KR20180043682A - Process for preparing organic zinc catalyst - Google Patents

Abstract

The present invention relates to a manufacturing method of an organic zinc catalyst capable of being used as a catalyst for manufacturing polyalkylene carbonate. More specifically, the present invention provides a manufacturing method of an organic zinc catalyst and a manufacturing method of a polyalkylene carbonate resin using an organic zinc catalyst manufactured thereby, wherein a specific alcohol solvent in a predetermined content range is used in a reaction of a zinc precursor and dicarboxylic acid, thereby realizing excellent catalyst activity in a manufacturing process of a polyalkylene carbonate resin and easily removing the remaining catalyst within the manufactured polyalkylene carbonate resin. The manufacturing method of an organic zinc catalyst comprises a step of forming a zinc dicarboxylate-based catalyst by conducting reaction of the zinc precursor and the dicarboxylic acid having 3 to 20 carbon atoms under liquid medium containing 1 to 8 volume% of the alcohol solvent having 10 to 23 carbon atoms.

Description

PROCESS FOR PREPARING ORGANIC ZINC CATALYST [0002]

The present invention relates to a process for preparing an organic zinc catalyst which can be used as a catalyst for the production of polyalkylene carbonate.

Since the Industrial Revolution, mankind has built a modern society by consuming a large amount of fossil fuels, while increasing the atmospheric carbon dioxide concentration and further promoting this increase by environmental destruction such as deforestation. Since global warming is caused by the increase of greenhouse gases such as carbon dioxide in the atmosphere and freon or methane, it is very important to reduce the atmospheric concentration of carbon dioxide which contributes to global warming. Are being carried out on a global scale.

Among them, the copolymerization reaction of carbon dioxide and epoxide found by Inoue et al. Is expected as a reaction to solve the problem of global warming, and it is actively studied not only in terms of fixation of chemical carbon dioxide but also in the use of carbon dioxide as carbon resources . Particularly, in recent years, the polyalkylene carbonate resin obtained by the polymerization of carbon dioxide and epoxide is widely regarded as a kind of biodegradable resin.

Various catalysts for the production of such polyalkylene carbonate resins have been studied and proposed, and zinc dicarboxylate catalysts such as zinc glutarate catalysts having zinc and dicarboxylic acid bonded thereto are known as typical catalysts Non-Patent Documents 1 to 3).

Such a zinc dicarboxylate catalyst, typically a zinc glutarate catalyst, is formed by reacting a zinc precursor and a dicarboxylic acid such as glutaric acid, and has a fine crystalline particle shape. However, zinc dicarboxylate catalysts in the form of such crystalline particles have various defects. For example, there is a problem that the polymerization activity of the catalyst is low, and there is a high risk that the catalyst will be incorporated into the product in the purification process after the polymerization reaction. Particularly, after the polyalkylene carbonate resin is produced, a part of the zinc dicarboxylate-based catalyst is left in the polyalkylene carbonate resin, and it is necessary to maintain the purity and color of the polyalkylene carbonate by removing it. However, when the dispersibility in the polymerization solvent is enhanced by using a surfactant or the like to enhance the activity of the zinc dicarboxylate catalyst, the catalyst is separated from the solution in which the polyalkylene carbonate resin obtained in the polymerization reaction is dissolved It may be difficult. Accordingly, it is very important to design a catalyst which is not only highly active but also capable of separating from a polyalkylene carbonate resin, compared with a conventional zinc dicarboxylate catalyst.

Therefore, there is a need for research into development of an organic zinc catalyst which exhibits high catalytic activity in the production of polyalkylene carbonate resin and which can easily separate the catalyst from the product in the purification process after polymerization.

 Phys. Chem. Chem. Phys. 5 (2003), 929-934  J. Am. Chem. Soc. 133 (2011), 13151-13161  J. Appl. Polym. Sci. 40 (2002), 3579-3591

The present invention provides a process for producing a catalyst for producing a polyalkylene carbonate resin, which is excellent not only in catalytic activity but also in that the catalyst can be easily removed in the produced polyalkylene carbonate resin .

In addition, the present invention provides a catalyst prepared by the above production method and a process for producing a polyalkylene carbonate resin using the same.

According to an embodiment of the present invention, a zinc precursor and a dicarboxylic acid having 3 to 20 carbon atoms are reacted with each other in a liquid medium containing 1 to 8% by volume of an alcohol solvent having 10 to 23 carbon atoms to form a zinc dicarboxylate Forming a catalyst based on an organometallic catalyst.

For example, the alcohol solvent may be selected from the group consisting of 1-decanol, 1-undecanol, 1-dodecanol, 1-tridecanol, 1- 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol, 1- octaecanol, 1-nonadecanol, 1-eicosanol, 1-heneicosanol, 1-docosanol and 1-trico And 1-tricosanol.

The liquid medium may be used together with the alcohol solvent in at least one solvent selected from the group consisting of toluene, benzene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, dimethyl carbonate, and diethyl carbonate . ≪ / RTI >

Under such liquid medium, a zinc precursor and a dicarboxylic acid are reacted to form a zinc dicarboxylate-based catalyst. Here, the zinc precursor is selected from the group consisting of _{ZnO, Zn (NO 3) 2} , Zn (acac) 2, Zn (OH) 2, Zn (OAc) 2, ZnSO 4, and Zn (ClO _{3) 2} 1 jong Or more.

The dicarboxylic acid which reacts with the zinc precursor may be selected from the group consisting of malonic acid (HOOC (CH ₂ ) COOH), succinic acid (HOOC (CH ₂ ) ₂ COOH) the group consisting of glutaric acid _{(glutaric acid, HOOC (CH 2} ) 3 COOH), adipic acid _{(adipic acid, HOOC (CH 2} ) 4 COOH), and pimelic acid _{(pimelic acid, HOOC (CH 2} ) 5 COOH) ≪ / RTI >

The dicarboxylic acid may be used in a ratio of 0.8 to 2 mol based on 1 mol of the zinc precursor.

The reaction of the zinc precursor and the dicarboxylic acid can be carried out at a temperature of 20 ° C to 110 ° C for 1 hour to 20 hours.

According to another embodiment of the present invention, there is provided a process for producing a polyalkylene carbonate resin, which comprises polymerizing a monomer including an epoxide and carbon dioxide in the presence of an organic zinc catalyst prepared by the above- do.

The organic zinc catalyst prepared according to the present invention not only achieves excellent catalytic activity in the production process of a polyalkylene carbonate resin by using a specific alcohol solvent in a predetermined content range in the reaction of a zinc precursor and a dicarboxylic acid There is an excellent effect that the residual catalyst can be easily removed in the produced polyalkylene carbonate resin.

FIG. 1 is a graph of an X-ray diffraction analysis (ZG: Example 1, ZG1: Comparative Example 1, ZG2: Comparative Example 2, Comparative Example 3) of an organozinc catalyst prepared according to Example 1 of the present invention and Comparative Examples 1 to 5 ZG3: Comparative Example 3, ZG4: Comparative Example 4, ZG5: Comparative Example 5).
2 is a transmission electron micrograph of an organic zinc catalyst prepared according to Example 1 of the present invention and Comparative Examples 1 to 5 (ZG1: Comparative Example 1, (B) ZG2: Comparative Example 2 ZG3: Comparative Example 3, (d) ZG: Example 1, (e) ZG4: Comparative Example 4, and (ZG5: Comparative Example 5).
3 is a photograph showing centrifugal separation results of a polyalkylene carbonate resin prepared using an organozinc catalyst prepared according to Example 1 of the present invention and Comparative Example 4 according to a catalyst separation test. [(A) Example 1, (b) Comparative Example 4].

Hereinafter, a method for preparing an organic zinc catalyst according to a preferred embodiment of the present invention, a method for producing a polyalkylene carbonate resin using the same, and the like will be described in more detail.

In the present invention, the terms first, second, etc. are used to describe various components, and the terms are used only for the purpose of distinguishing one component from another.

Moreover, the terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to be limiting of the present invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, the terms "comprising," "comprising," or "having ", and the like are intended to specify the presence of stated features, But do not preclude the presence or addition of one or more other features, integers, steps, components, or combinations thereof.

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

According to one embodiment of the invention, there is provided a process for preparing an organic zinc catalyst which can be used as a catalyst for the production of polyalkylene carbonate. The method of preparing the organic zinc catalyst comprises reacting a zinc precursor with a dicarboxylic acid having 3 to 20 carbon atoms under a liquid medium containing 1 to 8% by volume of an alcohol solvent having 10 to 23 carbon atoms to form a zinc dicarboxylate catalyst .

In particular, in the present invention, a zinc dicarboxylate-based catalyst is prepared by reacting a zinc precursor with a dicarboxylic acid by using a specific alcohol solvent in a predetermined content range as described later, thereby producing a polyalkylene carbonate resin The present invention has been accomplished by confirming that it is easy to remove the residual catalyst in the produced polyalkylene carbonate resin.

The alcohol solvent may be 1-decanol, 1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octaecanol, 1-nonadecanol, 1-eicosanol, 1-heneicosanol, 1-docosanol, and 1-tricoic acid (1 -tricosanol), and the like. Among them, 1-dodecanol and the like are preferable in terms of effective dissociation of the catalyst while improving the dispersibility to the polymerization solvent and improving the catalytic activity.

In particular, since dodecanol is an alcohol having 12 carbon atoms, it is expected that a long hydrocarbon chain will be exposed on the surface when the catalyst is coordinated on the surface of the catalyst. As a result, the surface of the organic zinc catalyst becomes more hydrophobic, and the organic zinc catalyst is likely to be dispersed in an organic solvent such as dichloromethane. However, if the amount of alcohol coordinated on the surface of the catalyst or the length of the hydrocarbon chain excessively increases, the dispersion of the catalyst becomes too high, and separation in the polymer solution may become difficult. If the amount of alcohol is small or the length of the hydrocarbon chain is too large If it is small, it may be disadvantageous in terms of improving dispersibility. Therefore, if a low-alcohol having a low carbon number such as ethanol or pentanol is used, it is difficult to achieve such improvement in catalyst performance.

The alcohol solvent should be contained in an amount of 1 to 8 vol%, preferably 4 to 6 vol%, based on the volume of the total solvent constituting the liquid medium. The use amount of the alcohol solvent should be not less than 1% by volume in view of improving the catalytic activity to a high degree, and if it exceeds 8% by volume, it is not easy to separate the catalyst from the polymer resin solution. can see.

The liquid medium may be mixed with the alcohol solvent in one or more solvents selected from the group consisting of toluene, benzene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, dimethyl carbonate, diethyl carbonate, As shown in FIG. The liquid medium solvent such as toluene may be contained in an amount of 99 to 92% by volume based on the total volume of the solvent.

Under such liquid medium, a zinc precursor and a dicarboxylic acid are reacted to form a zinc dicarboxylate-based catalyst.

As the zinc precursor, any zinc precursor previously used in the production of a zinc dicarboxylate-based catalyst may be used without any limitation. Specific examples of the zinc precursor include ZnO, Zn (NO ₃ ) ₂ , _{Zn (acac) 2, Zn (} OH) 2, Zn (OAc) 2, ZnSO 4, and Zn (ClO _{3) 2} And the like. Of these, zinc oxide (ZnO) is preferable in terms of improving the catalyst yield.

The zinc precursor is preferably used in an amount ranging from about 1 to about 10 parts by weight based on the weight of toluene. If less than 1 part by weight, toluene is used excessively. If the amount is more than 10 parts by weight, the dispersion and agitation of the organic zinc catalyst particles in toluene may not be performed properly.

The dicarboxylic acid which reacts with the zinc precursor may be selected from the group consisting of malonic acid (HOOC (CH ₂ ) COOH), succinic acid (HOOC (CH ₂ ) ₂ COOH) made of such as glutaric acid _{(glutaric acid, HOOC (CH 2} ) 3 COOH), adipic acid _{(adipic acid, HOOC (CH 2} ) 4 COOH), and pimelic acid _{(pimelic acid, HOOC (CH 2} ) 5 COOH) Lt; / RTI > Here, glutaric acid may suitably be used as the dicarboxylic acid in view of the activity of the organic zinc catalyst, and the zinc dicarboxylate organic zinc catalyst is preferably a zinc glutarate catalyst.

The amount of the dicarboxylic acid to be used may range from 0.8 to 2, more preferably from 1 to 1.5, or from 1.1 to 1.3, based on the molar ratio of the dicarboxylic acid / zinc precursor. If the molar ratio is less than 0.8, the amount of the dicarboxylic acid is small and it is difficult to sufficiently crystallize the organic zinc catalyst. If the molar ratio is more than 2, the dicarboxylic acid is excessively used, which may be economically disadvantageous. For example, the dicarboxylic acid may be used in an equivalent or excess moles of the zinc precursor, and more specifically about 0.8 to 2 moles, or about 1 to 1.5 moles, about 1.1 to 1.3 moles, Ratio. When the reaction step is carried out while maintaining the dicarboxylic acid in the same or excessive amount as the zinc precursor, the reaction may proceed slowly in the form of an excessive amount of the dicarboxylic acid molecules or ions surrounding the zinc precursor dispersed uniformly . As a result, the zinc precursor can react with the dicarboxylic acid component while hardly aggregating with each other, so that an organic zinc catalyst having thinner, more surface-widened and improved activity can be obtained.

The reaction step may be carried out in the above-mentioned liquid medium in which the reactants including the zinc precursor and the dicarboxylic acid are present. For example, the reaction may proceed in the form of a solution or dispersion in which the reactants are dissolved or dispersed, The solution or dispersion containing the zinc precursor may be added to the solution or dispersion containing the carboxylic acid, That is, a solution or dispersion containing a certain amount of zinc precursor is first added to a solution or dispersion containing a dicarboxylic acid to conduct a reaction, and then a solution or dispersion containing the remaining zinc precursor is added to the remaining solution or dispersion, . As a result, it is possible to carry out the entire reaction step while maintaining the molar ratio of the dicarboxylic acid in the reaction system. From this, it is possible to obtain a zinc dicarboxylate-type organozinc compound having a more uniform and fine- A catalyst can be produced. Further, the entire reaction step may be carried out while dropping the solution or dispersion containing the zinc precursor uniformly in droplets in a solution or dispersion containing the dicarboxylic acid.

The reaction step between the zinc precursor and the dicarboxylic acid may be carried out at a temperature of about 20 to 110 DEG C, preferably 50 to 100 DEG C for about 1 to 20 hours. Further, it is already described that the zinc precursor can be divided at equal intervals during the entire reaction time, and the molar ratio of the dicarboxylic acid in the reaction system can be maintained throughout the entire reaction step. By proceeding the reaction step under these reaction conditions, an organozinc catalyst exhibiting improved activity can be produced in high yield.

The organozinc catalyst thus synthesized can be further separated and washed and dried. At this time, the separation and washing process may be performed by filtering the solid slurry obtained after the reaction step between the zinc precursor and the dicarboxylic acid, followed by washing with acetone about 2 to 3 times. The purpose of this washing process is to remove residual solvent and residual dicarboxylic acid. In addition, the drying process can be performed by drying the solid organic zinc catalyst obtained after the separation and washing step in a convection oven at 60 ° C. to 130 ° C. for 6 to 12 hours.

In addition to the steps described above, the method for preparing the organic zinc catalyst may further include steps that are conventionally employed in the art to which the present invention belongs.

According to another embodiment of the present invention, there is provided an organozinc catalyst prepared by the above-described method. The organic zinc catalyst is a catalyst containing zinc dicarboxylate particles obtained by treating a specific alcohol in a predetermined content range. The particles have an average particle thickness of 30 nm or less and an argon concentration of 10 m < ² > / g or more An organic zinc catalyst is provided which is a monoclinic particle having an adsorbed Bruner-Emmett-Teller (BET) surface area.

Basically, the zinc dicarboxylate-based particles are monoclinic particles, which are non-porous particles in which void spaces are hardly present in the crystal when the van der Waals' radius of constituent atoms is considered.

In particular, the organic zinc catalyst is obtained by reacting a zinc precursor with a dicarboxylic acid under a liquid medium, and may preferably be one prepared by the above-described method. That is, the organic zinc catalyst is prepared under a liquid medium containing 1 to 8% by volume of an alcohol solvent having 10 to 23 carbon atoms as described above.

Therefore, the organozinc catalyst has a long hydrocarbon skeleton on the surface thereof as compared with an organozinc catalyst prepared without using an alcohol solvent satisfying the above conditions, so that smooth distribution in the polymerization process of polyalkylene carbonate can be expected. In addition, since the alcohol solvent can be effectively separated from the polyalkylene carbonate resin by using the alcohol solvent in a predetermined small amount of the optimized range, the catalytic activity in the polymerization experiment is very significant.

According to another embodiment of the present invention, there is provided a process for producing a polyalkylene carbonate using an organic zinc catalyst produced by the method as described above.

Except for the use as an organozinc catalyst according to the present invention, a conventionally known process for producing a polyalkylene carbonate can be applied without limitation. For example, there is provided a process for producing a polyalkylene carbonate resin comprising the step of solution polymerizing a monomer containing an epoxide and carbon dioxide in the presence of an organic zinc catalyst according to the present invention.

In the process for producing such a resin, the organic zinc catalyst can be used as a heterogeneous catalyst, and the polymerization step can proceed with solution polymerization in an organic solvent. As a result, the heat of reaction can be appropriately controlled and the molecular weight or viscosity of the polyalkylene carbonate resin to be obtained can be controlled easily.

In such a solution polymerization, the solvent includes, for example, methylene chloride, ethylene dichloride, trichloroethane, tetrachloroethane, chloroform, acetonitrile, propionitrile, dimethylformamide, N- Methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, acetone, cyclohexanone, trichlorethylene, methyl acetate, vinyl acetate, ethyl acetate, At least one selected from the group consisting of propyl acetate, butyl lactone, caprolactone, nitropropane, benzene, styrene, xylene and methyl propasol can be used. Among them, by using methylene chloride or ethylene dichloride as a solvent, it is possible to more effectively proceed the polymerization reaction.

The solvent may be used in a weight ratio of about 1: 0.5 to 1: 100 to the epoxide, and suitably in a weight ratio of about 1: 1 to 1:10. At this time, if the ratio is less than about 1: 0.5, the solvent does not function properly as a reaction medium, and it may be difficult to take advantage of the above-mentioned solution polymerization. When the ratio is more than about 1: 100, the concentration of the epoxide or the like may be relatively low, resulting in a decrease in productivity, and the molecular weight of the finally formed resin may be lowered or the side reaction may increase.

In addition, the organic zinc catalyst may be added in a molar ratio of about 1:50 to 1: 1000 relative to the epoxide. More preferably, the organozinc catalyst can be introduced at a molar ratio of about 1:70 to 1: 600, or about 1: 80 to 1: 300, relative to the epoxide. If the ratio is too small, it is difficult to exhibit sufficient catalytic activity in solution polymerization. On the other hand, if the amount is excessively large, by using an excessive amount of catalyst, by-products may not be produced, or by back- This can happen.

On the other hand, the pressure of the carbon dioxide is not particularly limited, but may be adjusted to preferably 0.1 to 20 MPa or 0.1 to 10 MPa, or 0.1 to 5 MPa in view of the reaction efficiency. Particularly, in the polymerization process for producing the polyalkylene carbonate resin using the organozinc catalyst of the present invention, only a certain amount of carbon dioxide is injected compared with the conventional polymerization process in which carbon dioxide is continuously injected.

The epoxide may be an alkylene oxide having 2 to 20 carbon atoms, which is substituted or unsubstituted with halogen or an alkyl group having 1 to 5 carbon atoms; A cycloalkylene oxide having 4 to 20 carbon atoms substituted or unsubstituted with halogen or an alkyl group having 1 to 5 carbon atoms; And styrene oxide having 8 to 20 carbon atoms substituted or unsubstituted with halogen or an alkyl group having 1 to 5 carbon atoms. Typically, as the epoxide, an alkylene oxide having 2 to 20 carbon atoms, which is substituted or unsubstituted with a halogen or an alkyl group having 1 to 5 carbon atoms, may be used.

Specific examples of such epoxides include ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, octene oxide, decene oxide, dodecene oxide, tetradecene oxide, hexadecene oxide, octadecene oxide, butadiene monoxide, Epichlorohydrin, epichlorohydrin, epichlorohydrin, epichlorohydrin, isopropyl glycidyl ether, butyl glycidyl ether, t-butyl glycidyl ether, 2-ethylhexyl Cyclododecene oxide, cyclododecene oxide, alpha-pinene oxide, 2,3-epoxy norbornene, limonene oxide, dieldrin, 2, 3-epoxycyclohexane, glycidyl ether, allyl glycidyl ether, cyclopentene oxide, cyclohexene oxide, cyclooctene oxide, 3-epoxypropylbenzene, styrene oxide, phenylpropylene oxide, stilbene oxide, chlorostilbene Methylphenyl ether, chlorophenyl-2,3-epoxypropyl ether, epoxypropylmethoxyphenyl ether, dipropylmethoxyphenyl ether, dipropylmethoxyphenyl ether, dipropylmethoxyphenyl ether, Biphenyl glycidyl ether, glycidyl naphthyl ether, and the like. Most typically, ethylene oxide is used as the epoxide.

In addition, the above-mentioned solution polymerization can be carried out at about 30 to 100 DEG C and about 10 to 70 bar for about 1 to 60 hours. For example, the solution polymerization may be carried out at about 50 to 90 DEG C and about 20 to 50 bar for about 2 to 10 hours.

Meanwhile, the remaining polymerization processes and conditions except for the above-mentioned matters may depend on conventional polymerization conditions for the production of the polyalkylene carbonate resin, and a further explanation thereof will be omitted.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited thereto.

[Example]

Example 1 Preparation of Organozinc Catalyst with Small Dodecanol Content

5.30 g of glutaric acid was dispersed in 100 mL of toluene and stirred for 30 minutes at 55 ° C. Then 5 mL of 1-dodecanol was added to the dispersion and further stirred for 30 minutes. Then, 2.72 g of zinc oxide was further added to the above dispersion and stirred for 3 hours. The obtained solid dispersion was filtered to obtain a solid powder, which was washed with 200 mL of acetone. The washed solid powder was dried in a convection oven at 80 캜 for 15 hours to finally obtain a propanol-treated organic zinc catalyst. The obtained catalyst was named ZG.

Comparative Example 1. Preparation of propanol-treated organozinc catalyst

An organic zinc catalyst treated with pentanol was obtained in the same manner as in Example 1, except that 5 mL of 1-propanol was used. The obtained catalyst was named ZG1.

Comparative Example 2. Preparation of pentanol-treated organozinc catalyst

An organic zinc catalyst treated with pentanol was obtained in the same manner as in Example 1, except that 5 mL of 1-pentanol was used. The obtained catalyst was named ZG2.

Comparative Example 3. Preparation of octanol-treated organozinc catalyst

Octanol-treated organic zinc catalyst was obtained in the same manner as in Example 1, except that 5 mL of 1-octanol was used. The obtained catalyst was named ZG3.

Comparative Example 4 Preparation of an Organozinc Catalyst with Dodecanol Over-Treatment

An organic zinc catalyst treated with pentanol was obtained in the same manner as in Example 1, except that 10 mL of 1-dodecanol was used. The obtained catalyst was named ZG4.

Comparative Example 5. Preparation of an organic alcohol catalyst without alcohol treatment

An organic zinc catalyst not treated with alcohol was obtained in the same manner as in Example 1, except that no alcohol was used. The obtained catalyst was named ZG5.

[Experimental Example]

Experimental Example 1. X-ray diffraction analysis

X-ray diffraction analysis results of the organic zinc catalysts (ZG, ZG1, ZG2, ZG3, ZG4, and ZG5) obtained in Example 1 and Comparative Examples 1 to 5 are shown in FIG. All of the organozinc catalysts clearly showed diffraction peaks corresponding to zinc glutarate in the range of 2 theta = 10 - 25 degrees, from which the corresponding catalysts were produced smoothly through the above Experiments and Comparative Examples At the same time, it can be seen that there is no significant difference between the catalysts in terms of crystal structure.

EXPERIMENTAL EXAMPLE 2 Transmission Electron Microscopy (TEM)

2 shows a photograph of the organic zinc catalysts (ZG, ZG1, ZG2, ZG3, ZG4, and ZG5) obtained in Example 1 and Comparative Examples 1 to 5 by transmission electron microscopy ZG1: Comparative Example 1, (B) ZG2: Comparative Example 2, (C) ZG3: Comparative Example 3, (D) ZG: 5]. As shown in Fig. 2, all of the produced catalysts showed catalyst particles at a level of several hundred micrometers (占 퐉).

Experimental Example 3: Preparation of polyalkylene carbonate resin

A polyalkylene carbonate resin was prepared in the following manner using the organic zinc catalysts (ZG, ZG1, ZG2, ZG3, ZG4, and ZG5) obtained in Example 1 and Comparative Examples 1 to 5 as catalysts .

First, 0.2 g of catalyst and 8.5 g of dichloromethane were placed in a stainless steel high-pressure reactor. Then, 10 g of ethylene oxide (EO) was added to the reactor, and carbon dioxide (CO ₂ ) was introduced into the reactor under a pressure of 30 bar. After polymerization was carried out at 70 ° C for 3 hours, unreacted ethylene oxide and carbon dioxide were removed together with the solvent dichloromethane. At this time, the amount (g) of the obtained polymer was quantitatively determined, and the activity of the catalyst per unit weight (g) of the catalyst was measured.

The catalyst activity for the polyalkylene carbonate resin production process using the organic zinc catalyst obtained in Example 1 and Comparative Examples 1 to 5 is as shown in Table 1 below.

catalyst Catalytic activity (g-polymer / g-catalyst) Example 1 (ZG) 41 Comparative Example 1 (ZG1) 22 Comparative Example 2 (ZG2) 20 Comparative Example 3 (ZG3) 25 Comparative Example 4 (ZG4) 43 Comparative Example 5 (ZG5) 26.9

As shown in Table 1, the organozinc catalyst (ZG) of Example 1 and the organozinc catalyst (ZG4) of Comparative Example 4, which were treated with dodecanol in the production of the polyalkylene carbonate resin, were subjected to separate alcohol treatment (ZG1, ZG2, ZG3) of Comparative Examples 1 to 3 treated with an organic zinc catalyst (ZG5) of Comparative Example 5 and propanol, pentanol, and octanol. This is believed to be attributable to the fact that dispersion of the reaction solvent phase of the organic zinc catalyst by the alcohol treatment of 10 or more carbon atoms is advantageous. In particular, the catalyst of Example 1 exhibited a higher polymerization activity, that is, an activity increase of more than 50% as compared with Comparative Example 5, compared with the organic zinc catalyst using low-carbon alcohol of Comparative Examples 1 to 3 and the general organic zinc catalyst of Comparative Example 5 You can see what you see directly.

Experimental Example 4. Separation of Catalyst from Polyalkylene Carbonate

200 mg of a polyalkylene carbonate resin prepared by using the organozinc catalyst (ZG) of Example 1 and the organozinc catalyst (ZG4) of Comparative Example 4 in Experimental Example 3 was dissolved in dichloromethane 6 (5,000 rpm, 10 minutes), and a photograph of the result of centrifugation of the polyalkylene carbonate resin thus measured according to the experiment is shown in FIG. 3. [(a) Example 1, (b) Comparative Example 4], and FIG. 3 shows a catalyst layer in which a yellow portion is centrifuged.

As shown in FIG. 3, it was confirmed that when the organic zinc catalyst treated with 5 mL of dodecanol was applied according to Example 1, the catalyst could be clearly separated from the polymer solution. On the other hand, in the case of using the organic zinc catalyst treated with 10 mL of dodecanol in accordance with Comparative Example 1, it can be seen that the catalyst is not separated from the polymer solution but is mixed in spite of performing the centrifugation process. From this, it can be confirmed that excessive use of excessive amount of alcohol in the amount of alcohol is difficult to separate due to excessive dispersion in the polymer solution.

In general, it is necessary to be able to separate the catalyst from the polymer resin solution, that is, the solution in which the polymer resin is dissolved in dichloromethane, by centrifugation at 5,000 to 10,000 rpm for about 10 to 20 minutes. When the catalyst is not separated as in the case of the ZG4 catalyst of Comparative Example 4, no matter how high the polymerization activity, the catalyst is excessively contained in the polymer resin.

Claims (9)

A step of reacting a zinc precursor with a dicarboxylic acid having 3 to 20 carbon atoms to form a zinc dicarboxylate catalyst under a liquid medium containing 1 to 8 vol% of an alcohol solvent having 10 to 23 carbon atoms Zinc catalyst.
The method according to claim 1,
The alcohol solvent may be selected from the group consisting of 1-decanol, 1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, Wherein the organic zinc catalyst is at least one selected from the group consisting of octadecanol, 1-nonadecanol, 1-eicosanol, 1-heneicosol, 1-dococanol and 1-tricoic acid.
The method according to claim 1,
Wherein the liquid medium comprises at least one solvent selected from the group consisting of toluene, benzene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, dimethyl carbonate, and diethyl carbonate. ≪ / RTI >
The method according to claim 1,
The zinc precursor is _{ZnO, Zn (NO 3) 2} , Zn (acac) 2, Zn (OH) 2, Zn (OAc) 2, ZnSO 4, and Zn (ClO ₃₎ 1 jong or more organic selected from the group consisting of ₂ Zinc catalyst.
The method according to claim 1,
Wherein the dicarboxylic acid is at least one member selected from the group consisting of malonic acid, succinic acid, glutaric acid, adipic acid, and pimelic acid.
The method according to claim 1,
Wherein the dicarboxylic acid is used in a ratio of 0.8 to 2 moles per 1 mole of the zinc precursor.
The method according to claim 1,
Wherein the reaction temperature is 20 ° C to 110 ° C.
The method according to claim 1,
Wherein the reaction time is 1 hour to 20 hours.
A process for producing a polyalkylene carbonate resin, which comprises polymerizing a monomer containing an epoxide and carbon dioxide in the presence of an organic zinc catalyst produced by the process of any one of claims 1 to 8.

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