KR20160013721A - Method for preparation of five-membered cyclic carbonate from carbon dioxide and epoxide by using alkanolamine as catalyst - Google Patents

Abstract

The present invention relates to a preparation method of a five-membered carbonate compound using an alkanolamine catalyst having a hydroxyl group. The synthesis of a five-membered carbonate compound is environment-friendly and has a simple process. In addition, the alkanolamine catalyst has excellent reactivity and stability, and thus a five-membered carbonate compound can be synthesized at high yield under moderate reaction conditions through hydrogen bonding of the hydroxyl group and synergistic effect of the amine.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preparing a five-membered carbonic acid carbonate from carbon dioxide and an epoxy compound using an alkanolamine as a catalyst,

The present invention is characterized in that a 5-membered ring carbonate compound can be easily synthesized from carbon dioxide and an epoxy compound under mild reaction conditions using an alkanolanime, which is a compound in which the hydrogen atom of ammonia is substituted with an aliphatic alcoholic OH group, as a catalyst To a process for producing a 5-membered ring carbonate compound.

In general, the technique of using carbon dioxide as a raw material for organic synthesis has been studied for a long time. Especially, a technique of synthesizing a 5-membered ring carbonate compound by reacting an epoxy compound with carbon dioxide attracts much attention in terms of manufacturing monomers for functional polymer materials.

Conventionally, diol and phosgene are used in order to obtain a 5-membered ring carbonate compound in a high yield, but it is difficult to handle due to the toxicity of phosgene, which causes a lot of difficulties in the process. Therefore, a method for synthesizing a 5-membered ring carbonate compound at a high yield under a safe condition is desperately required.

On the other hand, Patent Literature 1 discloses a technique of synthesizing a 5-membered ring carbonate compound at a high yield by using amines such as alkylamine, dialkylamine, triethylamine, etc. as a catalyst to convert carbon dioxide and ethylene oxide or propylene oxide into ethylene carbonate Or propylene carbonate is disclosed. However, the conditions of the synthesis reaction are higher than the reaction pressure of 34 atm and the reaction temperature of 100 ~ 400 ° C.

In Non-Patent Document 1, Soga et al. Have reacted propylene oxide with carbon dioxide for 3 days at a temperature of 120 to 180 ° C under a pressure of 40 atm using ZnTe ₂ , AlCl ₃ , Ti (OBu) ₄ , It is known that polypropylene carbonate of about 1800 to 3600 is synthesized.

In Non-Patent Document 2, Kihara et al. Have reported that polyglycidyl methacrylate reacts with gaseous carbon dioxide at 120 to 160 ° C to form poly [(2-oxo-1,3-dioxolan-4-yl) (Non-Patent Document 3) discloses that polyglycidyl methacrylate and carbon dioxide at normal pressure are mixed with an alkali metal halogen compound, NaI, and triphenylphosphine, as catalysts It is also known that poly DOMA is obtained by reacting at 100 ° C using.

In Non-Patent Document 4, Nishikubo et al. Used polystyrene prepared by co-copolymerizing styrene, divinylbenzene, and vinylbenzene chloride simultaneously with quaternary ammonium chloride or quaternary chloride salt as a catalyst, and using toluene as a solvent As a result of the reaction of carbon dioxide and phenylglycidyl ether at normal pressure and 80 ° C for 24 hours, it was known that the yield of phenoxymethylethylene carbonate was 30 to 95%. However, in this case, too, the structure of the catalyst was too dense, It is difficult for the reactant to approach the active site of the catalyst, so that the reaction yield is low and the reaction takes a long time.

The conventional addition reaction between the epoxy compound and carbon dioxide as described above has a problem in that a costly expensive organometallic catalyst is used or a process cost is high due to a high reaction condition. In addition, there is a problem in that the catalyst prepared according to the method of Nishikubo There is a problem that the diffusion resistance to the reactant is high and the stability is low and the yield is lowered.

On the other hand, in Patent Document 2, a tertiary alkanolamine compound is used as an effective absorbent for carbon dioxide. In non-patent reference 6, the absorption reaction of alkanolanime and carbon dioxide is absorbed by a carbon dioxide hydrolysis base catalytic reaction It is well known.

As described above, alkanolamine has been extensively used as an absorbent for carbon dioxide in a commercial process, but there is no known case that a catalyst is used as a catalyst for the addition reaction of carbon dioxide and an epoxy compound.

In the non-patent document 5, the hydrogen bonding of the hydroxyl group of the catalyst is caused by the synergistic effect with the halogen anion and the ring opening of the epoxy compound in the addition reaction of the carbon dioxide and the epoxy compound opening of the cells.

Accordingly, the present inventors have completed the present invention by synthesizing a 5-membered ring carbonate compound by using an alkanolanime having a hydroxyl group as a catalyst in an addition reaction of an epoxy compound and carbon dioxide.

Patent Document 1: United States Patent Publication No. 2773881 (registered on December 11, 1956) Glycol carbonate Patent Document 2: Korean Registered Patent No. 10-0259461 (registered on March 22, 2000) An absorbent which improves the carbon dioxide absorption performance of a tertiary alkanolamine by addition of a reaction activator

Non-Patent Document 1: Polymerization of propylene carbonate [(K. Soga et al., J. Polymer Science: Polymer Chemistry Edition, 15 (1997) 219] Non-Patent Document 2: Solid-state catalytic incorporation of carbon dioxide into oxirane-polymer. Conversion of poly (glycidyl methacrylate) to carbonate-polymer under atomospheric pressure [N. Kihara et al., J. Chemical Society: Chemical Communication, (1994) 937] Non-Patent Document 3: Incorporation of Carbon Dioxide into Poly (glycidyl methacrylate) [N. Kihara et al., Macromolecules, 25 (1992) 4824] Non-Patent Document 4: Insoluble polystyrene-bound quaternary onium salt catalysts for the synthesis of cyclic carbonates by the reaction of oxiranes with carbon dioxide [T. Nishikubo et al., J. Polymer Science, 31 (1993) 939] Non-Patent Document 5: Chitosan functionalized ionic liquid as a recyclable biopolymer-supported catalyst for cycloaddition of CO2 [J. Sun et al., Green Chem., 14 (2012) 14] Non-Patent Document 6: The Operational Characteristics of CO2 5 ton / day Absorptive Separation Pilot Plant [S. J. Park et al., Korean Chem. Eng. Res., 50 (2012) 128]

DISCLOSURE Technical Problem In order to solve the above problems, it is an object of the present invention to synthesize a 5-membered ring carbonate compound at a relatively low pressure and a low temperature using an alkanolamine having a hydroxyl group as a catalyst at a high yield And a method for producing a 5-membered cyclic carbonate compound using the alkanolamine as a catalyst.

In order to solve the above problems, the present invention provides a method for producing a five-membered carbonate compound characterized in that an epoxy compound and carbon dioxide are additionally reacted using an alkanolamine having a hydroxyl group as a catalyst As a solution.

The addition reaction is carried out by using an alkanolamine catalyst having a hydroxyl group at an initial pressure of 0.8 to 2.0 MPa, a reaction temperature of 110 to 140 ° C, a reaction time of 2 to 4 hours, a catalyst amount of 0.4 to 0.8 mmol < / RTI >

The alkanolamine is N - methyl ethanolamine [N -methylethanolamine (MEA)], triethanol amine [triethanolamine (TEA)], N , N - dimethylethanolamine [N, N -dimethylethanolamine (DMEA) ], N, N - (DMPA), and methyldiethanolamine (MDEA), and is characterized in that one of these solvents is selected from the group consisting of N , N- dimethylpropanolamine (DMPA) and methyldiethanolamine

The epoxy compound may be selected from the group consisting of propylene oxide, chloropropylene oxide, allyl glycidyl ether, 1,2-epoxy-5-hexene, , Glycidyl isobutyl ether, and styrene oxide is selected from the group consisting of glycidyl isobutyl ether and styrene oxide.

According to the present invention, by synthesizing a 5-membered ring carbonate compound using an alkanolamine having a hydroxyl group as a catalyst, it is possible to obtain a compound having a hydroxyl group Hydrogen bonding has an advantage of synthesizing a 5-membered ring carbonate compound at a relatively low pressure and a low temperature due to a synergistic effect with amines at a high yield.

The present invention relates to a method for preparing a 5-membered cyclic carbonate compound from an epoxy compound and carbon dioxide by using an alkanolamine having a hydroxyl group as a catalyst.

Kind of the alkanolamines (alkanolamine) used in the present invention is N - methyl ethanolamine [N -methylethanolamine (MEA)], triethanol amine [triethanolamine (TEA)], N , N - dimethylethanolamine [N, N -dimethylethanolamine (DMEA)], N, N - dimethyl propanol amine [N, N -dimethylpropanolamine (DMPA) ] and methyl diethanol amine [methyldiethanolamine (MDEA)].

The alkanolamine catalyst used in the present invention is characterized in that it has high reactivity under mild reaction conditions due to the synergistic effect of the hydrogen bond of the hydroxyl group and the amine.

It is characterized by using only the epoxy compound and carbon dioxide without using any solvent by using the catalyst, and the production method of the 5-membered ring carbonate compound by the addition reaction is as follows.

The alkanolamine, which is a catalyst added in the present invention, is added in a molar ratio of epoxy compound to catalyst of 100 to 0.4 to 0.8. If the amount of the added catalyst is less than 0.4, the carbon dioxide and the epoxy compound do not sufficiently react with each other, so that the unreacted epoxy compound may remain in the reactant. When the amount of the catalyst exceeds 0.8, The mixing of the catalyst is poor and the catalytic activity may decrease.

The reaction conditions for the synthesis of the 5-membered cyclic carbonate compound are preferably 2 to 4 hours at 110 to 140 ° C and 0.8 to 2.0 MPa (initial pressure of carbon dioxide), and the initial pressure, reaction temperature or reaction time of carbon dioxide If the amount is less than the above-mentioned range, there is a fear that the yield of the product is reduced. If the amount is exceeded, the product may be decomposed or the yield may decrease.

The epoxy compounds which can be used in the above reaction include propylene oxide, chloropropylene oxide, allyl glycidyl ether, 1,2-epoxy- 5-hexene, glycidyl isobutyl ether, styrene oxide, and the like.

Hereinafter, the present invention will be described in detail with reference to examples. However, the scope of the present invention is not limited to these examples.

In order to observe the effect of the alkanolamine having a hydroxyl group on the structure of the catalyst, a reaction of synthesizing a 5-membered ring carbonate compound by the addition reaction of propylene oxide with carbon dioxide was carried out without using a solvent Respectively.

(Examples 1 to 5 and Comparative Example 1)

Examples 1 to 5 and Comparative Example 1 [Table 1] as an alkanolamine-containing catalyst as described in Example 1, is N, N - dimethylethanolamine [N, N -dimethylethanolamine (DMEA)], Example 2 N, N - dimethyl propanol amine [N, N -dimethylpropanolamine (DMPA) ], example 3 is methyl diethanolamine [methyldiethanolamine (MDEA)], example 4 triethanolamine [triethanolamine (TEA)], example 5 is N - methyl ethanolamine [N -methylethanolamine (MEA)] and Comparative example 1 was used as the catalyst of the ethanolamine [ethanolamine (EA)], respectively.

Examples 1 to 5 and Comparative Example 1 were prepared by dissolving 42.8 mmol of propylene oxide at 120 ° C and 1.0 MPa (molar ratio) using 0.8 mol% catalyst (propylene oxide, PO) (Initial pressure of carbon dioxide) for 3 hours to synthesize propylene carbonate (PC). The results are shown in Table 1 below.

Example catalyst PC yield (%) Example 1 DMEA 82 Example 2 DMPA 91 Example 3 MDEA 76 Example 4 TEA 93 Example 5 MEA 71 Comparative Example 1 EA 50

As can be seen from the above Table 1, as the electron density was increased from the primary amine to the tertiary amine in the alkanolamine, the basicity became higher and the higher reactivity was shown. As the number of hydroxyl groups increased, the hydrogen As the number of bonds increased, the yield was high.

(Examples 6 to 9)

The reaction was carried out under the same conditions as in Example 2, but the yield of PC was measured by changing the initial pressure of carbon dioxide. The results are shown in Table 2 below.

Example Carbon dioxide initial pressure (MPa) PC yield (%) Example 6 0.8 88 Example 2 1.0 91 Example 7 1.2 93 Example 8 1.4 93 Example 9 2.0 92

As can be seen from the above Table 2, as the pressure of carbon dioxide increases from 0.8 MPa to 1.4 MPa, the absorption of carbon dioxide increases and the yield of PC increases. If the pressure is higher, the carbon dioxide reacts with PO, The yield of PC was decreased by the dilution effect which interferes with the contact of the PC.

(Examples 10 to 12)

The reaction was carried out under the same conditions as in Example 2, and the yield of PC was measured by varying the reaction temperature. The results are shown in Table 3 below.

Example Reaction temperature (캜) PC yield (%) Example 10 110 84 Example 2 120 91 Example 11 130 95 Example 12 140 92

As can be seen from the above Table 3, the yield of PC increased from 110 ° C to 130 ° C, but the yield decreased more than 140 ° C because the generated PC was decomposed at high temperatures do.

(Examples 13 to 16)

The reaction was carried out under the same conditions as in Example 2, and the yield of PC was measured by varying the reaction time. The results are shown in Table 4 below.

Example Reaction time (hours) PC yield (%) Example 13 2 80 Example 14 2.5 89 Example 2 3 91 Example 15 3.5 93 Example 16 4 93

As can be seen in Table 4, the reaction time steadily increases until 3.5 hours. However, when the reaction time was more than 3.5 hours, the equilibrium reaction was reached.

(Examples 17 to 19)

The reaction was carried out under the same conditions as in Example 2, and the yield of PC was measured by varying the amount of the catalyst, and the results are shown in Table 5 below.

Example The catalyst mol% PC yield (%) Example 17 0.4 79 Example 18 0.5 88 Example 19 0.6 90 Example 2 0.8 91

As can be seen from the above Table 5, the reactivity was increased up to 0.6 mol% (Example 19) as the amount of the catalyst was increased, and the reactivity was not greatly increased as the amount of the catalyst was increased thereafter. It is considered that the amount of DMPA in the synthesis of propylene carbonate by the addition reaction of propylene oxide with carbon dioxide is 0.6 mmol%.

(Examples 20 to 24)

The reaction was carried out under the same conditions as in Example 2 except that the 5-membered ring carbonate compound was prepared by changing the epoxy compound used and the yield was shown in Table 6 below.

Example Epoxy compound Yield of 5-membered carbonates (%) Example 2 Propylene oxide 91 Example 20 Chloropropylene oxide 92 Example 21 Allyl glycidyl ether 87 Example 22 1,2-epoxy-5-hexene 82 Example 23 Glycidyl isobutyl ether 88 Example 24 Styrene oxide 83

As shown in Table 6, it can be seen that the DMPA catalyst is effective for the addition reaction of various types of epoxy compounds with carbon dioxide.

(Comparative Examples 2 to 4)

In the present Comparative Examples 2 to 4, the reaction was carried out under the same conditions as in Example 2 to identify the hydroxyl group of the alkanolamine. Trimethylamine (0.8 mol% PO 5-membered cyclic carbonate compound was prepared by using a catalyst prepared by mixing either H ₂ O (based on 1.1 mol% based on PO) and methanol (based on 0.8 mol% based on PO), and comparing the measured yields, Respectively.

Comparative Example catalyst PC yield (%) 2 Trimethylamine 8 3 Trimethylamine / H ₂ O 55 4 Trimethylamine / methanol 69

As can be seen from the above Table 7, the use of the common secondary and tertiary amines alone (Comparative Example 2) and the use of H ₂ O (Comparative Example 3) or methanol (Comparative Example 4) Comparative Examples 3 and 4 show a higher yield of PC because the reaction is accelerated by promoting the ring opening of the epoxy compound by the hydrogen bonding of H ₂ O and methanol and the synergistic effect of amine. Here, the comparison of Example 2 shows that PC is synthesized at a higher yield than that of Comparative Example 4, indicating that DMPA having a hydroxyl group together is more advantageous in addition reaction of an epoxy compound with carbon dioxide.

Therefore, as shown in the above examples, the alkanolamine catalyst is excellent in reactivity and stability, and has a low temperature due to the hydrogen bonding of the hydroxyl group and the synergistic effect of amine And it was confirmed that a 5 - membered ring carbonate compound can be synthesized with a high yield at a low pressure.

The present invention described above is not necessarily limited to the above configuration, and various substitutions, modifications, and changes may be made without departing from the technical spirit of the present invention.

Claims (5)

Wherein an alkanolamine catalyst having a hydroxyl group is used to cause addition reaction of carbon dioxide and an epoxy compound.
The method according to claim 1,
The alkanolamine is triethanolamine (triethanolamine), N, N - dimethylethanolamine (N, N -dimethylethanolamine), N , N - dimethyl propanol amine (N, N -dimethylpropanolamine), methyl diethanolamine (methyldiethanolamine), N -methyl ethanolamine process for producing a five-membered carbonate compound selected from one or (N -methylethanolamine), characterized in that used as the catalyst.
3. The method according to any one of claims 1 to 2,
Wherein the addition reaction is carried out at a temperature of 110 to 140 占 폚 and a carbon dioxide pressure of 0.8 to 2.0 MPa for 2 to 4 hours.
The method according to claim 1,
Wherein the amount of the alkanolamine catalyst to be added is such that the molar ratio of the epoxy compound to the catalyst is 100 to 0.4 to 0.8.
The method according to claim 1,
The epoxy compound is preferably an epoxide derivative selected from the group consisting of propylene oxide, chloropropylene oxide, allyl glycidyl ether, 1,2-epoxy-5-hexene, glycidyl isobutyl ether and styrene oxide To obtain a 5-membered cyclic carbonate compound.