KR100239222B1 - Phase transfer catalyst and preparation of 5-membered cyclic carbonate compound using the catalyst - Google Patents

Abstract

In the present invention, the polystyrene-based polymer support by polymerizing 55-89 parts by weight of styrene and 1-20 parts by weight of divinylbenzene, by adding 10-40 parts by weight of vinylbenzene chloride to the partial polymer obtained in step (a) Forming a support, and supporting the support with a halogenated trialkylbenzylammonium (R ₃ -benzylammonium-X: the alkyl group (R) is an alkyl group having 2-8 carbons, X is Cl or Br) Using a process for producing a phase transfer catalyst comprising a, and the phase transfer catalyst prepared by this method, by reacting the carbon dioxide and epoxide derivatives for 2 to 24 hours at a normal pressure of 50 to 120 ℃ to prepare a five-membered ring carbonate compound A method is provided. According to the present invention, the recovery and reuse of the catalyst is easy and the five-membered ring carbonate can be produced in a high yield in a relatively short time.

Description

Method for preparing phase transfer catalyst and method for preparing 5-membered ring carbonate compound using catalyst prepared by this method

The present invention relates to a method for preparing a phase transfer catalyst and a method for preparing a 5-membered ring carbonate compound using a catalyst prepared by the method, and more particularly, to a polymer carrier type in which a quaternary ammonium salt is supported on a polystyrene polymer support. A method for producing a phase transfer catalyst and a method for producing a 5-membered ring carbonate by reacting carbon dioxide, known as a global warming gas, with an epoxide under normal pressure conditions using the catalyst.

The technique of using carbon dioxide as a raw material for organic synthesis has been studied for a long time, and the technique of synthesizing 5-membered ring carbonate by reacting epoxide and carbon dioxide has attracted much attention in terms of monomer production of functional polymer materials.

Conventionally, diol and phosgene are used to obtain 5-membered ring carbonate in high yield, but due to the toxicity of phosgene, there are many difficulties in the process. Therefore, there is an urgent need for a method for synthesizing five-membered ring carbonate in high yield under safe conditions.

US Patent No. 2,773,881 discloses a process for synthesizing ethylene carbonate or propylene carbonate from carbon dioxide and ethylene oxide or propylene oxide using amines such as alkylamines, dialkylamines, triethylamines as catalysts. However, the conditions of the synthesis reaction is relatively high, the reaction pressure is higher than 34 atm and the reaction temperature is also 100 ℃ ~ 400 ℃.

Soga et al. (K. Soga, Y, Tazuke, S. Hosoda and S. Ikeda, J. Polymer Science: Polymer Chemistry Edition, 15, 219-229, 1977) are also organometallic compounds ZnEt ₂ , AlCl ₃ , It was reported that propylene carbonate having a molecular weight of about 1800-3600 was synthesized by reacting propylene oxide and carbon dioxide for 3 days at 40 atm and 120-180 ° C. using Ti (OBu) ₄ as a catalyst.

Kihara et al. (N. Kihara and T. Endo, J. Chemical Society: Chemical Communication, 937, 1994) disclose that polyglycityl methacrylate is reacted with gaseous carbon dioxide at 120-160 ° C. It was reported that oxo-1,3-dioxolan-4-yl) methyl methacrylate) (polyDOMA) was synthesized. In addition, polyglycidyl methacrylate and atmospheric carbon dioxide were reacted at 100 ° C using a mixture of alkali metal halogenide NaI and triphenylphosphine as a catalyst to obtain polyDOMA (N. Kihara and T. Endo, Macromolecules, 25 4824, 1992).

In addition, Nishikubo et al. (T, Nishikubo, A. Kameyama, J. Yamashita, M. Tomoi and W. Fukuta, J. Polymer Science, 31, 939-947, 1993) also showed styrene, divinylbenzene, vinylbenzene chloride. Quaternary ammonium chloride or quaternary phosphate salt was attached to polystyrene prepared by copolymerization at the same time and used as a catalyst. Toluene was used as a solvent to react carbon dioxide and phenylglycidyl ether at atmospheric pressure at 80 ° C. for 24 hours. As a result, phenoxymethylethylene carbonate was obtained in a yield of 30 to 95%. However, even in this case, since the structure of the catalyst is too dense to cause diffusion resistance, it is difficult for the reactants to approach the active point of the catalyst, so the reaction yield is low and the reaction takes a long time.

As described above, since the addition reaction of the conventional epoxide and carbon dioxide is mainly performed using expensive organometallic catalyst or quaternary ammonium salt catalyst as a phase transfer catalyst in the liquid state, it is difficult to separate and recover the catalyst after the reaction. This costs a lot. In addition, even in the case of the catalyst prepared according to the Nishikubo method, the diffusion resistance to the reactants was severe and there was a problem that the yield was lowered.

The technical problem to be achieved by the present invention to solve the above problems is to provide a method for preparing a phase transfer catalyst of a stable form supported on a polymer support relatively easily.

Another object of the present invention is to provide a method for synthesizing a 5-membered ring carbonate in a short time at a low temperature of atmospheric pressure using the phase transfer catalyst prepared by the above method.

In order to achieve the above object, in the present invention, (a) partially polymerizing 55-89 parts by weight of styrene and 1-20 parts by weight of divinylbenzene, and (b) vinylbenzene chloride 10- to the partial polymer obtained in step (a). Adding 40 parts by weight to polymerize to form a polystyrene-based polymer support, and (c) halogenated trialkylbenzylammonium (R ₃ -benzylammonium-X: the alkyl group (R) has 2 to 8 carbon atoms in the support). Alkyl group, X is Cl or Br) is provided a method for producing a phase transfer catalyst comprising the step of supporting.

Another object of the present invention is achieved by a method of preparing a 5-membered ring carbonate compound by reacting carbon dioxide and an epoxide derivative for 2 to 24 hours at a normal pressure of 50-120 ° C. using a phase transfer catalyst prepared by the above method. do.

In the reaction, as the solvent, a solvent generally used in a 5-membered ring carbonate synthesis reaction may be used as it is, preferably an aprotic solvent, and examples thereof include dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). There is).

Hereinafter, the present invention will be described in more detail.

The phase transfer catalyst according to the present invention has a form in which a quaternary ammonium salt is supported as a catalyst component on a polymer support, and the catalyst is present in a stable state at room temperature. The polystyrene-based polymer used as a support for the catalyst is obtained by partially polymerizing styrene and divinylbenzene and then polymerizing by adding vinylbenzene chloride, wherein the content of each component is 55-89 wt% based on the starting material, It is preferable that the divinylbenzene is 1-20% by weight and the vinylbenzene chloride is 10-40% by weight, and thus the polystyrene-based polymer finally obtained has thermosetting properties and is significantly improved in terms of material transfer properties and mechanical properties. When the content of divinylbenzene is less than 1% by weight, the mechanical strength is lowered, and when the content of divinylbenzene is more than 20% by weight, it is difficult for the reactants to access the catalytic active region. In addition, when the content of vinylbenzene chloride is less than 10% by weight, the supporting amount of the quaternary ammonium salt serving as a catalyst component is reduced, and when it exceeds 40% by weight, it is difficult for the reactants to penetrate into the carrier. Therefore, it is important to keep the content of each component in the above range.

The catalyst of the present invention is prepared by dissolving the composition containing the main components in water, partially polymerized at 20 to 50 ° C., and then adding vinylbenzene chloride and polymerizing to prepare a polystyrene-based polymer in a grafted form. It carries a quaternary ammonium salt. The method is as follows. First, quaternization occurs when tertiary amine is dissolved in dimethylformamide and reacted with a polymer support under a nitrogen atmosphere of 70-80 ° C. By this method, the phase transfer catalyst in the state where the quaternary ammonium salt is supported on the polystyrene crab support is finally obtained.

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

<Example 1>

Tributylamine was added to a polystyrene-based polymer support prepared by mixing 73% by weight of styrene and 12% by weight of divinylbenzene for 4 hours at 35 ° C for partial polymerization, and then polymerizing by adding 15% by weight of vinylbenzene chloride. Phase transfer catalyst carrying tributylbenzeneammonium chloride was prepared. A solution of 60 mmol of glycidyl methacrylate (GMA) in 100 mL of dimethylformamide (DMF) and the phase transfer catalyst (0.8 mmol based on the quaternary ammonium salt supported on the catalyst) were injected into a 300 mL Pyrex reactor. When heated slowly, the temperature of the reactor reaches 100 ℃ and the air on the solution is evacuated to carbon dioxide so that only carbon dioxide is present in the reactor and carbon dioxide is continuously supplied at a very small flow rate of about 3 mL / min. Stirring speed was set to 500rpm and the reaction was started simultaneously with stirring to carry out the reaction for 6 hours, and the reactor was cooled to separate the product. The yield of (2-oxo-1,3-dioxolan-yl) methyl methacrylate (DOMA) as the 5-membered ring carbonate produced was 67.7% based on the number of moles of GMA put into the reactor.

<Example 2-3>

The reaction was carried out under the same conditions as in Example 1, but DOMA was prepared using a catalyst in which the halogen atoms of the quaternary ammonium salt supported on the polymer support were replaced with bromine and iodine, respectively, and the yields at that time are shown in Table 1. .

TABLE 1

Yield of DOMA according to the kind of halogen atom of quaternary ammonium salt

Example Halogen atom yield(%) One Cl 81.7 2 Br 69.3 3 I 55.4

As can be seen from Table 1, when the quaternary ammonium salt of the catalyst is chloride, the yield of DOMA was shown to be the highest, and in the case of iodide, the yield is not preferable.

<Example 4-8>

The reaction was carried out under the same conditions as in Example 1, but when the catalyst was prepared, the content of divinylbenzene was changed to 1 to 20% by weight, and correspondingly, the reaction was carried out while the content of styrene was changed to 65 to 84% by weight. After preparing the DOMA using a catalyst prepared by supporting a quaternary ammonium salt on the prepared polymer support, the yield is measured and shown in Table 2.

TABLE 2

DOMA Yield According to Divinylbenzene Content in Polymer Support of Catalyst

Example Divinylbenzene Content (wt%) Styrene Content (wt%) Yield (%) One 12 73 81.7 4 One 84 68.9 5 2 81 74.2 6 6 77 78.8 7 16 69 71.6 8 20 65 65.3

As can be seen from Table 2, the yield was generally satisfactory in all the examples, but especially when the divinylbenzene content was about 6 to 12% by weight, DOMA was obtained at the highest yield.

<Example 9-11>

The reaction was carried out under the same conditions as in Example 1, except that the polymer support was prepared while changing the content of vinylbenzene chloride to 10 to 40% by weight, and the quaternary ammonium salt was supported on the prepared polymer support. After using to prepare DOMA, the yield is measured and shown in Table 3.

TABLE 3

DOMA Yield According to Vinylbenzene Chloride Content in Polymer Supports of Catalysts

Example Vinylbenzene chloride content (% by weight) Yield (%) 9 10 69.6 One 20 81.7 10 30 82.1 11 40 74.4

As can be seen from Table 3, the maximum yield of DOMA is shown when a catalyst having a vinylbenzene chloride content of 30% by weight is used.

<Example 12-13>

The reaction was carried out under the same conditions as in Example 1, but a 5-membered ring carbonate synthesis reaction was carried out while changing a solvent to prepare DOMA, and the yield thereof was shown in Table 4 below.

TABLE 4

DOMA yield depending on the type of solvent

Example Type of solvent Yield (%) 12 toluene 22.4 13 DMSO 65.4 One DMF 81.7

From Table 4, it can be seen that DOMA can be obtained in a high yield when using DMSO or DMF as an aprotic solvent as compared with using toluene as a solvent.

<Example 14-16>

The reaction was carried out under the same conditions as in Example 1, after synthesis of DOMA using a catalyst prepared by changing the carbon number of the alkyl group of the quaternary ammonium salt supported on the polymer support to 2 to 8, and then measuring the yield of the following table 5 is shown.

TABLE 5

DOMA Yield According to Carbon Number of Alkyl Group of Quaternary Ammonium Salts of Catalysts

Example Carbon number of alkyl group Yield (%) 14 2 68.7 One 4 81.7 15 6 78.5 16 8 72.9

The yield of DOMA was found to be the highest when using a catalyst having tributylbenzeneammonium chloride having 4 carbon atoms in the alkyl group.

<Example 17-18>

The reaction was carried out under the same conditions as in Example 1, but DOMA was prepared using the catalyst prepared while changing the partial polymerization time to 4 to 16 hours, and the yield thereof was shown in Table 6 below.

TABLE 6

DOMA yield according to partial polymerization time during catalyst preparation

Example Partial polymerization time (hours) Yield (%) One 4 81.7 17 8 76.4 18 16 69.2

The yield was the highest when the catalyst obtained when the partial polymerization time of styrene and divinylbenzene was made into 4 hours was used.

<Example 19-24>

The reaction was carried out under the same conditions as in Example 1, the catalyst was separated, dried, and reused several times to carry out 5-membered ring carbonate synthesis to prepare DOMA, and the yield thereof was shown in Table 7 below.

TABLE 7

DOMA yield according to the number of uses of the catalyst

Example Number of consecutive uses Yield (%) 19 2 82.1 20 4 81.4 21 6 81.7 22 8 81.5 23 10 80.9 24 12 46.6

As shown in Table 7, the catalyst of the present invention shows the same DOMA yield as the initial stage even after being recovered and reused up to 10 times. In the case of 12 reuses, part of the catalyst was stripped off the support and the yield decreased. Therefore, it is preferable to set the appropriate reuse frequency to 10 times or less.

<Comparative Example 1-3>

The reaction was carried out under the same conditions as in Example 1, but after the synthesis of DOMA using a catalyst obtained by supporting tetrabutylammonium chloride on an inorganic metal oxide such as silica or alumina, the yield was measured and shown in Table 7 below. .

TABLE 8

DOMA yield according to the type of carrier

Comparative Example Body Yield (%) One SiO ₂ 42.3 2 α-Al ₂ O ₃ 0 3 γ-Al ₂ O ₃ 25.8

As can be seen from Table 8, when alumina or silica is used as a carrier, the yield of DOMA is much lower than when the polymer support of the present invention is used as a carrier.

<Comparative Example 4>

The reaction was carried out under the same conditions as in Example 1, but DOMA was synthesized using a catalyst obtained by simultaneously polymerizing styrene, divinylbenzene, and vinylbenzene chloride. In this case, the yield was 65.2%, which is the case of synthesizing DOMA using a catalyst prepared by Example 1 of the present invention, that is, a method of partially polymerizing styrene and divinylbenzene and then mixing and polymerizing vinylbenzene chloride. It was significantly lower than the yield of 81.7%.

As described above, according to the five-membered ring carbonate synthesis method using the catalyst prepared according to the method of the present invention, there is no difficulty in recovering the catalyst, and the catalyst can be recovered and reused. can do.

Claims (5)

(a) partially polymerizing 55-89 parts by weight of styrene and 1-20 parts by weight of divinylbenzene; and (b) adding 10-40 parts by weight of vinylbenzene chloride to the partial polymer obtained in step (a) to polymerize. Forming a polymeric support, and (c) halogenated trialkylbenzylammonium (R ₃ -benzylammonium-X: the alkyl group (R) is an alkyl group having 2-8 carbons, and X is Cl or Br) Method for producing a phase transfer catalyst, characterized in that it comprises a step of supporting). Using a phase transfer catalyst prepared by the method of claim 1, the carbon dioxide and the epoxide derivative at a normal pressure of 50 to 120 ℃ for a 2 to 24 hours, the method of producing a five-membered ring carbonate compound. The method according to claim 2, wherein an aprotic solvent is used as a reaction solvent of the reaction. 4. The process of claim 3 wherein said aprotic solvent is dimethylformamide (DMF) or dimethylsulfoxide (DMSO). 3. The method of claim 2, wherein the epoxide derivative is glycidyl methacrylate and the 5-membered ring carbonate is (2-oxo-1,3-dioxolan-4-yl) methyl methacrylate (DOMA). How to feature.