the mixtures thereof. Mode for the Invention
[6] A more complete appreciation of the invention, and many of the attendant advantages thereof, will be better appreciated by reference to the following detailed de¬ scription.
[7] In order to prepare the asymmetric linear carbonate according to the present invention, a transesterification of symmetric linear carbonate with linear ester compound is carried out according to the following Reaction 1 in the presence of a basic catalyst.
[8] <Reaction 1>
[9]
[10]
[11] In Reaction 1, R , R , and R can be independently a linear alkyl group, a branched alkyl group, or a cyclic alkyl group. Preferably, R and R are different from each other
and independently a Cl-ClO linear alkyl group, a C3-C10 branched alkyl group, or a C5-C10 cyclic alkyl group, and R is preferably a methyl group or an ethyl group. ( Cl-ClO represents the number of carbon atoms is 1 to 10.)
[12] The symmetric linear carbonate can be a linear alkyl carbonate, a branched alkyl carbonate, or a cyclic alkyl carbonate, and preferably can be a Cl-ClO linear alkyl carbonate, a C3-C10 branched alkyl carbonate, or a C5-C10 cyclic alkyl carbonate. For example, the symmetric linear carbonate may include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, di-n-butyl carbonate, and di-t-butyl carbonate having C1-C4 linear alkyl groups. The linear ester compound can be represented by formula RCOOR , wherein R and R are independently an organic group such as a linear alkyl group, a branched alkyl group, or a cyclic alkyl group. Preferably, R is a methyl group or an ethyl group, and R is a Cl-ClO linear alkyl group, a C3-C10 branched alkyl group, or a C5-C10 cyclic alkyl group. The preferable linear ester compound is acetate compound, and the exemplary acetate compound includes methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, n-butyl acetate, t-butyl acetate, the mixtures thereof, and so on. Preferably, the symmetric linear carbonate and the linear ester compound (symmetric linear carbonate : linear ester compound) are used in the molar ratio of 1: 10 to 10: 1, and more preferably in the molar ratio of 1: 9 to 9: 1, and most preferably in the molar ratio of 1: 1.5 to 1: 4 to maximize the reaction yield. If the amounts of the symmetric linear carbonate and the linear ester compound are beyond the above mentioned range, the reaction yield of the final product, namely asymmetric linear carbonate decreases.
[13]
[14] The basic catalyst for the transesterification reaction may include nucleophilic or reductive metal salt. The preferable basic catalyst includes alkoxide salt of a group IA or a group 2A metal, amide salt of a group IA or a group 2A metal, metal hydride, more preferably hydride of a group IA or a group 2A metal, and the mixtures thereof. Examples of the basic catalyst include lithium methoxide(LiOCH ), lithium ethoxide(LiOC H ), sodium methoxide(NaOCH ), lithium amide(LiNH ), calcium hydride(CaH ) and so on. The preferable amount of the catalyst in the present invention is 0.01 to 10 weight% with respect to the total amount of the symmetric linear carbonate and the linear ester compound, and more preferably 0.1 to 5 weight%. If the amount of the catalyst is less than 0.01 weight% with respect to the total amount of the symmetric linear carbonate and the linear ester compound, the reaction rate decreases. If the amount of the catalyst is more than 10 weight% with respect to the total amount of the symmetric linear carbonate and the linear ester compound, it is eco¬ nomically unfavorable without additional advantages.
[15]
[16] The transesterification reaction can be carried out in a conventional reactor by a conventional batch process or continuous process. The preferable transesterification reaction temperature is 500C to 2500C. When the transesterification reaction is carried out by a batch process, the preferable reaction temperature is 700C to 1200C. If the reaction temperature is less than 500C, the productivity of the reaction decreases because of the slowdown of reaction rate. If the reaction temperature is more than 2500C, the reactants may be decomposed, and various byproducts can be produced. The pressure of the transesterification reaction can be widely varied without limitation, but the transesterification reaction can be preferably carried out in atmospheric pressure. The reaction time of the transesterification reaction can also be widely varied without limitation. Preferably, the transesterification reaction can be carried out for 0.1 hour to 10 hour, and more preferably for 0.5 hour to 4 hour. The transesterification reaction can be carried out until the composition of reaction product is not changed. The variation in the composition of reaction product can be determined by sampling the reaction product periodically during the reaction, and by analyzing the sampled reaction product with a gas chromatography.
[17]
[18] After the transesterification reaction, the asymmetric linear carbonate is separated from the transesterification product. The separation of the asymmetric linear carbonate can be carried out by using a conventional distillation process at atmospheric or reduced pressure. When the reaction product is distillated at atmospheric or reduced pressure, compounds in the reaction product are successively distilled according to their boiling points. For example, after the transesterification of dimethyl carbonate with ethyl acetate, the reaction product is successively distilled in order of methyl acetate (boiling point: 58°C), ethyl acetate (boiling point: 77°C) dimethyl carbonate (boiling point: 900C), ethyl methyl carbonate, and diethyl carbonate (boiling point: 127°C). The separated symmetric linear carbonate and linear ester compound can be recovered and reused.
[19]
[20] Hereinafter, the preferable examples are provided for better understanding of the present invention. However, the present invention is not limited to the following examples.
[21]
[22] [Example 1]
[23] 1.3 mole ( 117g) of dimethyl carbonate(DMC), 2.6 mole (229g) of ethyl acetate(EA), and 1.35g (0.1 weight%) of LiOCH as a catalyst were added to a 500 ml reaction flask equipped with a condenser and containing a magnetic stirring bar. The mixtures were stirred while being heated to 78°C for carrying out the transesterification
reaction. The vapor generated during the reaction was sent to the condenser, condensed in the condenser, and was refluxed to the reactor. The reaction product was sampled periodically, and the composition of the reaction product was analyzed with a gas chro¬ matography. After 3 hours, from the moment at which the temperature of the reactor reached to 780C, the composition of the reaction product was not changed any more, and the reaction was completed. After completion of the reaction, the reaction product was analyzed with a gas chromatography. The gas chromatography analysis indicated that methyl acetate(MA) and ethyl methyl carbonate(EMC) were newly generated, and the molar ratio of methyl acetate(MA): ethyl acetate(EA) was determined to be 1 : 1, and the molar ratio of dimethyl carbonate(DMC): ethyl methyl carbonate(EMC): diethyl carbonate(DEC) was determined to be 1 : 2 : 1, and the reaction yield of ethyl methyl carbonate(EMC) was 50% with respect to dimethyl carbonate(DMC). Next, the reaction product was distilled at atmospheric pressure in a distillation tower having the number of theoretical plates of 50 and reflux ratio of more than 5 to produce ethyl methyl carbonate having the purity of 99% (Distillation yield: 80%).
[24]
[25] [Example 2]
[26] Except for using 0.5 weight% (1.73g) of LiNH instead of 0. lweight% of LiNH as the catalyst, and carrying out the reaction for 4 hours, the asymmetric linear carbonate was prepared in the same manner as described in Example 1. After completion of the reaction, the reaction product was analyzed with a gas chromatography. The gas chro¬ matography analysis indicated that the molar ratio of methyl acetate: ethyl acetate was determined to be 1 : 1, and the molar ratio of dimethyl carbonate: ethyl methyl carbonate: diethyl carbonate was determined to be 1 : 2 : 1, and the reaction yield of ethyl methyl carbonate was 50% with respect to dimethyl carbonate. Next, the reaction product was distilled at atmospheric pressure in a distillation tower having the number of theoretical plates of 50 and reflux ratio of more than 5 to produce ethyl methyl carbonate having the purity of 99% (Distillation yield: 78%).
[27]
[28] [Example 3]
[29] Except for using 1.3 mole (153g) of diethyl carbonate(DEC) and 2.6 mole (192.4g) of methyl acetate(MA) instead of 1.3 mole of dimethyl carbonate and 2.6 mole of ethyl acetate, the asymmetric linear carbonate was prepared in the same manner as described in Example 1. After completion of the reaction, the reaction product was analyzed with a gas chromatography. The gas chromatography analysis indicated that the molar ratio of ethyl acetate: methyl acetate was determined to be 1:1, and the molar ratio of diethyl carbonate: ethyl methyl carbonate: dimethyl carbonate was determined to be 1 : 2 : 1, and the reaction yield of ethyl methyl carbonate was 50% with respect to diethyl
carbonate. Next, the reaction product was distilled at atmospheric pressure in a dis¬ tillation tower having the number of theoretical plates of 50 and reflux ratio of more than 5 to produce ethyl methyl carbonate having the purity of 99% (Distillation yield: 81%).
[30]
[31] [Comparative Example 1]
[32] Except for using 2.5mole (115g) of ethanol instead of 2.6 mole of ethyl acetate, and carrying out the reaction for 4 hours, the asymmetric linear carbonate was prepared in the same manner as described in Example 1. After completion of the reaction, the reaction product was analyzed with a gas chromatography. The gas chromatography analysis indicated that the reaction product included 4.6 weight% of unreacted ethanol, 9.4 weight% of methanol (byproduct), and the molar ratio of dimethyl carbonate: ethyl methyl carbonate: diethyl carbonate was determined to be 1: 1.6: 1, and the reaction yield of ethyl methyl carbonate was 44% with respect to dimethyl carbonate.
[33]
[34] As described above, the method for preparing asymmetric linear carbonate according to the present invention can prevent the deterioration of the catalyst activity, and accordingly can produce the asymmetric linear carbonate with high yield in a short time. In the present invention, byproducts are not produced, and the asymmetric linear carbonate and a catalyst can be easily separated, which results in the production of the asymmetric linear carbonate of high purity.
[35]
[36] While this invention has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims
[1] A method for preparing asymmetric linear carbonate comprising the steps of: carrying out a transesterification of symmetric linear carbonate with linear ester compound in the presence of a basic catalyst; and separating the asymmetric linear carbonate from the transesterification product.
[2] The method for preparing asymmetric linear carbonate of claim 1, wherein the linear ester compound is acetate compound.
[3] The method for preparing asymmetric linear carbonate of claim 1, wherein the linear ester compound is selected from the group consisting of methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, n-butyl acetate, and t-butyl acetate.
[4] The method for preparing asymmetric linear carbonate of claim 1, wherein the basic catalyst is nucleophilic or reductive metal salt.
[5] The method for preparing asymmetric linear carbonate of claim 1, wherein the basic catalyst is selected from the group consisting of lithium methoxide, lithium ethoxide, sodium methoxide, lithium amide, calcium hydride and the mixtures thereof, and the amount of the basic catalyst is 0.01 to 10 weight% with respect to the total amount of the asymmetric linear carbonate and the linear ester compound.
[6] The method for preparing asymmetric linear carbonate of claim 1, wherein the step of separating the asymmetric linear carbonate is carried out by a distillation of the transesterification product.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2004-0093601 | 2004-11-16 | ||
| KR1020040093601A KR20060054533A (en) | 2004-11-16 | 2004-11-16 | Method for preparing unsymmetric linear carbonate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2006054833A1 true WO2006054833A1 (en) | 2006-05-26 |
Family
ID=36407353
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/KR2005/003490 WO2006054833A1 (en) | 2004-11-16 | 2005-10-19 | Method for preparing asymmetric linear carbonate |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR20060054533A (en) |
| TW (1) | TW200633973A (en) |
| WO (1) | WO2006054833A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172519A (en) * | 2011-12-23 | 2013-06-26 | 中国科学院兰州化学物理研究所 | Synthetic method of methyl ethyl carbonate |
| EP3363779A4 (en) * | 2015-11-24 | 2019-06-19 | Daikin Industries, Ltd. | Production method of asymmetric chain carbonate |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102644180B1 (en) * | 2020-11-26 | 2024-03-05 | 롯데케미칼 주식회사 | Preparation method of linear carbonates using a catalyst with excellent solubility |
| KR102644183B1 (en) * | 2020-11-27 | 2024-03-05 | 롯데케미칼 주식회사 | Method for preparation of different kind of linear carbonates by using acidic ion exchange resin |
| WO2023096301A1 (en) * | 2021-11-23 | 2023-06-01 | 주식회사 엘지화학 | Asymmetric linear carbonate and method for preparing asymmetric linear carbonate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0710811A (en) * | 1993-06-24 | 1995-01-13 | Mitsubishi Chem Corp | Production of dialkyl carbonate |
| US5760273A (en) * | 1995-10-25 | 1998-06-02 | Mitsubishi Chemical Corporation | Process for producing unsymmetrical chain carbonic acid ester |
| US5962720A (en) * | 1997-05-29 | 1999-10-05 | Wilson Greatbatch Ltd. | Method of synthesizing unsymmetric organic carbonates and preparing nonaqueous electrolytes for alkali ion electrochemical cells |
| KR20000055022A (en) * | 1999-02-02 | 2000-09-05 | 유현식 | The preparation of non-symmetric dialkylated carbonates |
-
2004
- 2004-11-16 KR KR1020040093601A patent/KR20060054533A/en not_active Application Discontinuation
-
2005
- 2005-10-19 WO PCT/KR2005/003490 patent/WO2006054833A1/en active Application Filing
- 2005-11-04 TW TW094138816A patent/TW200633973A/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0710811A (en) * | 1993-06-24 | 1995-01-13 | Mitsubishi Chem Corp | Production of dialkyl carbonate |
| US5760273A (en) * | 1995-10-25 | 1998-06-02 | Mitsubishi Chemical Corporation | Process for producing unsymmetrical chain carbonic acid ester |
| US5962720A (en) * | 1997-05-29 | 1999-10-05 | Wilson Greatbatch Ltd. | Method of synthesizing unsymmetric organic carbonates and preparing nonaqueous electrolytes for alkali ion electrochemical cells |
| KR20000055022A (en) * | 1999-02-02 | 2000-09-05 | 유현식 | The preparation of non-symmetric dialkylated carbonates |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172519A (en) * | 2011-12-23 | 2013-06-26 | 中国科学院兰州化学物理研究所 | Synthetic method of methyl ethyl carbonate |
| EP3363779A4 (en) * | 2015-11-24 | 2019-06-19 | Daikin Industries, Ltd. | Production method of asymmetric chain carbonate |
| US10774028B2 (en) | 2015-11-24 | 2020-09-15 | Daikin Industries, Ltd. | Production method of asymmetric chain carbonate |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20060054533A (en) | 2006-05-22 |
| TW200633973A (en) | 2006-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3686205B1 (en) | Method for producing alkali metal sulfate salt | |
| JP5048508B2 (en) | Method for producing asymmetric linear carbonate | |
| CN105541664B (en) | A kind of method for synthesizing cyanoacrylate | |
| KR910003334B1 (en) | Process for the preparation of unsaturated carboxylic acid amides | |
| WO2006054833A1 (en) | Method for preparing asymmetric linear carbonate | |
| CN101210005A (en) | Method for preparing fluoroethylene carbonate | |
| CN114149401A (en) | Synthesis method of vinyl ethylene carbonate | |
| CN109020849B (en) | Preparation method of deuterated dimethyl sulfoxide | |
| CN111773755A (en) | Method and device for preparing methyl ethyl carbonate by using bulkhead reaction rectifying tower | |
| JPH0710811A (en) | Production of dialkyl carbonate | |
| EP0300794B1 (en) | Preparation of cyclic carbonate | |
| CN103709032B (en) | Preparation method for catalytically synthesizing dibutyl carbonate by proline ionic liquid | |
| CN112321428A (en) | Synthesis method of R- (+) -2- (4-hydroxyphenoxy) ethyl propionate | |
| CN106146302B (en) | The preparation method of propionic ester | |
| CN101445476B (en) | Chemosynthesis method for Alpha-ethyl-2-oxo-1-methyl pyrrolidineacetate | |
| TWI843292B (en) | Unsymmetric linear carbonate and method for preparing thereof | |
| CN109265431B (en) | Synthesis process of 3-acetyl-10, 11-dihydro-5H-dibenzo [ C, G ] chromen-8 (9H) -one | |
| CN115745952B (en) | Preparation method of ethylene sulfite | |
| US9263769B2 (en) | Process for the production of low flammability electrolyte solvents | |
| CN116249587A (en) | Method for producing asymmetric linear carbonates | |
| EP0019374B1 (en) | By-product recycling process in the production of lower alkyl 3.3-dimethyl-4-pentenoate esters | |
| CN105384761A (en) | Preparation method for lithium borane trioxalate | |
| JP2002105064A (en) | Method of producing high-purity oxazolidinone | |
| JP5623103B2 (en) | Process for producing N-acyl- (2S) -oxycarbonyl- (5R) -phosphonylpyrrolidine derivatives | |
| US20240124384A1 (en) | Unsymmetric linear carbonate and method for preparing thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KM KP KZ LC LK LR LS LT LU LV LY MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
| AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU LV MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 05808669 Country of ref document: EP Kind code of ref document: A1 |