WO2015072815A1

WO2015072815A1 - Organic zinc catalyst, preparation method therefor, and method for preparing polyalkylene carbonate resin by using same

Info

Publication number: WO2015072815A1
Application number: PCT/KR2014/011081
Authority: WO
Inventors: 김성경; 박승영; 조현주
Original assignee: 주식회사 엘지화학
Priority date: 2013-11-18
Filing date: 2014-11-18
Publication date: 2015-05-21

Abstract

The present invention relates to: an organic zinc catalyst having a more uniform and finer particle size due to the inhibition of aggregation among catalyst particles during a preparation step, thereby exhibiting more improved activities in a polymerization step for preparing a polyalkylene carbonate resin; a preparation method therefor; and a method for preparing a polyalkylene carbonate resin by using the same. The organic zinc catalyst is a zinc dicarboxylate-based organic zinc catalyst used in a reaction for preparing a polyalkylene carbonate resin from carbon dioxide and an epoxide, wherein a monocarboxylic acid-derived residue having a C_3-15 aliphatic hydrocarbon group (wherein at least one oxygen or carboxyl group can or cannot be contained in the aliphatic hydrocarbon group) is coupled to at least one end of the zinc dicarboxylate-based organic zinc catalyst.

Description

【Specification】

[Name of invention]

Organic zinc catalyst, preparation method thereof and preparation method of polyalkylene carbonate resin using same

Technical Field

The present invention is an organic zinc catalyst that suppresses agglomeration between catalyst particles during the production process, has a more uniform and finer particle size, and thus exhibits an improved activity in the polymerization process for producing a polyalkylene carbonate resin, a method for preparing the same, and It relates to a method for producing a polyalkylene carbonate resin using the same.

Background Art

Since the Industrial Revolution, mankind has built up a modern society by consuming large amounts of fossil fuels, but on the one hand, increasing atmospheric carbon dioxide concentrations, and further promoting this increase by environmental destruction such as deforestation. Since global warming is caused by an increase in 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 has a high contribution to global warming. A variety of studies are being conducted on a global scale.

. In this case, the reaction of copolymerization of carbon dioxide and epoxide found by Inoue et al. Is expected as a reaction to solve the problem of global warming, and is active not only from the viewpoint of chemical carbon dioxide fixing but also from the use of carbon dioxide as a carbon resource. Is being studied. In particular, in recent years, polyalkylene carbonate resins obtained by polymerization of the carbon dioxide and epoxide have gained much attention as a kind of biodegradable resins.

Various catalysts for the preparation of such polyalkylene carbonate resins have been researched and proposed in the past, and zinc dicarboxylate-based catalysts such as zinc glutarate catalysts in which zinc and dicarboxylic acid are combined are known.

However, such zinc dicarboxylate-based catalysts, typically zinc glutarate catalysts, react with dicarboxylic acids such as zinc precursors and glutaric acid. It forms and takes the form of fine crystalline particles. By the way, in the process of manufacturing such a catalyst, the groove | channel between catalyst particles often generate | occur | produces, and in many cases, it has a comparatively large particle size and a nonuniform particle shape. Due to such a large and nonuniform particle size, when the polymerization process for producing polyalkylene carbonate resin is performed using the zinc catalyst dicarocarboxylate-based catalyst, the contact area between the reactants and the catalyst is not secured and polymerization is performed. There was a drawback that the activity was not fully expressed

Due to these drawbacks, there is a continuous demand for the development of a catalyst-related technology that can suppress catalyst particle aggregation of the catalyst production process and to provide a catalyst exhibiting improved activity and the like.

[Content of invention]

[Problem to solve]

The present invention is suppressed and the aggregation between the particles during manufacture, more uniform and also the fine particle size to have, thereby producing a polyalkyl with an organic zinc catalyst showing an improved activity in the polymerization process for the production of alkylene carbonate resin, thereof in accordance with _i To provide a way.

This invention also provides the manufacturing method of the polyalkylene carbonate resin using the said organic zinc catalyst.

[Measures of problem]

. The present invention is a zinc dicarboxylate organic zinc catalyst used in the reaction for producing a polyalkylene carbonate resin from carbon dioxide and epoxide,

At least one end of the zinc dicarboxylate-based organic zinc catalyst, an aliphatic hydrocarbon group having 3 to 15 carbon atoms (however, the aliphatic hydrocarbon group may or may not include one or more oxygen or carbonyl groups). Provided is an organic zinc catalyst having a monocarboxylic acid-derived residue bonded thereto.

The present invention also provides a zinc precursor, a ^{"dicarboxylic} acid, monomethyl having an aliphatic hydrocarbon group having a carbon number of 3 to 15 (however, may not be included groups aliphatic hydrocarbons, include a one or more oxygen or carbonyl or.) It provides a method for producing the organic zinc catalyst comprising the step of reacting a carboxylic acid.

In addition, the present invention, in the presence of the organic zinc catalyst, epoxide and It provides a method for producing a polyalkylene carbonate resin comprising the step of polymerizing a monomer including carbon dioxide. Hereinafter, an organic zinc catalyst according to an embodiment of the present invention, a method for preparing the same, and a method for preparing a polyalkylene carbonate resin using the same will be described in detail.

According to one embodiment of the invention, the zinc dicarboxylate-based organic zinc catalyst used in the reaction for producing a polyalkylene carbonate resin from carbon dioxide and epoxide, at least one side of the zinc dicarboxylate-based zinc catalyst An organic zinc having a moiety derived from a monocarboxylic acid having an aliphatic hydrocarbon group having 3 to 15 carbon atoms (wherein the aliphatic hydrocarbon group may or may not include one or more oxygen or carbonyl groups) at the terminal of A catalyst is provided.

The organic zinc catalyst of the embodiment is a monocarboxylic acid-derived moiety having an aliphatic hydrocarbon group having 3 to 15 carbon atoms at at least one end thereof in the structure of a known zinc dicarboxylate-based organic zinc catalyst. (Residue having a structure of aliphatic hydrocarbon having 3 to 15 carbon atoms)-(C = 0) -O- ″) is bonded to have a structure end-capped with these residues.

According to the structural properties end capped with such end capping structures, particularly aliphatic hydrocarbon group-containing structures having relatively long chain lengths, relatively hydrophobic end capping structures can suppress aggregation between catalyst particles from each other. Therefore, the organozinc catalyst is suppressed between the catalyst particles during the manufacturing process, it can exhibit a more uniform and fine particle size.

As a result, when the copolymerization of carbon dioxide and epoxide is carried out using the organic zinc catalyst of this embodiment and a polyalkylene carbonate resin is produced, the contact area between the reactant for copolymerization and the organic zinc catalyst particles is increased and the copolymerization is performed. It was confirmed that the activity can be greatly improved.

Accordingly, the organic zinc catalyst of the embodiment has a more uniform and fine particle diameter by suppressing aggregation between catalyst particles during the manufacturing process, and shows an improved activity in the polymerization process for producing polyalkylene carbonate resin, such a polymerization process Very preferably. Such organic zinc catalysts may basically comprise a chain structure equivalent to previously known zinc dicarboxylate-based catalysts. That is, the organic zinc catalyst may have a structure in which zinc, a dicarboxylate, for example, an aliphatic dicarboxylate having 3 to 20 carbon atoms or an aromatic dicarboxylate having 8 to 40 carbon atoms is bonded. , The monocarboxylic acid-derived residue may be bonded to the terminal. For example, the organic zinc catalyst may have a chemical structure of Formula 1:

[General 1]

In Formula 1, R1 and R3 are each independently an aliphatic hydrocarbon group having 3 to 15 carbon atoms derived from a monocarboxylic acid (however, the aliphatic hydrocarbon group may or may not include one or more oxygen or carbonyl groups). ), And R2 may represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 40 carbon atoms derived from dicarboxylic acid or dicarboxylate.

In the structure of the organic zinc catalyst of one embodiment, the dicarboxylate is an aliphatic dicarboxylate having 3 to 20 carbon atoms, such as glutarate, malonate, succinate, or adipate, terephthalate, isophthalate, homo It may be any of aromatic dicarboxylates having 8 to 40 carbon atoms, such as phthalate or phenylglutarate. However, the dicarboxylate is glutarate in view of the activity of the organic zinc catalyst. The zinc dicarboxylate-based organic zinc catalyst is preferably a zinc glutarate-based catalyst. Such dicarboxylates are aliphatic dicarboxylic acids having 3 to 20 carbon atoms, such as dicarboxylic acids such as glutaric acid, malonic acid, succinic acid or adipic acid, and terephthalic acid, isophthalic acid and homo. It is derived from aromatic dicarboxylic acids having 8 to 40 carbon atoms such as phthalic acid or phenyl glutaric acid, and can be formed by reaction of these dicarboxylic acids with zinc. In addition, the moiety bonded and capped to at least one end of the organic zinc catalyst may include 3 to 15 carbon atoms, or 4 to 15 carbon atoms, or an aliphatic carbon of 6 to 15 carbon atoms, with or without one or more oxygen or carbonyl groups. It may be derived from a monocarboxylic acid having a hydrocarbon group, representative examples of such a monocarboxylic acid, valeric acid; Lauric acid; 3,5-dioxonucleosanic acid; 3,5,7-trioxo-dodecanoic acid; Keto acids such as acetoacetic acid or levulinic acid; Black is 4-oxo-4H-1-benzopyran-2-carboxylic acid (4-oxo-4H-1 -benzopyran-2-carboxycarboxylic acid) or 5-hydroxy-4-oxo-4H-pyran- Oxo carboxylic acids such as 2-carboxylic acid (5-Hydroxy-4-oxo-4H-pyran-2-carboxylic acid), and two or more kinds of mixtures selected for these cases may be used. Of course you can. As the monocarboxylic acid-derived residue is capped at the end of the organic zinc catalyst, the pores between the catalyst particles are more effectively suppressed during the catalyst preparation process, and an organic zinc catalyst showing improved activity with a uniform and fine particle size is appropriately Can be made and provided. However, it is apparent that the organic zinc catalyst may be end capped with a monocarboxylic acid-derived residue through reaction with various monocarboxylic acids.

If an organic zinc catalyst end-capped with a monocarboxylic acid having an aliphatic hydrocarbon group having less than 3 carbon atoms (for example, propionic acid, etc.) is used, it is difficult for the aliphatic hydrocarbon group to exhibit stratified hydrophobicity and coagulation between catalyst particles. It can be difficult to suppress. For this reason, it may become difficult to obtain an organic zinc catalyst having a fine and uniform particle diameter, and the polymerization activity of the organic zinc catalyst may become insufficient.

In addition, in the organic zinc catalyst of the single-group embodiment, the monocarboxylic acid-derived residues are more capped at both ends of the zinc dicarboxylate-based organic zinc catalyst in order to more effectively suppress aggregation during the catalyst preparation process. As appropriate, the monocarboxylic acid-derived moiety is about 0.1 to 0.5 moles, or about 0.2 to 0.5 moles, and black is about 1 mole of the dicarboxylate-derived moiety bound to the organic zinc catalyst. It is appropriate that they are bonded in a ratio of 0.2 to 0.4 mol.

In addition, the organic zinc catalyst of the above-described embodiment is about 0.2 to 0.9 / ffli, or about 0.3 to 0.8 ΛΠ, as the aggregation between the catalyst particles is suppressed during the manufacturing process Or in the form of uniform particles having an average particle diameter of about 0.5 to 0.7 and a standard deviation of about 0.05 to 0.3 μιη, or about 0.05 to Q.2, or about 0.05 to 0.1 Λπ. As such, when the organic zinc catalyst is used as a catalyst in the production of polyalkylene carbonate resin by copolymerization of carbon dioxide and epoxide, the contact area between the catalyst particles and the reactant may be increased, thereby improving activity. On the other hand, according to another embodiment of the invention, there is provided a method for producing the organic zinc catalyst of the above-described embodiment. Such a production method may include, for example, a zinc precursor, a dicarboxylic acid, and an aliphatic hydrocarbon group having 3 to 15 carbon atoms (however, the aliphatic hydrocarbon group may or may not include one or more oxygen or carbonyl groups). Reacting a monocarboxylic acid having a may be included.

More specifically, in the production method, the reaction step may include reacting the zinc precursor, the dicarboxylic acid, and further adding the monocarboxylic acid to react.

According to this production method, after reacting the zinc precursor and the dicarboxylic acid to prepare a zinc dicarboxylate catalyst, monocarboxylic acid is added to suppress the aggregation between the additional catalyst particles while end capping each catalyst. In one embodiment, an organic zinc catalyst may be prepared. As such, an organic zinc catalyst of one embodiment, which exhibits a more uniform and finer particle size and improved activity, can be prepared.

In this manufacturing process, the zinc precursor may be zinc oxide or zinc hydroxide, or zinc such as zinc acetate (Zn (0 ₂ CCH ₃ ) ₂ ), zinc nitrate (Zn (N0 ₃ ) ₂ ) or zinc sulfate (ZnS0 ₄ ). Salts may be used, and any zinc precursors previously used in the preparation of zinc dicarboxylate catalysts may be 'used' without any limitation. In addition, since examples of the dicarboxylic acid and the monocarboxylic acid have already been described above, further description thereof will be omitted. And in the method for producing the catalyst, the reaction step of the dicarboxylic acid is about

The reaction may be performed for about 0.5 to 10 hours at a silver degree of 40 to 90 ^° C., and the reaction of the monocarboxylic acid may be performed for about 1 to 20 hours at a temperature of about 80 to 150 ^° C. As a result, agglomeration between the catalyst particles during the catalyst preparation process can be effectively suppressed while ensuring the proper production of the zinc dicarboxylate-based catalyst, so that a catalyst having a more uniform and finer particle size and excellent activity can be produced properly. Can be.

In addition, in the preparation of the catalyst, the monocarboxylic acid may be used in a ratio of about 0.1 to 0.5 moles per 1 mole of the dicarboxylic acid, the dicarboxylic acid is about 1.0 to 1 mole of the zinc precursor To 1.5 mol. As a result, agglomeration between the catalyst particles during the catalyst preparation process is more effectively suppressed while ensuring proper production of the zinc dicarboxylate-based catalyst having excellent activity, so that a catalyst having a more uniform and finer particle size and excellent activity can be produced properly. Can be.

On the other hand, according to another embodiment of the present invention, there is provided a method for producing a polyalkylene carbonate resin comprising the step of polymerizing a monomer comprising epoxide and carbon dioxide ί in the presence of the above-described organic zinc catalyst.

In the preparation method of such a catalyst, the organic zinc catalyst may be used in the form of a heterogeneous catalyst, and the polymerization step may proceed to 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 easily controlled.

In this solution polymerization, solvents include methylene chloride, ethylene dichloride, trichloroethane, tetrachloroethane, chloroform, acetonitrile propionitrile, dimethylformamide, Ν-methyl-2-pyridoneone dimethyl sulfoxide, Nitromethane, 1,4-dioxane, nucleic acid, toluene, tetrahydrofuran, methyl ethyl ketone, methyl amine ketone, methyl isobutyl ketone, acetone, cyclonuclear xanone, trichloroethylene, methyl acetate, vinyl acetate, ethyl acetate It may be used propyl acetate, butyl lactone, caprolactone, nitropropane, at least one selected from benzene, styrene, xylene, and the group consisting of methyl Pro pajol _(me thyl propasol). Of these, by using methylene chloride or ethylene dichloride as a solvent, the progress of the polymerization reaction can be made more effective.

The solvent may be used in a weight ratio of about 1: 0.5 to 1: 100 relative to the epoxide, and may be suitably used in a weight ratio of about 1: 1 to 1:10. At this time, if the ratio is too small, less than about 1: 0.5, the solvent may not function properly as a reaction medium and it may be difficult to take advantage of the above-described solution polymerization. In addition, when the ratio exceeds about 1: 100, the concentration of epoxide and the like may be relatively lowered, which may lower productivity, and may lower the molecular weight of the finally formed resin or increase side reactions.

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 organic zinc catalyst may be added in 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 show a catalytic catalytic activity during solution polymerization. On the contrary, if the ratio is too large, an excessive amount of catalyst is used to produce inefficient and by-products, or back-biting of the resin due to heating in the presence of a catalyst. ) May occur.

On the other hand, examples of the epoxide include an alkylene oxide having 2 to 20 carbon atoms unsubstituted or substituted with halogen or an alkyl group having 1 to 5 carbon atoms; Cycloalkylene oxide having 4 to 20 carbon atoms unsubstituted or substituted with halogen or alkyl group having 1 to 5 carbon atoms; And a styrene oxide having 8 to 20 carbon atoms substituted or unsubstituted with halogen or an alkyl group having 1 to 5 carbon atoms. Representatively, the epoxide may be an alkylene oxide having 2 to 20 carbon atoms unsubstituted or substituted with halogen or an alkyl group having 1 to 5 carbon atoms.

Specific examples of such epoxides include ethylene oxide, propylene oxide, butene oxide, pentene oxide, nuxene oxide, octene oxide, decene oxide, dodecene oxad, tetradecene oxide, nuxadecene oxide, octadecene oxide, butadiene monooxide, 1 , 2-epoxy-7-octene, epifluorohydrin, epichlorohydrin, epibromohydrin, isopropyl glycidyl ether, butyl glycidyl ether, t-butyl glycidyl ether, 2-ethyl Nucleosil glycidyl ether, allyl glycidyl ether, cyclopentene oxide, cyclonuxene oxide, cyclooctene oxide, cyclododecene oxide, alpha-pinene oxide, 2,3-epoxynorbornene, limonene oxide, dieldrin, 2, 3-epoxypropylbenzene, styrene oxide, phenylpropylene oxide, Ben-oxide, stilbene oxide, chloro, dichloro-stilbene oxide and 1,2-epoxy-3-phenoxy propane, benzyloxymethyl-oxirane, a glycidyl-ether, phenyl, chlorophenyl-2,3-epoxypropyl ether, Epoxypropyl mesoxyphenyl ether, biphenyl glycidyl ether, glycidyl naphthyl ether, and the like. Most typically, ethylene oxide is used as the epoxide.

In addition, the solution polymerization described above may be performed at about 50 to 100 ^° C. and about 15 to 50 bar for about 1 to 60 hours. In addition, the solution polymerization is about

At 70 to 9 C C and about 20 to 40 bar, it is more appropriate to carry out for about 3 to 40 hours.

Meanwhile, except for the above-described matters, the polymerization process and conditions may be followed by conventional polymerization conditions for preparing the polyalkylene carbonate resin, and thus, further description thereof will be omitted.

[Effects of the Invention]

According to the present invention, there is provided an organic zinc catalyst for producing a polyalkylene carbonate resin having a finer and more uniform particle size and exhibiting excellent activity because the aggregation between the catalyst particles is effectively suppressed during the catalyst preparation process, and a method for producing the same. Can be.

[Brief Description of Drawings]

1 and 2 are SEM photographs of the organic zinc catalyst prepared in Example 1 and Comparative Example 1, respectively.

[Specific contents to carry out invention]

Hereinafter, preferred embodiments are presented to help understand the invention. However, the following examples are only to illustrate the invention, not limited to the invention only. Example 1 Preparation of Organic Zinc Catalyst

In a 250 mL equilateral bottom flask, 100 mL was added to ruene and dispersed under reflux by addition of 6.6 g (0.05 mol) of glutaric acid and 0.1 mL of acetic acid. Subsequently, heating was performed at a temperature of 55 ^° C. for 30 minutes, and 4.1 g (0.05 mol) of ππΟ was added to 50 mL of toluene and dispersed, which was added to the dispersion of glutaric acid, followed by stirring for 3 hours. Thereafter, 0.02 m of valeric acid was slowly added by pipette and heated at 0 ^° C. for 4 hours. After a white solid is formed, it is filtered and acetone / ethanol Washed and dried in a vacuum oven at 130 ^° C. In this way, the organic zinc catalyst of Example 1 was prepared and its chemical structure was confirmed. Moreover, the SEM photograph of this organic zinc catalyst is shown in FIG. As a result of the SEM analysis, it was confirmed that the organic zinc catalyst of Example 1 had a standard deviation of an average particle diameter of about 0.52 Λπ and a particle diameter of about 0.27 mm 3. Example 2: Preparation of Organic Zinc Catalyst

An organic zinc catalyst of Example 2 was prepared in the same manner as in Example 1, except that lauric acid was used instead of valeric acid in Example 1, and the chemical structure thereof was confirmed. In addition, such an organic zinc catalyst was confirmed through SEM analysis, and as a result, the organic zinc catalyst of Example 2 was confirmed to have a standard deviation of an average particle diameter? _Of about 0.48 and a particle diameter of about 0.28. Example 3: Preparation of Organic Zinc Catalyst

An organic zinc catalyst of Example 3 was prepared in the same manner as in Example 1, except that acetoacetic acid was used instead of valeric acid in Example 1, and the chemical structure thereof was confirmed. In addition, such an organic zinc catalyst was confirmed through SEM analysis, and as a result, the organic zinc catalyst of Example 3 was found to have a standard deviation of an average particle diameter of about 0.57 and a particle diameter of about 0.23. Example 4: Preparation of Organic Zinc Catalyst

The organic zinc catalyst of Example 4 was prepared in the same manner as in Example 1, except that 5-hydroxy-4-oxo-4H-pyran-2-carboxylic acid was used instead of valeric acid in Example 1. The chemical structure was confirmed. In addition, such an organic zinc catalyst was confirmed through SEM analysis, and as a result, the organic zinc catalyst of Example 4 was confirmed to have a standard deviation of an average particle diameter of about 0.51 mm 3 and a particle diameter of about 0.28 mm. Comparative Example 1: Preparation of Organic Zinc Catalyst

An organic zinc catalyst of Comparative Example 1 was prepared in the same manner as in Example 1, except that valeric acid was not used in Example 1, and the chemical structure thereof was obtained. Confirmed. In addition, the SEM photograph of such an organic zinc catalyst is shown in FIG. Comparative Example 2: Preparation of Organic Zinc Catalyst

An organic zinc catalyst of Comparative Example 2 was prepared in the same manner as in Example 1, except that propionic acid was used instead of valeric acid in Example 1, and the chemical structure thereof was confirmed. In addition, such an organic zinc catalyst was confirmed through SEM analysis, and as a result, the organic zinc catalyst of 2 was found to have a standard deviation of an average particle diameter of about 0.73 mm 3 and a particle diameter of about 0.34 1. 1 and 2, and the respective examples and comparative examples described above, Examples 1 to 2

An organic zinc catalyst prepared using a monocarboxylic acid having an aliphatic hydrocarbon group having 3 to 15 carbon atoms at 4 does not use such a monocarboxylic acid (Comparative Example 1), or a monocarboxylic acid having a hydrocarbon group having less than 3 carbon atoms bonded thereto. It was confirmed to have a more uniform and finer particle diameter compared to the organic zinc catalyst prepared using (propionic acid) (Comparative Example 2). Polymerization Example:

Polyethylene carbonate was polymerized and prepared in the following manner using the catalysts of Examples 1 to 4 and Comparative Examples 1 and 2.

First, in a glove box, 0.4g of catalyst and 8.52g of dichloromethane (methylene chloride) were placed in a high pressure reactor, followed by 8.9g of ethylene oxide. Then pressurized to 30 bar with carbon dioxide in the reactor. The polymerization was carried out at 70 ^° C. for 3 hours. After the reaction was completed, unreacted carbon dioxide and ethylene oxide were removed together with the solvent dichloromethane. The remaining solids were quantified after complete drying to determine the amount of polyethylene carbonate produced. The activity and yield of the catalyst according to the polymerization results are summarized in Table 1 below. TABLE 1

Referring to Table 1, in the case of the catalysts of Examples 1 to 4, it showed that the activity is excellent compared to Comparative Examples 1 and 2, it is possible to manufacture the polyethylene carbonate in excellent yield.

Claims

[Patent Claims]

[Claim 1]

As a zinc dicarboxylate type organic zinc catalyst used for reaction which produces carbon dioxide and polyalkylene carbonate resin from an epoxide,

An organic zinc catalyst having a monocarboxylic acid-derived residue having an aliphatic hydrocarbon group having 3 to 15 carbon atoms with or without one or more oxygen or carbonyl groups bound to at least one end of the zinc dicarboxylate-based organic zinc catalyst .

[Claim 2]

The organic zinc catalyst of claim 1, wherein the zinc dicarboxylate-based organic zinc catalyst is a catalyst in which zinc, an aliphatic dicarboxylate having 3 to 20 carbon atoms or an aromatic dicarboxylate having 8 to 40 carbon atoms is bonded.

[Claim 3]

The organic zinc catalyst according to claim 1, wherein the zinc dicarboxylate organic zinc catalyst is a zinc glutarate catalyst. ^

[Claim 4]

According to claim 1, wherein the monocarboxylic acid is valeric acid, lauric acid, 3,5-dioxonucleoanoic acid 3,5, 7-trioxo-dodecanoic acid, acetoacetic acid (Acetoacetic acid), rubulic acid ( Levulinic acid), 4-oxo-4H-1-benzopyran-2-carboxylic acid (4-oxo-4H-1 -benzopyran-2-carboxylic acid) and 5-hydroxy-4-oxo-4H-pyran- An organic zinc catalyst comprising at least one member selected from the group consisting of 2-carboxylic acids (5-Hydroxy-4-oxo-4H-pyran-2-carboxylic acid).

[5.] ^"

The organic zinc catalyst according to claim 1, wherein the monocarboxylic acid-derived residue is bonded at a ratio of 0.1 to 0.5 moles with respect to 1 mole of the dicarboxylate-derived residue of the organic zinc catalyst.

[Claim 6]

The organic zinc catalyst according to claim 1, having a standard deviation of the average particle diameter of 0.2 to 0.9 mm 3 and the particle diameter of 0.05 to 0.3 μπ].

[Claim 7]

With zinc precursor,

Dicarboxylic acid,

A process for preparing the organic zinc catalyst of claim 1, comprising the step of reacting a monocarboxylic acid having an aliphatic hydrocarbon group having 3 to 15 carbon atoms with or without one or more oxygen or carbonyl groups.

[Claim 8]

The method of claim 7, wherein the reaction step comprises the steps of reacting a zinc precursor, dicarboxylic acid,

Method for producing an organic zinc catalyst comprising the step of further adding the monocarboxylic acid to react.

[Claim 9]

8. The zinc precursor according to claim 7, wherein the zinc precursor is selected from the group consisting of zinc oxide, zinc hydroxide, zinc acetate (Zn (0 ₂ CCH ₃ ) ₂ ), zinc nitrate (Zn (N0 ₃ ) ₂ ) and zinc sulfate (ZnS0 ₄ ). A process for the preparation of an organic zinc catalyst comprising a selected compound.

[Claim 101]

According to claim 8, wherein the reaction step of the dicarboxylic acid is carried out for 0.5 to 10 hours at a temperature of 40 to 90 ^° C, the reaction step of the monocarboxylic acid is 1 to 20 at a temperature of 80 to 15 C C Process for preparing an organic zinc catalyst that proceeds over time.

[Claim 1 11]

_. The method of claim 7, wherein the monocarboxylic acid is used in an amount of 0.1 to 0.5 moles with respect to 1 mole of the dicarboxylic acid.

[Claim 12]

8. The dicarboxylic acid according to claim 7, wherein the dicarboxylic acid is used per mole of the zinc precursor.

A process for producing an organic zinc catalyst used at a ratio of 1.0 to 1.5 moles.

[Claim 13]

A process for producing a polyalkylene carbonate resin comprising polymerizing a monomer comprising epoxide and carbon dioxide in the presence of the organic zinc catalyst of claim 1.

[14.] ^"

The method for producing a polyalkylene carbonate resin according to claim 13, which is subjected to solution polymerization in an organic solvent.