KR101627018B1 - Method for preparing carbonic ester using organometallic compound - Google Patents
Method for preparing carbonic ester using organometallic compound Download PDFInfo
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- KR101627018B1 KR101627018B1 KR1020130117400A KR20130117400A KR101627018B1 KR 101627018 B1 KR101627018 B1 KR 101627018B1 KR 1020130117400 A KR1020130117400 A KR 1020130117400A KR 20130117400 A KR20130117400 A KR 20130117400A KR 101627018 B1 KR101627018 B1 KR 101627018B1
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- carbonic ester
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- 150000002902 organometallic compounds Chemical class 0.000 title claims abstract description 44
- 150000002148 esters Chemical class 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 21
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 239000010936 titanium Substances 0.000 claims description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 abstract description 22
- 150000002736 metal compounds Chemical class 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 150000002430 hydrocarbons Chemical group 0.000 abstract description 6
- 230000008929 regeneration Effects 0.000 abstract description 3
- 238000011069 regeneration method Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 150000004651 carbonic acid esters Chemical class 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- -1 silicon alkoxide compound Chemical class 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/025—Silicon compounds without C-silicon linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/2224—Compounds having one or more tin-oxygen linkages
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- 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
The method for producing a carbonic ester according to the present invention comprises reacting an organic metal compound represented by the following general formula (1), carbon dioxide and an alcohol having 1 to 10 carbon atoms to produce a carbonic ester. The above production method can produce a carbonic ester at a high yield without the regeneration and recycle process of the organometallic compound.
[Chemical Formula 1]
In Formula 1, M a is a Group 4 or a Group 14 metal and, R 1, R 2 and R 3 are each independently a hydrocarbon group having 1 to 10, a is an integer from 0 to 2, n is 1 to Lt; / RTI >
Description
The present invention relates to a method for producing a carbonic ester using an organometallic compound. More specifically, the present invention relates to a method for producing carbonic ester using an organometallic compound which can produce a carbonic ester at a high yield, without using a specific organometallic compound, carbon dioxide and alcohol, and without recycling and recycling of the organometallic compound will be.
Carbonic acid esters are monomers that are usefully used in the production of polycarbonate, and many studies related to the production thereof are under way. Conventionally, carbonic acid esters were prepared through reaction with alcohol using phosgene as a carbonyl source. However, this method has a problem of using a very toxic phosgene as well as a problem of using a chlorine-based solvent and a problem of treating a by-product neutral salt .
In order to solve the problems associated with the use of phosgene, a method for producing carbonic ester using carbon monoxide as a carbonyl source has been developed. However, when carbon monoxide is used as a carbonyl source, the reaction rate and yield are low, and the use of poisonous carbon monoxide at high pressure increases the risk of explosion and requires a great deal of cost for ensuring stability. In addition, there is a fear that side reactions such as generation of carbon dioxide may occur due to oxidation of carbon monoxide.
Also, a method has been developed in which carbon dioxide is reacted with ethylene oxide or the like to synthesize a cyclic carbonic ester and then react it with methanol to produce dimethyl carbonate. This method is an excellent method because it is not harmful to carbon dioxide which is a raw material, it uses corrosive substances such as hydrochloric acid, or rarely generates corrosive substances. However, side reactions in which ethylene glycol is produced may occur, and it is difficult to safely transport ethylene or ethylene oxide, which is a raw material of ethylene oxide, and there are limitations related to plant location and the like.
Recently, a method for producing carbonic acid ester by reacting carbon dioxide with an organic metal compound has been studied. It has been found that the carbonic ester is separated from the mixture produced by the above method and the residue can regenerate the organometallic compound through reaction with alcohol. That is, since the organic metal compound used in the reaction can be recycled, it can be reused in the carbonic ester formation reaction, and there is no problem due to transportation or the like. As such an organometallic compound, there is disclosed a compound in the form of Sn (R) 2 (OR ') 2 (R and R': different alkyl groups) having a center metal tin and two alkyl and alkoxy groups 2001-523783, 2006-548937, 2006-513613, 2006-095140, 2005-511122, 2003-556375, 2001-396545, 2001-396537, etc.). However, the known organometallic compounds have a low reactivity and a low yield of carbonic ester production, which is a problem to be solved.
An object of the present invention is to provide a method for producing a carbonic ester in which a carbonic ester can be synthesized at a high yield without using an organometallic compound, carbon dioxide and an alcohol, and without regeneration and recycling of an organometallic compound.
The above and other objects of the present invention can be achieved by the present invention described below.
One aspect of the present invention relates to a method for producing a carbonic ester. The preparation method comprises reacting an organic metal compound represented by the following formula (1), carbon dioxide and an alcohol having 1 to 10 carbon atoms to produce a carbonic ester:
[Chemical Formula 1]
In Formula 1, M a is a Group 4 or a Group 14 metal and, R 1, R 2 and R 3 are each independently a hydrocarbon group having 1 to 10, a is an integer from 0 to 2, n is 1 to Lt; / RTI >
In an embodiment, the M a may be titanium (Ti), tin (Sn), or zirconium (Zr).
In an embodiment, each of R 1 , R 2 and R 3 may independently be methyl, ethyl, propyl, butyl, pentyl, hexyl or phenyl.
In an embodiment, the reaction may be carried out at a temperature of 130 to 230 ° C and a carbon dioxide pressure of 10 to 200 bar.
Another aspect of the invention relates to organometallic compounds for the production of carbonic ester. The organometallic compound is represented by the formula (1).
INDUSTRIAL APPLICABILITY The present invention has the effect of providing a method for producing a carbonic ester which can synthesize carbonic ester at a high yield without using a specific organometallic compound, carbon dioxide and alcohol and without recycling and recycling of the organometallic compound.
1 is a 1 H-NMR spectrum of an organometallic compound prepared according to Production Example 1 of the present invention.
2 is a 1 H-NMR spectrum of an organometallic compound prepared according to Production Example 2 of the present invention.
Hereinafter, the present invention will be described in detail.
The method for producing a carbonic ester according to the present invention comprises the steps of simultaneously reacting an organometallic compound represented by the following general formula (1), carbon dioxide and an alcohol having 1 to 10 carbon atoms to produce a carbonic ester.
[Chemical Formula 1]
In the above formula (1), M a is a Group 4 or Group 14 metal such as titanium (Ti), tin (Sn), or zirconium (Zr) in the periodic table, and R 1 , R 2 and R 3 are each independently For example, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, preferably a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, Lt; / RTI > a is an integer of 0 to 2, and n is an integer of 1 to 3.
The organometallic compound of the present invention includes an oxygen (O) -metal (M a ) -oxy (O) -silicon (Si) -oxy (O) bond and includes, for example, a metal oxide And a silicon alkoxide compound represented by the following general formula (3).
(2)
(3)
In the formulas (2) and (3), M a , R 1 , R 2 , R 3 and a are the same as defined in the above formula (1).
In an embodiment, the reaction may be carried out according to Scheme 1 below.
[Reaction Scheme 1]
For example, the reaction can be carried out at a temperature of 150 to 170 DEG C and a pressure of atmospheric pressure.
In the above process, the molar ratio of the metal oxide compound represented by
(Ion Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES), nuclear magnetic resonance spectroscopy (NMR) spectroscopy (NMR) ) And the like.
The alcohol used in the present invention may be represented by the following general formula (4).
[Chemical Formula 4]
R 4 OH
In Formula 4, R 4 may be a hydrocarbon group having 1 to 10 carbon atoms, such as an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, preferably a methyl group, an ethyl group, a propyl group, a butyl group , Pentyl group, hexyl group, or phenyl group. For example, R 4 may be the same hydrocarbon group as R 1 , R 2 and R 3, and specifically may be the same hydrocarbon group as R 3 .
Specific examples of the alcohol include, but are not limited to, methanol, ethanol, propanol, butanol, pentanol, hexanol, and phenol.
The carbonic ester prepared according to the method for producing a carbonic ester of the present invention can be represented by the following general formula (5).
[Chemical Formula 5]
R 5 OCOOR 6
In Formula 5, R 5 and R 6 each independently represent a hydrocarbon group having 1 to 10 carbon atoms, for example, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, preferably a methyl group, an ethyl group , A propyl group, a butyl group, a pentyl group, a hexyl group, or a phenyl group. Wherein R 5 and R 6 may be derived from the alcohol R 4 in the general formula (4) and R 2 and R 3 of the organometallic compound of the formula (1).
The reaction can be carried out by a conventional batch reaction, for example at temperatures of 130 to 230 DEG C, preferably 140 to 190 DEG C and at a carbon dioxide pressure of 10 to 200 bar, preferably 40 to 150 bar . In this range, the reaction rate is high and carbonic ester can be produced with high yield.
Typically, the batch reaction is carried out in consideration of the conversion rate and the reactor volume, and is a liquid phase process that is not superheated.
In addition, the reaction of the present invention uses a liquid reaction product of an alcohol having 1 to 10 carbon atoms, carbon dioxide and a solid organometallic compound as gas phase reactants, and requires no additional solvent. That is, it may be a homogeneous reaction in which carbon dioxide and an organic metal compound are melted and reacted with the alcohol. The reaction may be carried out at a stirring rate of, for example, 300 to 1,000 rpm, preferably 400 to 500 rpm and a reaction time of 0.5 to 24 hours, preferably 1 to 3 hours, And the viscosity of the solvent and the like, it is preferable to perform in the region where the mass transfer of the interface between the carbon dioxide and the alcohol is maximum. Such a batch reaction can be easily performed by a person having ordinary skill in the art to which the present invention belongs.
For example, it can be understood that the above-mentioned production method produces a carbonic ester by the reaction shown in the following reaction formula (2).
[Reaction Scheme 2]
In an embodiment, the organometallic compound may be used in an amount of 1 to 30 moles, preferably 5 to 15 moles, per 100 moles of the alcohol. Carbonic acid esters can be produced at a high yield in the above range.
The method for producing a carbonic ester of the present invention is a method for simultaneously reacting the organometallic compound, carbon dioxide and an alcohol having 1 to 10 carbon atoms, in which a carbonic ester can be obtained in a high yield and a separate regeneration and recycling step of an organometallic compound is not required It is economical.
Hereinafter, the present invention will be described in more detail by way of examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.
Example
Manufacturing example 1: Preparation of organometallic compounds
(60 mmol) of dibutyltin oxide (Bu 2 SnO) and 19.2 g (60 mmol) of silicone butoxide (Si (OBu) 4 ) were placed in a 75 ml autoclave reactor having an external heater and stirred at the same time The mixture was reacted at 150 to 170 ° C for 2 hours and then cooled to room temperature to obtain an organometallic compound represented by the following formula (1a). The metal and alkoxy groups of the organometallic compound thus prepared were confirmed using an inductively coupled plasma spectrophotometer (ICP-AES) and a nuclear magnetic resonance spectrometer (NMR). As a result of ICP-AES elemental analysis, a 1 H-NMR spectrum in which the Sn: Si (molar ratio) was about 1: 1 and the butoxy group can be confirmed is shown in FIG. 1 ( 1 H NMR: δ0.93 = CH 3 , .38 = CH 2, δ1.47 = CH 2, δ2.54 = OCH 2).
[Formula 1a]
In the above formula (1a), Bu is an n-butyl group.
Manufacturing example 2: Preparation of organometallic compounds
29.2 g (120 mmol) of dibutyltin oxide (Bu 2 SnO) and 19.2 g (60 mmol) of silicon butoxide (Si (OBu) 4 ) were placed in a 75 ml autoclave reactor having an external heater, To 170 ° C for 2 hours, and then cooled to room temperature to prepare an organometallic compound represented by the following formula (1b) as a transparent liquid. The metal and alkoxy groups of the organometallic compound thus prepared were confirmed using an inductively coupled plasma spectrophotometer (ICP-AES) and a nuclear magnetic resonance spectrometer (NMR). As a result of ICP-AES elemental analysis, a 1 H-NMR spectrum in which Sn: Si (molar ratio) was about 2: 1 and a butoxy group can be confirmed is shown in FIG. 2 ( 1 H NMR: δ0.93 = CH 3 , .38 = CH 2, δ1.47 = CH 2, δ2.54 = OCH 2).
[Chemical Formula 1b]
In the above formula (1b), Bu is an n-butyl group.
Example One
7.3 g (13.2 mmol) of the organometallic compound represented by the above formula (1a) and 27.2 g (367.3 mmol) of n-butanol were charged into a 75 ml autoclave reactor having an external heater and heated to 150 ° C. at the same time as stirring, And the mixture was reacted at 150 DEG C and 120 bar for 1 hour, and then cooled to room temperature. Carbon dioxide was vented and returned to atmospheric pressure. The reaction liquid was analyzed by gas chromatography, and it was confirmed that di-n-butyl carbonate was obtained in a yield of 101.5%.
Example 2
The reaction was carried out in the same manner as in Example 1 except for using 10.4 g (13.2 mmol) of the organometallic compound represented by Formula 1b instead of 7.3 g (13.2 mmol) of the organometallic compound represented by Formula 1a. After completion of the reaction, the reaction solution was analyzed by gas chromatography, and it was confirmed that di-n-butyl carbonate was obtained in a yield of 82.0%.
Comparative Example One
Except that 5.0 g (13.2 mmol) of an organometallic compound (Bu 2 Sn (OBu) 2 ) represented by the following formula (6a) was used in place of 7.3 g (13.2 mmol) of the organometallic compound represented by the above formula The reaction was carried out in the same manner as in Example 1. After completion of the reaction, the reaction solution was analyzed by gas chromatography, and it was confirmed that di-n-butyl carbonate was obtained in a yield of 69.2%.
[Chemical Formula 6a]
Comparative Example 2
Except that 8.0 g (13.2 mmol) of an organometallic compound (Bu 2 SnOBu) 2 O represented by the following formula 6b was used instead of 7.3 g (13.2 mmol) of the organometallic compound represented by the above formula (1a) The reaction was carried out in the same manner as in Example 1. After completion of the reaction, the reaction solution was analyzed by gas chromatography, and it was confirmed that di-n-butyl carbonate was obtained in a yield of 31.0%.
[Formula 6b]
Comparative Example 3
7.3 g (13.2 mmol) of the organometallic compound represented by the above formula (1a) was placed in an internal volume 75 ml autoclave reactor having an external heater, and the mixture was heated to 150 ° C. at the same time as the stirring. Carbon dioxide was then introduced to 120 bar, And 120 bar for 1 hour, and then cooled to room temperature. After the carbon dioxide was vented to return to atmospheric pressure, the reaction liquid was analyzed by gas chromatography, and it was confirmed that di-n-butyl carbonate was obtained in a yield of 53.0%.
Comparative Example 4
Except that 4.5 g (13.2 mmol) of titanium butoxide (Ti (OBu) 4 ) was used instead of 7.3 g (13.2 mmol) of the organometallic compound represented by the above formula (1a) . After completion of the reaction, the reaction solution was analyzed by gas chromatography, and it was confirmed that di-n-butyl carbonate was obtained in a yield of 40.0%.
The reaction conditions and the yield of carbonic ester are shown in Table 1 below.
(° C)
(bar)
(h)
(%)
Property evaluation method
(1) Evaluation of yield: After the reaction, the reaction solution was analyzed by gas chromatography.
Carbonic acid ester yield (%) = (moles of produced carbonate ester / number of moles of organic metal compound added) x 100
From the results shown in Table 1, it can be seen that the organic metal compounds of the present invention can produce carbonic ester at a higher yield than conventional organometallic compounds (Comparative Examples 1 and 2) under the same reaction conditions. Further, it can be seen that carbonic ester can be produced at a higher yield than Comparative Example 4 in which carbonic acid ester is produced in comparison with Comparative Example 3 in which no alcohol is used together and Comparative Example 4 in which titanium butoxide (Ti (OBu) 4 ) alone is used have.
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 (5)
[Chemical Formula 1]
In the above formula (1), M a is titanium (Ti), tin (Sn), or zirconium (Zr), R 1 , R 2 and R 3 are each independently a hydrocarbon group having 1 to 10 carbon atoms, 2, and n is an integer of 1 to 3.
[Chemical Formula 1]
In the above formula (1), M a is titanium (Ti), tin (Sn), or zirconium (Zr), R 1 , R 2 and R 3 are each independently a hydrocarbon group having 1 to 10 carbon atoms, 2, and n is an integer of 1 to 3.
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| KR1020130117400A KR101627018B1 (en) | 2013-10-01 | 2013-10-01 | Method for preparing carbonic ester using organometallic compound |
| PCT/KR2014/000460 WO2015050292A1 (en) | 2013-10-01 | 2014-01-16 | Method for preparing carbonate by using organometallic compound |
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| KR1020130117400A KR101627018B1 (en) | 2013-10-01 | 2013-10-01 | Method for preparing carbonic ester using organometallic compound |
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| KR101627018B1 true KR101627018B1 (en) | 2016-06-03 |
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| US3307973A (en) * | 1964-01-17 | 1967-03-07 | Glidden Co | Dialkylstannoxy organometallic compounds and condensation products |
| US5034455A (en) * | 1988-05-31 | 1991-07-23 | General Electric Company | Curable silicone caulk compositions |
| DE3903145A1 (en) * | 1989-02-02 | 1990-08-09 | Wacker Chemie Gmbh | METHOD FOR POLYMERIZING POLAR COMPOUNDS |
| RU2206571C1 (en) * | 2002-01-16 | 2003-06-20 | Общество с ограниченной ответственностью "Пента-91" | Method for preparing organometallohydroxy- stannates |
| AU2003257764A1 (en) * | 2002-08-07 | 2004-02-25 | Asahi Kasei Chemicals Corporation | Process for producing carbonic ester |
| CN102112482B (en) * | 2008-08-08 | 2016-01-20 | 旭化成化学株式会社 | The manufacture method of alkyltin alkoxides compound and use the manufacture method of carbonic ether of this compound |
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