KR20180007574A - Organic zinc supported catalyst, preparation method of the catalyst, and preparation method of poly(alkylene carbonate) resin using the catalyst - Google Patents

Abstract

The present invention relates to an organic zinc supported catalyst, a preparation method thereof and a method for preparing a poly(alkylene carbonate) resin using the catalyst. The organic zinc supported catalyst according to the present invention shows improved activities in a polymerization process for manufacturing a poly(alkylene carbonate) resin and can easily collect poly(alkylene carbonate) after polymerization.

Description

Technical Field [0001] The present invention relates to an organic zinc-supported catalyst, an organic zinc-supported catalyst, a method for producing the same, and a method for producing a polyalkylene carbonate resin using the catalyst. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to an organic zinc-supported catalyst which exhibits improved activity in the course of polymerization for the production of polyalkylene carbonate resin and which can be recovered easily after polymerization, a method for producing the same, and a process for producing a polyalkylene carbonate resin using the catalyst will be.

The polyalkylene carbonate is an amorphous transparent resin, unlike an aromatic carbonate which is an engineering plastic of a similar type, has only an aliphatic structure, and is synthesized by a copolymerization reaction under a catalyst in which carbon dioxide and epoxide are used as monomers. These polyalkylene carbonates have excellent transparency, elongation and oxygen barrier properties, exhibit biodegradability, and are completely decomposed into carbon dioxide and water during combustion, leaving no carbon residue.

Accordingly, various catalysts for the production of polyalkylene carbonate resins have been studied and proposed, and zinc dicarboxylate-based catalysts such as zinc glutarate catalysts having zinc and dicarboxylic acid bonded thereto are known as typical catalysts.

Such a zinc dicarboxylate catalyst, typically a zinc glutarate catalyst, is formed by reacting a zinc precursor with a dicarboxylic acid, such as glutaric acid, and is in the form of a fine crystalline particle. However, it has been difficult to control the zinc dicarboxylate type catalyst in the form of crystalline particles so as to have a uniform and fine particle size in its production process. Conventional zinc dicarboxylate catalysts have a particle size on the nanometer scale, but as agglomerates of the catalyst particles in the medium are formed, agglomerates having a larger particle diameter and a smaller surface area are formed. Thus, the production of a polyalkylene carbonate resin There is a problem that the catalytic activity decreases.

In this connection, it has been found that the smaller the size of the zinc precursor used in the preparation of the zinc dicarboxylate-based catalyst, the greater the effect on the activity increase of the produced catalyst.

Generally zinc oxide powder used as a zinc source (zinc precursor) in the manufacture of zinc dicarboxylate catalysts is an ionic binder having a particle size of several tens to several hundred nanometers and a specific surface area of about 10 m < 2 > / g . These zinc oxide powders have a very high polarity and are well dispersed in polar solvents, but in non-polar solvents, the particles aggregate together to form very large aggregates. When the catalyst synthesis reaction is carried out in the state where the particles are aggregated, the heterogeneous reaction proceeds in the entire reaction system, and the heterogeneity of the produced catalyst crystals is increased and the activity of the catalyst is also low.

In this regard, International Patent Publication No. WO 2011/107577 discloses a method of synthesizing a catalyst after surface treatment of a zinc source used in the production of an organozinc catalyst with an organosilane to increase the specific surface area of the zinc source. However, since the surface modification of the zinc source using the organosilane must be preceded by several steps (such as reaction, selection, and drying), the above-described method has a limit in that the manufacturing process is not efficient compared to the effect of improving the catalytic activity.

For this reason, conventionally known zinc dicarboxylate catalysts often have relatively large particle sizes and nonuniform particle morphologies. However, when the above-described zinc dicarboxylate catalyst is applied to a polymerization process for producing a polyalkylene carbonate resin, a sufficient contact area between the reactant and the catalyst can not be ensured and the polymerization activity can not be sufficiently expressed have.

In addition, existing zinc dicarboxylate-based catalysts require depolymerization of the polymerized polyalkylene carbonate resin by a backbiting reaction, and hence removal from the resin after completion of the polymerization. For this purpose, it is possible to use a method in which a coagulant is added and then the catalyst is physically removed by using a filter, or the catalyst is chemically removed by using an ion exchange resin. However, removal of the zinc dicarboxylate-based catalyst using these methods requires a lot of energy and further processing including a step of lowering the viscosity by further adding a solvent, removing the catalyst and then removing the solvent, There is a problem that the catalyst used in the polymerization is difficult to be reused.

The present invention provides an organic zinc-supported catalyst which exhibits improved activity in the polymerization process for the production of a polyalkylene carbonate resin and is easy to recover after polymerization.

Also, the present invention provides a process for producing the organic zinc-supported catalyst.

In the present invention, a method for producing a polyalkylene carbonate resin using the organic zinc catalyst is provided.

According to the present invention

A carbon support surface-treated with at least one macromolecular compound selected from the group consisting of a cationic polymer, an anionic polymer, and an amphoteric polymer; And

A zinc dicarboxylate compound supported on a carbon support surface-treated with the polymer compound

An organic zinc supported catalyst is provided.

Further, according to the present invention,

A polymeric compound selected from the group consisting of a cationic polymer, an anionic polymer, and an amphoteric polymer, and a carbon support are mixed in a solvent, and a solution of a mixture of a cationic group, an anionic group, and an amphoteric group selected from the group consisting of a cationic group, Forming a carbon support into which at least two ionic groups have been introduced; And

Reacting a zinc precursor with a dicarboxylic acid having 3 to 20 carbon atoms in a solution containing the carbon support to form a zinc dicarboxylate compound supported on the carbon support

≪ / RTI > is provided.

According to the present invention, there is also provided 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-supported catalyst.

Hereinafter, an organic zinc-supported catalyst according to embodiments of the present invention, a method for producing the same, and a method for producing a polyalkylene carbonate resin using the catalyst will be described in detail.

Prior to that, unless explicitly stated to the contrary, the terminology is used merely to refer to a specific embodiment and is not intended to limit the invention.

The singular forms as used herein include plural forms as long as the phrases do not expressly contradict it.

Means that a particular feature, region, integer, step, operation, element and / or component is specified, and that other specific features, regions, integers, steps, operations, elements, components and / And the like.

As used herein, the term "supported catalyst" refers to a catalyst prepared by fixing a catalyst having activity to a desired chemical reaction on a support having inert activity to enhance the activity of the catalyst or to obtain additional advantages have. At this time, the catalyst may be chemically or physically fixed to the pores on the surface or inside of the support.

Therefore, the term "organozinc supporting catalyst" means an organozinc catalyst, such as a zinc dicarboxylate catalyst having activity in the production of a polyalkylene carbonate resin, in the presence of a covalent bond or a coordination bond May be referred to as being fixed by chemical bonding or by physical force such as adhesion, adhesion, adsorption, or at least part of which is embedded.

I. Organozinc Supported Catalyst

According to one embodiment of the invention,

A carbon support surface-treated with at least one macromolecular compound selected from the group consisting of a cationic polymer, an anionic polymer, and an amphoteric polymer; And

A zinc dicarboxylate compound supported on a carbon support surface-treated with the polymer compound

An organic zinc supported catalyst is provided.

As a result of continuous research by the present inventors, it has been found that a catalyst in which a reaction product of a zinc precursor and a dicarboxylic acid is carried on a carbon support surface-treated with a polymer compound such as a cationic polymer, an anionic polymer, an amphoteric polymer, It was confirmed that the catalyst showed a high dispersibility in the solution for the polymerization of carbonates while suppressing the catalyst aggregation and exhibited an improved polymerization activity.

This effect is expected to be due to the fact that the organozinc catalyst, which is difficult to disperse well in the nonpolar solvent used as a medium in the preparation of the catalyst, may be inhibited from intermixing due to ionic bonding with the surface treated carbon support. Furthermore, since the surface-treated carbon support can prevent catalyst aggregation even after the catalyst is dried, it is considered that the organic zinc catalyst exhibits high activity.

That is, the organozinc catalyst supported on the surface-treated carbon support has a low density and a large surface area, so that the distance between the catalyst particles is distanced by the carbon support having a large surface area. As a result, the polymer having a high viscosity is uniformly distributed And can form conditions in which the monomer can easily access the active site of the catalyst.

In this embodiment, the carbon support is a carbon support.

The carbon support may have various shapes such as a one-dimensional acicular shape, a two-dimensional plate shape, a three-dimensional spherical shape, or a rod shape. Preferably, the carbon support may be advantageous to inhibit aggregation of the organozinc catalyst, with spherical particles connected or in a similar form.

For example, the carbon support may be a carbon nanotube, a graphite, a graphene, an activated carbon, a mesoporous carbon, a carbon black, a carbon nano- At least one selected from the group consisting of carbon nanofibers, carbon nanowires, carbon nanohorns, carbon aerogels, carbon nanoring, and fullerenes (C60) Lt; / RTI >

Particularly, in this embodiment, the carbon support is surface-treated with a polymer compound having a charge. That is, the carbon support is coated with a polymer compound having at least a part of the surface of the carbon support, and an ionic group having a charge is introduced.

Since the organic zinc-supported catalyst of the embodiment includes the carbon support surface-treated with the polymer having charge, it can exhibit higher activity than the catalyst prepared without such a carbon support, It has an advantage that it is easy.

According to one embodiment of the present invention, the polymer compound having the charge may be a surfactant, a synthetic polymer having charge, or an ion exchange resin; Preferably, it may be at least one polymer compound selected from the group consisting of a cationic polymer, an anionic polymer, and an amphoteric polymer.

Examples of the cationic polymer include poly (allylamine hydrochloride), poly (ethylene imine), poly (L-lysine), poly (ethyleneimine) (Diallyldimethyl ammonium chloride), poly (vinylamine hydrochloride), poly (2- (dimethylamino) ethyl methacrylate) (poly (2- dimethylamino) ethyl methacrylate), and poly (amido amine) (poly (amido amine)).

The anionic polymer may be selected from the group consisting of polyglutamic acid, polyacrylic acid, poly (styrene sulfonate), carboxymethyl cellulose, cellulose sulfate, At least one compound selected from the group consisting of dextran sulfate, heparin sulfate, and poly (methylene-co-guanidine).

The ampholytic polymer may be at least one selected from the group consisting of cocamidopropyl betaine, octyl betaine, cetyl betaine, and stearyl betaine. Compounds are exemplified.

On the other hand, the organic zinc-supported catalyst according to one embodiment of the present invention includes a zinc dicarboxylate compound supported on a carbon support surface treated with the polymer compound.

The zinc dicarboxylate compound is a reaction product of a zinc precursor and a dicarboxylic acid having 3 to 20 carbon atoms and is supported by chemical or physical bonding with an ionic group on a carbon support surface treated with the polymer.

Here, the zinc precursor is zinc oxide (ZnO), zinc sulfate (ZnSO _4), chlorate, zinc _{(Zn (ClO 3) 2)} , zinc nitrate _{(Zn (NO 3) 2)} , zinc acetate (Zn (OAc) ₂₎ , And zinc hydroxide (Zn (OH) ₂ ).

The dicarboxylic acid having 3 to 20 carbon atoms may be at least one compound selected from the group consisting of malonic acid, glutaric acid, succinic acid, adipic acid, terephthalic acid, isophthalic acid, homophthalic acid, and phenylglutaric acid .

Specifically, the zinc dicarboxylate-based compound may be at least one selected from the group consisting of zinc malonate, zinc glutarate, zinc succinate, zinc adipate, zinc terephthalate, zinc isophthalate, zinc homophthalate, and zinc phenyl glutarate ≪ / RTI > Preferably, zinc glutarate is advantageous as the zinc dicarboxylate compound in view of the activity of the organic zinc-supported catalyst.

The zinc dicarboxylate compound is produced by chemically reacting the zinc precursor and the dicarboxylic acid on the carbon support. Accordingly, an organic zinc-supported catalyst can be formed on the carbon support without a separate process for supporting the zinc dicarboxylate compound.

The dicarboxylate compound may be supported on at least a part of the carbon support surface treated with the polymer compound in the form of a coating or attached thereto or in the form of a flake on a carbon support surface treated with the polymer May be carried.

According to one embodiment of the present invention, the zinc dicarboxylate compound may be supported on the carbon support to form a thin film having a thickness of 10 nm to 100 nm and a flake having a size of 20 nm to 700 nm.

II. Method for producing organic zinc catalyst

On the other hand, according to another embodiment of the invention,

A polymeric compound selected from the group consisting of a cationic polymer, an anionic polymer, and an amphoteric polymer, and a carbon support are mixed in a solvent, and a solution of a mixture of a cationic group, an anionic group, and an amphoteric group selected from the group consisting of a cationic group, Forming a carbon support into which at least two ionic groups have been introduced; And

Reacting a zinc precursor with a dicarboxylic acid having 3 to 20 carbon atoms in a solution containing the carbon support to form a zinc dicarboxylate compound supported on the carbon support

≪ / RTI > is provided.

First, at least one polymer compound selected from the group consisting of a cationic polymer, an anionic polymer, and an amphoteric polymer and a carbon support are mixed in a solvent, and a mixture of a cationic group, an anionic group, and an amphoteric group A step of forming a carbon support into which at least one selected ionic group is introduced is performed.

The above step can be carried out by mixing and stirring the carbon support and the polymer compound in a solvent. At this time, a process commonly used in the surface treatment of a solid such as an ultrasonic treatment may be added.

The above step is a wet process, and the solvent in this step may be any organic or aqueous solvent in which the surface treatment of the carbon precursor by the polymer can be carried out smoothly.

Examples of such solvents include at least one solvent selected from the group consisting of toluene, hexane, dimethylformamide, ethanol, and water.

The carbon support may be various types such as one-dimensional needle-shaped, two-dimensional plate-like, three-dimensional spherical or rod-like supports. Preferably, the carbon support may be advantageous to inhibit aggregation of the organozinc catalyst, with spherical particles connected or in a similar form.

For example, the carbon support may be a carbon nanotube, a graphite, a graphene, an activated carbon, a mesoporous carbon, a carbon black, a carbon nano- At least one selected from the group consisting of carbon nanofibers, carbon nanowires, carbon nanohorns, carbon aerogels, carbon nanoring, and fullerenes (C60) Lt; / RTI >

Examples of the cationic polymer include poly (allylamine hydrochloride), poly (ethylene imine), poly (L-lysine), poly Poly (diallyldimethyl ammonium chloride), poly (vinylamine hydrochloride), poly (2- (dimethylamino) ethyl methacrylate) (poly (2- dimethylamino) ethyl methacrylate), and poly (amido amine) (poly (amido amine)).

The anionic polymer may be selected from the group consisting of polyglutamic acid, polyacrylic acid, poly (styrene sulfonate), carboxymethyl cellulose, cellulose sulfate, At least one compound selected from the group consisting of dextran sulfate, heparin sulfate, and poly (methylene-co-guanidine).

Wherein the ampholytic polymer is at least one compound selected from the group consisting of cocamidopropyl betaine, octyl betaine, cetyl betaine, and stearyl betaine. For example.

In this step, the polymer may be used in an amount of 1 to 500 wt%, or 1 to 300 wt%, or 5 to 150 wt%, or 10 to 100 wt%, based on the carbon support. That is, the polymer is preferably used in an amount of 1% by weight or more with respect to the carbon support, so that the surface treatment of the carbon support can be sufficiently performed. However, when the polymer is excessively mixed, the polymer may participate in the reaction of the zinc precursor and the dicarboxylic acid to induce a side reaction or affect the composition of the medium, thereby deteriorating the crystallinity of the catalyst, Aggregation of the support may be caused. Therefore, it is preferable that the polymer is used in an amount of not more than 500% by weight based on the carbon support.

As a non-limiting example, the process of surface treating a carbon support may be carried out as follows. Dissolves at least one polymer compound selected from the group consisting of a cationic polymer, an anionic polymer and an amphoteric polymer in distilled water. When a salt such as KNO ₃ is further added thereto, the bonding between the polymer compound and the carbon support can be promoted. The carbon support is then placed. The hydrophobic carbon support is not mixed with the distilled water. However, if the carbon support is mixed with the distilled water, the hydrophobic component of the polymer compound and the carbon support bind to the surface of the carbon support and the cation portion or the anion portion is exposed to the carbon support. . This is washed three times with distilled water using a centrifuge and dried to obtain a surface-treated carbon support.

Next, a step of reacting a zinc precursor with a dicarboxylic acid having 3 to 20 carbon atoms in a solution containing the carbon support is performed to form a zinc dicarboxylate compound supported on the carbon support.

In this step, the zinc dicarboxylate compound is formed by the reaction of the zinc precursor and the dicarboxylic acid, and at the same time, the zinc dicarboxylate compound is supported on the carbon support. That is, an organic zinc-supported catalyst may be formed on the carbon support without a separate process for supporting the zinc dicarboxylate compound.

At this time, the reaction of the zinc precursor and the dicarboxylic acid may be carried out in the presence of a solvent capable of uniformly dispersing or dissolving the dicarboxylic acid. For example, the reaction can be carried out by adding a solvent, a dicarboxylic acid, and the surface-treated carbon support into a stirrer, adding a zinc precursor thereto, and stirring. Alternatively, the surface-treated carbon support and the zinc precursor may be introduced into the bed type reactor, and then the solvent and the dicarboxylic acid may be circulated to conduct the reaction.

In the reaction step, the zinc precursor may include zinc oxide (ZnO), zinc sulfate (ZnSO ₄ ), zinc chlorate (Zn (ClO ₃ ) ₂ ), zinc nitrate (Zn (NO ₃ ) ₂ ) OAc) ₂ ), and zinc hydroxide (Zn (OH) ₂ ) can be used.

The dicarboxylic acid having 3 to 20 carbon atoms may be at least one compound selected from the group consisting of malonic acid, glutaric acid, succinic acid, adipic acid, terephthalic acid, isophthalic acid, homophthalic acid, and phenylglutaric acid. Can be used.

The dicarboxylic acid may be used in the same or an excessive molar amount as the zinc precursor. Specifically, the reaction may be carried out at a molar ratio of 1 mole of the zinc precursor to 1 to 1.5 moles of the dicarboxylic acid, or about 1.1 to 1.3 moles of the zinc precursor. When the reaction proceeds while maintaining the dicarboxylic acid in the same or excess amount as the zinc precursor, the reaction may proceed slowly in the form of the dicarboxylic acid molecules or ions surrounding the uniformly dispersed zinc precursor.

In the reaction step, any organic or aqueous solvent known to be capable of uniformly dispersing or dissolving the dicarboxylic acid may be used as the solvent. Specific examples of such a solvent include at least one solvent selected from the group consisting of toluene, hexane, dimethylformamide, acetone, methanol, ethanol, and water.

The solvent may be added in an appropriate amount such that the carbon support is sufficiently immersed, and may be preferably added in an amount of 2 to 1000 moles relative to 1 mole of the dicarboxylic acid. More preferably, the solvent may be added in an amount of 5 to 100 moles, or 10 to 50 moles, per mole of the dicarboxylic acid. In the above range, the dicarboxylic acid is appropriately dispersed in the solvent, and the progress of the catalyst synthesis reaction can be effectively performed.

The reaction of the zinc precursor and the dicarboxylic acid can be carried out at a temperature of about 40 to 130 DEG C for about 1 to 48 hours. According to one embodiment of the present invention, the reaction is carried out in the presence of the solvent at a temperature of about 40 to 80 ° C. for about 1 to 24 hours, followed by further reaction at a temperature of about 80 to 130 ° C. for about 1 to 24 hours . By controlling the reaction temperature or time, a catalyst in which a zinc dicarboxylate compound having a uniform shape is uniformly supported on the carbon support can be produced.

The method of manufacturing the organic zinc-supported catalyst of the embodiment may further include washing and drying the prepared organic zinc-supported catalyst.

The washing step may be repeated several times using a solvent that can be used in the above reaction until the unreacted reactant remains. In addition, the drying step may be performed by vacuum drying at a temperature of 40 to 200 ° C.

III. Using the catalyst Polyalkylene Carbonate  Method of producing resin

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

In the method for producing such a resin, the organic zinc-supported catalyst may be used as a heterogeneous catalyst, and the polymerization step may proceed with solution polymerization in an organic solvent. That is, the polymerization step can proceed with solution polymerization capable of continuous contact of the reaction mixture containing the epoxide, carbon dioxide and the solvent with the organic zinc-supported catalyst. 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, dichloromethane, 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, butyllactone, caprolactone, nitropropane, benzene, styrene, xylene, and methyl propasol can be used. Among them, the polymerization reaction can proceed more effectively by using a chlorinated solvent such as dichloromethane, ethylene dichloride, trichloroethane, tetrachloroethane or chloroform.

The solvent may be used at a weight of 0.1 to 100 times the weight of the epoxide, and may be suitably used at a weight of 0.5 to 50 times. At this time, when the solvent is used at a weight of less than 0.1 times, the solvent does not function properly as a reaction medium, and it may be difficult to take advantage of the above-mentioned solution polymerization. In addition, when the solvent is used in a weight of more than 100 times, the concentration of epoxide or the like may be relatively low, resulting in a decrease in productivity and a decrease in the molecular weight of the finally formed resin or an increase in side reaction.

The carbon dioxide may be introduced into the reaction mixture at about 1 to 10 moles per mole of epoxide. More preferably, the carbon dioxide may be introduced at about 2 to 5 moles per mole of epoxide. When the amount of carbon dioxide is less than 1 mole, the content of the polyalkylene glycol in the byproduct tends to increase, and when it is used in excess of 10 moles, it is not effective due to the introduction of excess monomer.

On the other hand, as the epoxide, 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 may be used as the epoxide.

In addition, the above-mentioned solution polymerization can be carried out at a temperature of 50 to 90 DEG C and a pressure of 15 to 50 bar for 1 to 60 hours. It is more preferable that the solution polymerization is carried out at a temperature of 70 to 90 DEG C and a pressure of 20 to 40 bar for 3 to 40 hours. Under the above conditions, the polymerization reaction promoted by the organic zinc-supported catalyst according to one embodiment can proceed effectively.

In one embodiment of the present invention, the organic zinc-supported catalyst may further include a step of thoroughly washing the catalyst or the reactor containing the catalyst after polymerization, and storing the catalyst in a solvent such that the catalyst is not dried. Accordingly, the stored organic zinc-supported catalyst can be reused in the subsequent polymerization. Specifically, the stored organic zinc-supported catalyst may be used three or more times.

Except for the above-mentioned matters, the other polymerization processes and conditions may depend on conventional polymerization conditions for the production of the polyalkylene carbonate resin, so that further explanation thereof will be omitted.

The organic zinc supported catalyst according to the present invention can exhibit an improved activity in the polymerization process for the production of the polyalkylene carbonate resin and is easy to recover after the polymerization of the polyalkylene carbonate.

1 is a graph showing the results of measurement of permeability with time for the catalyst obtained in Example 1 and Comparative Example 1. [(a) Catalyst of Example 1; (b) the catalyst of Comparative Example 1].
FIG. 2 is a photograph showing the result of separating the catalyst from the resin after synthesizing a polyalkylene carbonate resin using the catalyst obtained in Example 1 and Comparative Example 1. [(a) Using the catalyst of Example 1 ; (b) when the catalyst of Comparative Example 1 is used].

BRIEF DESCRIPTION OF THE DRAWINGS Fig. However, the following embodiments are intended to illustrate the invention, but the invention is not limited thereto.

Example  One

(1) 6 g of poly (allylamine hydrochloride) and 1.8 g of carbon black (Vulcan XC-72) were placed in 1500 ml of water and ultrasonicated in an ultrasonic bath for 1 hour Thereafter, the mixture was stirred for one day to obtain a surface-treated carbon black with poly (allylamine hydrochloride).

(2) In a 100 ml round-bottomed flask, 2.64 g (17.3 mmol) of glutaric acid and 0.364 g of the surface-treated carbon black were added to 50 ml of toluene and dispersed under reflux, And heated for 30 minutes. 1.36 g of ZnO powder was added to the solution, followed by stirring for 3 hours. The formed solid was separated using a centrifuge. The separated solid was washed three times with acetone / ethanol and then dried in a vacuum oven at 130 ° C to obtain 3.5 g of zinc glutarate supported catalyst.

Comparative Example  One

In a 100 ml round-bottomed flask, 2.64 g (17.3 mmol) of glutaric acid and 0.364 g of carbon black (Vulcan XC-72) were added to 50 ml of toluene and dispersed under reflux. Min. 1.36 g of ZnO powder was added to the solution, followed by stirring for 3 hours. The formed solid was separated using a centrifuge. The separated solid was washed three times with acetone / ethanol and then dried in a vacuum oven at 130 ° C to obtain 3.5 g of zinc glutarate supported catalyst.

Comparative Example  2

In a 100 ml round-bottomed flask, 2.64 g (17.3 mmol) of glutaric acid was added to 50 ml of toluene and dispersed under reflux, followed by heating at 55 ° C for 30 minutes. 1.36 g of ZnO powder was added to the solution, followed by stirring for 3 hours. The formed solid was separated using a centrifuge. The separated solid was washed three times with acetone / ethanol and then dried in a vacuum oven at 130 ° C to obtain 3.2 g of zinc glutarate catalyst.

Test Example  One

(Measurement of permeability of catalyst)

The catalysts obtained in Example 1 and Comparative Example 1 were placed in dichloromethane, respectively, and the transmittance was measured with a dispersion stability measuring instrument TURBISCAN LAB ^™ (Formulaction Co., Ltd.) over time. The results are shown in FIG. 1 a) the catalyst of Example 1; (b) the catalyst of Comparative Example 1].

The equipment is a device for measuring the transmittance with time by dispersing a solvent and a catalyst in a vial of 4 cm. In the graph of Fig. 1, the X-axis shows the transmittance according to height. Since the vials in the equipment are standing up, precipitation in the direction of gravity leads to gradual clearance from the upper part of the solvent, and it is possible to measure the increase of the transmittance.

Referring to FIG. 1, it can be seen that since the catalyst of Example 1 easily precipitates in a solvent, the carbon support and the catalyst disappear with time in the supernatant and show high transmittance. On the other hand, it can be confirmed that the catalyst of Comparative Example 1 does not cause the change of the permeability because the precipitation of the hydrophobic carbon support does not occur.

Test Example  2

(Preparation of polyethylene carbonate)

The catalysts of Example 1 and Comparative Examples 1 and 2 were used to produce polyethylene carbonate in the following manner.

In the glove box, 0.2 g of catalyst and 8.5 g of dichloromethane were charged to the autoclave and 8.5 g of ethylene oxide was added. Carbon dioxide was then injected into the reactor and pressurized to 30 bar. The polymerization reaction was carried out at 70 DEG C for 3 hours. After the reaction, unreacted carbon dioxide and ethylene oxide were removed together with dichloromethane as a solvent. To determine the amount of polyethylene carbonate produced, the remaining solids were completely dried and quantitated. The activity and the yield of the catalyst according to the polymerization results are shown in Table 1 below.

catalyst Activity of catalyst (g-polymer / g-catalyst) Example 1 40.5 Comparative Example 1 40.0 Comparative Example 2 21.0

Test Example  3

(Ease of catalyst recovery)

After the execution of Test Example 2, the polyethylene carbonate obtained by using the catalyst of Example 1 and the resin obtained by using the catalyst of Comparative Example 1 were respectively added to dichloromethane to dissolve the resin. The solution in which the resin was dissolved was centrifuged at 5000 RPM for 5 minutes to observe the separation state of the catalyst and the resin. The results are shown in FIG. 2 (a) when the catalyst of Example 1 was used; (b) when the catalyst of Comparative Example 1 is used].

Referring to Fig. 2, the catalyst of Example 1 was separated to such a degree that it could be recovered by centrifugation. On the other hand, the catalyst of Comparative Example 1 was still dispersed in the solution and could not be recovered by centrifugation alone.

Claims (15)

A carbon support surface-treated with at least one polymer compound selected from the group consisting of a cationic polymer, an anionic polymer, and an amphoteric polymer; And
A zinc dicarboxylate compound supported on a carbon support surface-treated with the polymer compound
≪ / RTI >
The method according to claim 1,
The carbon support may be selected from the group consisting of carbon nanotubes, graphite, graphene, activated carbon, mesoporous carbon, carbon black, carbon nanofiber, At least one compound selected from the group consisting of carbon nanowires, carbon nanohorns, carbon aerogels, carbon nanorings, and fullerenes (C60) Zinc supported catalyst.
The method according to claim 1,
The cationic polymer may be selected from the group consisting of poly (allylamine hydrochloride), poly (ethylene imine), poly (L-lysine) Poly (diallyldimethyl ammonium chloride), poly (vinylamine hydrochloride), poly (2- (dimethylamino) ethyl methacrylate) (poly (2- (dimethylamino) ethyl methacrylate), and poly (amido amine) (poly (amido amine));
The anionic polymer may be selected from the group consisting of polyglutamic acid, polyacrylic acid, poly (styrene sulfonate), carboxymethyl cellulose, cellulose sulfate, At least one compound selected from the group consisting of dextran sulfate, heparin sulfate, and poly (methylene-co-guanidine);
Wherein the ampholytic polymer is at least one compound selected from the group consisting of cocamidopropyl betaine, octyl betaine, cetyl betaine, and stearyl betaine, , Organozinc supported catalyst.
The method according to claim 1,
The zinc dicarboxylate compound is a reaction product of a zinc precursor and a dicarboxylic acid having 3 to 20 carbon atoms;
Wherein the zinc precursor is zinc oxide (ZnO), zinc sulfate (ZnSO _4), chlorate, zinc _{(Zn (ClO 3) 2)} , zinc nitrate _{(Zn (NO 3) 2)} , zinc acetate (Zn (OAc) _2), and Zinc hydroxide (Zn (OH) ₂ );
Wherein the dicarboxylic acid having 3 to 20 carbon atoms includes at least one compound selected from the group consisting of malonic acid, glutaric acid, succinic acid, adipic acid, terephthalic acid, isophthalic acid, homophthalic acid, and phenylglutaric acid. Zinc supported catalyst.
The method according to claim 1,
Wherein the zinc dicarboxylate compound is a thin film having a thickness of 10 to 500 nm.
A polymeric compound selected from the group consisting of a cationic polymer, an anionic polymer, and an amphoteric polymer, and a carbon support are mixed in a solvent, and a solution of a mixture of a cationic group, an anionic group, and an amphoteric group selected from the group consisting of a cationic group, Forming a carbon support into which at least two ionic groups have been introduced; And
Reacting a zinc precursor with a dicarboxylic acid having 3 to 20 carbon atoms in a solution containing the carbon support to form a zinc dicarboxylate compound supported on the carbon support
Lt; RTI ID = 0.0 > 1, < / RTI >
The method according to claim 6,
The carbon support may be selected from the group consisting of carbon nanotubes, graphite, graphene, activated carbon, mesoporous carbon, carbon black, carbon nanofiber, At least one compound selected from the group consisting of carbon nanowires, carbon nanohorns, carbon aerogels, carbon nanorings, and fullerenes (C60) A method for producing a zinc supported catalyst.
The method according to claim 6,
The cationic polymer may be selected from the group consisting of poly (allylamine hydrochloride), poly (ethylene imine), poly (L-lysine) Poly (diallyldimethyl ammonium chloride), poly (vinylamine hydrochloride), poly (2- (dimethylamino) ethyl methacrylate) (poly (2- (dimethylamino) ethyl methacrylate), and poly (amido amine) (poly (amido amine));
The anionic polymer may be selected from the group consisting of polyglutamic acid, polyacrylic acid, poly (styrene sulfonate), carboxymethyl cellulose, cellulose sulfate, At least one compound selected from the group consisting of dextran sulfate, heparin sulfate, and poly (methylene-co-guanidine);
Wherein the ampholytic polymer is at least one compound selected from the group consisting of cocamidopropyl betaine, octyl betaine, cetyl betaine, and stearyl betaine, , An organic zinc supported catalyst.
The method according to claim 6,
Wherein the zinc precursor is zinc oxide (ZnO), zinc sulfate (ZnSO _4), chlorate, zinc _{(Zn (ClO 3) 2)} , zinc nitrate _{(Zn (NO 3) 2)} , zinc acetate (Zn (OAc) _2), and Zinc hydroxide (Zn (OH) ₂ );
Wherein the dicarboxylic acid having 3 to 20 carbon atoms includes at least one compound selected from the group consisting of malonic acid, glutaric acid, succinic acid, adipic acid, terephthalic acid, isophthalic acid, homophthalic acid, and phenylglutaric acid. Zinc supported catalyst.
The method according to claim 6,
Wherein the reaction of the zinc precursor with a dicarboxylic acid having 3 to 20 carbon atoms proceeds in the presence of at least one solvent selected from the group consisting of toluene, hexane, dimethylformamide, ethanol, and water.
The method according to claim 6,
Wherein the reaction between the zinc precursor and the dicarboxylic acid having 3 to 20 carbon atoms proceeds in a molar ratio of 1 mole of the zinc precursor to 1 to 1.5 mole of the dicarboxylic acid.
Polymerizing a monomer containing an epoxide and carbon dioxide in the presence of the organic zinc supported catalyst according to claim 1
≪ / RTI >
13. The method of claim 12,
Wherein the step of polymerizing the monomer proceeds by solution polymerization in an organic solvent.
14. The method of claim 13,
Wherein the solvent is added at a weight of 0.1 to 100 times the weight of the epoxide.
14. The method of claim 13,
Wherein the solution polymerization is carried out at a temperature of 50 to 90 DEG C and a pressure of 15 to 50 bar for 1 to 60 hours.

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