WO2015072814A1

WO2015072814A1 - Method for preparing polyalkylene carbonate resin

Info

Publication number: WO2015072814A1
Application number: PCT/KR2014/011080
Authority: WO
Inventors: 김성경; 조현주; 강성균; 박승영; 최현
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 a method for preparing a polyalkylene carbonate resin, wherein remarkable catalytic activities can be maintained during a polymerization step by inhibiting aggregation among catalyst particles during polymerization. The method for preparing a polyalkylene carbonate resin can comprise a step of polymerizing monomers comprising an epoxide and carbon dioxide in the presence of a zinc dicarboxylate-based organic zinc catalyst and a dispersant, and the dispersant can comprise at least one selected from the group consisting of a C_1-10 alkyl acrylate, a C_1-10 alkyl methacrylate, a C_1-20 monocarboxylic acid having an oxo group in a molecular structure, and a polyether-based polymer having a C_2-6 alkylene oxide repeating unit.

Description

【Specification】

[Name of invention]

Process for producing polyalkylene carbonate resin

Technical Field

The present invention relates to a method for producing a polyalkylene carbonate resin in which aggregation between catalyst particles is suppressed during polymerization and excellent catalyst activity can be maintained during the polymerization process.

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 the concentration of carbon dioxide in the atmosphere, 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.

Among them, the reaction of copolymerization of carbon dioxide and epoxide found by Inoue et al. Is expected as a reaction to solve the global warming problem, and is actively studied not only from the viewpoint of chemical carbon dioxide fixing but also from the use of carbon dioxide as a carbon resource. It is becoming. In particular, in recent years, polyalkylene carbonate resins obtained by polymerization of carbon dioxide and epoxide have been widely spotlighted 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 as representative catalysts.

However, such zinc dicarboxylate-based catalysts, typically zinc glutarate catalysts, are formed by reacting dicarboxylic acids such as zinc precursors and glutaric acid, and have a form of fine crystalline particles. By the way, the zinc dicarboxylate-based catalyst in the form of crystalline particles has often caused a void between the catalyst particles during the polymerization process. If a cross between these catalyst particles occurs, When proceeding the polymerization process for the production of polyalkylene carbonate resin, there is a disadvantage that the sufficient contact area between the reactant and the catalyst is not secured, the polymerization activity by the catalyst is not sufficiently expressed.

Due to these drawbacks, there is a continuous demand for the development of a technology capable of producing a polyalkylene carbonate resin while maintaining excellent activity by inhibiting puncture between catalyst particles during the polymerization process. .

[Content of invention]

[Problem to solve]

The present invention provides a method for producing a polyalkylene carbonate resin in which aggregation between catalyst particles is suppressed in polymerization, so that excellent catalytic activity can be maintained during the polymerization process.

[Measures of problem]

The present invention includes a step of polymerizing a zinc dicarboxylate-based organic zinc catalyst and a monomer including an epoxide and carbon dioxide in the presence of a dispersant, wherein the dispersant is an alkyl acrylate having 1 to 10 carbon atoms and 1 to 1 carbon atoms.

At least one selected from the group consisting of 10 alkylmethacrylates, monocarboxylic acids having 1 to 20 carbon atoms having oxo (0X0) groups in the molecular structure and polyether polymers having alkylene oxide repeat units having 2 to 6 carbon atoms It provides a method for producing a polyalkylene carbonate resin comprising a. Hereinafter, a method for preparing a polyalkylene carbonate resin according to an embodiment of the present invention will be described in detail.

According to one embodiment of the invention, an epoxide in the presence of a zinc dicarboxylate organic zinc catalyst and a dispersant. And polymerizing a monomer comprising carbon dioxide,

The dispersant is an alkyl acrylate having 1 to 10 carbon atoms, an alkyl methacrylate having 1 to 10 carbon atoms, a monocarboxylic acid having 1 to 20 carbon atoms having an oxo (0X0) group in the molecular structure, and an alkylene oxide having 2 to 6 carbon atoms. Provided is a method for producing a polyalkylene carbonate resin comprising at least one member selected from the group consisting of polyether polymers having units. In the method for producing a polyalkylene carbonate resin of one embodiment, together with a zinc dicarboxylate organic zinc catalyst, a predetermined dispersant, more specifically alkyl acrylates of 1 to 10 carbon atoms, alkyl methacrylate of 1 to 10 carbon atoms Particular dispersants of polyether based polymers having monocarboxylic acids having 1 to 20 carbon atoms or alkylene oxide repeating units having 2 to 6 carbon atoms having an oxo (0X0) group in the molecular structure are used.

As a result of continuous experiments by the present inventors, it was confirmed that such a dispersant can effectively suppress aggregation between catalyst particles in the process of preparing a polyalkylene carbonate resin by polymerizing monomers including epoxide and carbon dioxide. This is because the hydrophilic group of the dispersant, for example, oxygen or carbonyl group, etc. surrounds each catalyst particle, and the remaining hydrocarbon-based hydrophobic groups of the dispersant can effectively inhibit the contact between the catalyst particles in the reaction medium to effectively suppress aggregation between the catalyst particles. Because it is expected.

As such, as the aggregation between the catalyst particles is effectively suppressed during the polymerization process, the organozinc catalyst can maintain a more uniform and fine particle state during the polymerization, and thus the contact area with the monomers is in contact with the monomer throughout the polymerization. It can exhibit excellent activity.

Thus, according to one embodiment, excellent catalytic activity is maintained continuously during the polymerization, so that the polyalkylene carbonate resin can be produced more effectively with excellent yield.

On the other hand, when other materials which do not correspond to the above specific dispersant, for example, general monocarboxylic acid such as propionic acid or acetic acid that do not have an oxo group, or general acrylic acid, may not contain hydrophilic or hydrophobic groups appropriately. As a result, it is difficult to properly surround the catalyst particles during the polymerization, and it is difficult to effectively suppress the contact between the catalyst particles. For this reason, aggregation between catalyst particles is not suppressed properly during superposition | polymerization, and activity of a catalyst may fall significantly with progress of a polymerization reaction. On the other hand, it will be described in more detail with respect to the production of polyalkylene carbonate resin according to the production method of the embodiment. In the production method of the above embodiment, alkyl acrylate or alkyl having 1 to 10, or 3 to 8 carbon atoms. Methacrylates, polyethers having 1 to 20 carbon atoms having oxo (0X0) groups in the molecular structure or monocarboxylic acids having 5 to 15 carbon atoms or alkylene oxide repeating units having 2 to 6 carbon atoms or 2 to 4 carbon atoms It is possible to use a specific dispersant in the copolymer increases, more ^specific, examples of such dispersants, haeksil methacrylic jjeyi agent, 3,5-dioxo-nuclear Sano acid, 3,5,7- tree-oxo-dodecanoyl acid, or propylene An oxide (P0) -ethylene oxide (EO) block copolymer etc. are mentioned, Of course, 2 or more types selected from these can also be used together.

By using this specific dispersant, it is possible to more effectively suppress the aggregation between the organic zinc catalyst particles, while not inhibiting the catalytic activity.

Moreover, in the manufacturing method of the said polyalkylene carbonate resin, a zinc dicarboxylate type organic zinc catalyst is used, This organic zinc catalyst is a zinc precursor, C3-C20 aliphatic dicarboxylic acid, or C8-C40. It can be used as a catalyst obtained by reacting an aromatic dicarboxylic acid.

More specifically, in the preparation of such an organic zinc catalyst, the zinc precursor may be zinc oxide, zinc hydroxide, zinc acetate (Zn (0 ₂ CCH ₃ ) ₂ ), zinc nitrate (Zn (NO ₃ ) ₂ ) or zinc sulfate Any zinc precursor that has previously been used for the preparation of zinc dicarboxylate catalysts such as (ZnSO ₄ ) and the like can be used without any particular limitation.

As the aliphatic dicarboxylic acid or aromatic dicarboxylic acid reacting with such a zinc precursor, any aliphatic dicarboxylic acid having 3 to 20 carbon atoms or aromatic dicarboxylic acid having 8 to 40 carbon atoms can be used. And, more specifically, aliphatic dicarboxylic acid selected from the group consisting of malonic acid, glutaric acid, succinic acid and adipic acid, or aromatic dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid, homophthalic acid and phenylglutaric acid Acids and the like can be used. However, in view of the activity of the organic zinc catalyst and the like, the aliphatic dicarboxylic acid, for example, glutaric acid, may be used to convert the zinc dicarboxylate-based organic zinc catalyst into a zinc glutarate-based catalyst. proper.

And the dicarboxylic acid is from about 1.0 to 1 mole of the zinc precursor. 1.5 mol, or about 1.1 to 1.4 mol. Thereby, while ensuring the proper production of the zinc dicarboxylate-based catalyst having excellent activity, interspersing of the catalyst particles during the catalyst preparation process is suppressed, so that a catalyst showing a more uniform and finer particle size and excellent activity can be appropriately obtained.

On the other hand, the production of the organic zinc catalyst by the reaction of the zinc precursor and dicarboxylic acid may proceed in a liquid medium, the liquid medium can uniformly dissolve or disperse the zinc precursor and / or dicarboxylic acid. Any organic solvent known to be used can be used. Specific examples of such organic solvents include one or more organic solvents selected from the group consisting of toluene, DMF (dimethylformamide), ethane and methane.

. In addition, the reaction step between the zinc precursor and the dicarboxylic acid may proceed for about 5 to 24 hours at a temperature of about 30 to "0 ^° C. The organic zinc catalyst prepared under such conditions has a more uniform and finer particle diameter. Together can exhibit excellent catalytic activity.

The aforementioned organic zinc catalyst has a finer average particle diameter of about 0.3 to 1.0, black about 0.3 to 0.8 Λΐι, black about 0.5 to 0.7, and about 0.3 or less, black about 0.05 to 0.3 / m, or about 0.05 to 0.2 / zm, or in the form of uniform particles having a standard deviation of a particle diameter of about 0.05 to 0.1. In particular, due to the use of a dispersant during the polymerization process, it is possible to maintain such a uniform and fine particle diameter even in the polymerization process for the production of polyalkylene carbonate resin, so that a sufficient contact area with the reactants such as the monomer is maintained throughout the polymerization and excellent Catalytic activity can be shown during polymerization. As a result, according to one embodiment, it is possible to produce a polyalkylene carbonate resin in a higher yield.

On the other hand, in the above-described method for producing a polyalkylene carbonate resin, the organic zinc catalyst may be used as a heterogeneous catalyst, the polymerization step may be carried out by solution polymerization in an organic solvent. As a result, the heat of reaction can be properly 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-pyridone, dimethyl sulfoxide, nitromethane, 1,4-dioxane, nucleic acid, toluene, tetrahydrofuran, methylethylketone, methylamine Ketones, methyl isobutyl ketone, acetone, cyclonuxanonone, trichloroethylene, methyl acetate, vinyl acetate, ethyl acetate, propyl acetate, butyrolactone, caprolactone, nitropropane, benzene, styrene, xylene and methylpropazole ( Methyl propas) may be used one or more selected from the group consisting of. Also in the case of using methylene chloride or ethylene dichloride as a solvent, the progress of a polymerization reaction can be made more effective.

The solvent is about 1: 0.5 to 1: 1 relative to the epoxide _. It can be used in the weight ratio of 100, Preferably it can be used in the weight ratio of about 1: 1-1: 10. At this time, if the ratio is too small, less than about 1: 0.5, the solvent may not function properly as the 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 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 during solution polymerization. On the contrary, if the ratio is excessively large, an excessive amount of catalyst may be used, resulting in inefficient by-products, or back-biting of the resin due to heating in the presence of a catalyst. This can happen.

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 a C 2 to C 20 unsubstituted or substituted with a halogen or an alkyl group having 1 to 5 carbon atoms. Alkylene oxides can be used. Specific examples of such epoxides include ethylene oxide, propylene oxide, butene oxide, pentene oxide, nuxene oxide, octene oxide, decene oxide, dodecene oxide, 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 Hexyl 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, Tilbene oxide, chlorostalbene oxide, dichlorostilbene oxide, 1,2-epoxy-3-phenoxypropane, benzyloxymethyl oxirane, glycidyl-methylphenyl ether, chlorophenyl-2,3-epoxypropyl ether, epoxy Propyl 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 more suitably carried out at about 70 to 90 ^° C and about 20 to 40 bar, for about 3 to 40 hours.

On the other hand, the other polymerization process and conditions except for the above may be followed according to the conventional polymerization conditions for the production of polyalkylene carbonate resin, etc., further description thereof will be omitted.

[Effects of the Invention】

. According to the present invention, due to the use of a specific dispersant, in the process of producing a polyalkylene carbonate resin by polymerizing monomers including epoxide and carbon dioxide, the puncturing between the catalyst particles can be effectively suppressed. Therefore, during the polymerization process, the organic zinc catalyst can maintain a more uniform and finer particle state during the polymerization, and thus can exhibit excellent activity throughout the polymerization while contacting the monomer with a sufficient contact area. Thus, according to one embodiment, excellent catalytic activity is maintained continuously during the polymerization, so that the polyalkylene carbonate resin can be produced more effectively with excellent yield.

[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. Preparation Example 1 Preparation of Organic Zinc Catalyst

In a 250 mL equilateral bottom flask, 100 mL was added to luene and dispersed under reflux by addition of 6.6 g (0.05 mol) of glutaric acid and 10 mL of acetic acid. Subsequently, the mixture was heated for 30 minutes at a temperature of 55 ^° C., and 4.1 g (0.05 mol) of Zn 0 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, it was heated at 110 ^° C for 4 hours. After a white solid had formed it was filtered, washed with acetone / ethanol and dried in a vacuum oven at 130 ^° C. In this way, the organic zinc catalyst of Preparation Example 1 was prepared, and its chemical structure was confirmed. In addition, such an organic zinc catalyst was confirmed through SEM analysis, and as a result, it was confirmed that the organic zinc catalyst of Preparation Example 1 had a standard deviation of an average particle diameter of about 0.6 / im and a particle diameter of about 0.18 /. Example 1:

First, 0.4 g of the catalyst of Preparation Example 1, 10 mg of dispersant (hexyl methacrylate) and 8.52 g of dichloromethane (methylene chloride) were added into a high pressure reaction vessel in a glove box, followed by 8.9 g of ethylene oxide (ethylene). oxide). Then pressurized to 30 bar with carbon dioxide in the reactor. The polymerization reaction was carried out for 3 hours at 70 ° C. After completion of the reaction, Mibanung's 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. Example 2:

In Example 1, polyethylene carbonate was prepared in the same manner as in Example 1, except that 10 mg of 3,5,7-trioxo-dodecanoic acid was used instead of nucleus methacrylate as the dispersant. 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. Example 3:

In Example 1, polyethylene carbonate was prepared in the same manner as in Example 1, except that 10 mg of 3,5-dioxonuxanoic acid was used instead of nucleus methacrylate as the dispersant. 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. Example 4:

In Example 1, except that 10 mg of propylene oxide (PO) -ethylene oxide (EO) block copolymer (Mw: 8000; Sigma Aldrich Co. I) was used as dispersant instead of nucleus methacrylate. In the same manner, polyethylene carbonate was prepared. 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. Comparative Example 1:

In Example 1, polyethylene carbonate was prepared in the same manner as in Example 1, except that no dispersant was used. The remaining solids were quantified after complete drying to determine the ^' amount of polyethylene carbonate prepared. The activity and yield of the catalyst according to the polymerization results are summarized in Table 1 below. Comparative Example 2:

In Example 1, instead of nucleus methacrylate as the dispersant, 10 mg of Polyethylene carbonate was prepared in the same manner as in Example 1 except for using propionic acid. The remaining solids were quantified after complete drying to determine the amount of polyethylene carbonate produced. According to the polymerization results, the activity and yield of the catalyst are summarized in Table 1 below.

TABLE 1

Referring to Table 1, in Examples 1 to 4, despite using the same catalysts as Comparative Examples 1 and 2, these catalysts can maintain and express excellent activity during polymerization, and polyethylene carbonate can be produced with excellent yield. It was confirmed.

This is predicted because, depending on the use of a specific dispersant, the spat between the catalyst particles in the above-mentioned polymerization process is more effectively suppressed, and as a result, excellent catalytic activity is not inhibited during the polymerization process.

In contrast, the propionic acid used in Comparative Example 2 does not effectively suppress aggregation between the catalyst particles during the polymerization, so that the relative decrease in the catalytic activity appears to be large in Comparative Example 2.

Claims

【Patent Claims】

【Claim 1】

It includes the step of polymerizing monomers containing epoxide and carbon dioxide in the presence of a zinc dicarboxylate-based organic zinc catalyst and a dispersant,

The dispersant is an alkyl acrylate with 1 to 10 carbon atoms, and 1 to 10 carbon atoms.

10 alkyl methacrylate, a monocarboxylic acid with 1 to 20 carbon atoms having an oxo (0 A method for producing a polyalkylene carbonate resin comprising the above.

【Claim ² 】

According ^to claim 1, wherein the dispersant is hexyl methacrylate, 3,5-dioxohexanoic acid, 3,5,7-trioxo-dodecanoic acid, and propylene oxide (PO)-ethylene oxide (EO) A method for producing a polyalkylene carbonate resin comprising at least one selected from the group consisting of block copolymers.

【Claim 3】

The method of claim 1, wherein the zinc dicarboxylate-based organic zinc catalyst is a poly catalyst obtained by reacting a zinc precursor with an aliphatic dicarboxylic acid having 3 to 20 carbon atoms or an aromatic dicarboxylic acid having 8 to 40 carbon atoms. Method for producing alkylene carbonate resin.

【Claim 4】

The method of claim 3, wherein the aliphatic dicarboxylic acid or aromatic dicarboxylic acid is a dicarboxylic acid selected from the group consisting of malonic acid, glutaric acid, succinic acid, adipic acid, terephthalic acid, isophthalic acid, homophthalic acid, and phenylglutaric acid. Method for producing polyalkylene carbonate resin containing boxylic acid.

【Claim 5】

The method of claim 3, wherein the zinc precursor is zinc oxide, zinc hydroxide, or acetic acid. A method for producing a polyalkylene carbonate resin containing zinc (Zn(O ₂ CCH ₃ ) ₂ ), zinc nitrate (Zn(N0 ₃ ) ₂ ) or zinc sulfate (ZnSO ₄ ).

【Claim 6】.

The method for producing a polyalkylene carbonate resin according to claim 3, wherein the aliphatic dicarboxylic acid or aromatic dicarboxylic acid is used and reacted at a ratio of 1.0 to 1.5 mole based on 1 mole of the zinc precursor.

【Claim 7】

The method of claim 1, wherein the zinc dicarboxylate-based organic zinc catalyst is in the form of particles having an average particle diameter of 0.3 to 1.0 and a standard deviation of the particle diameter of 0.3/im or less, and is used during polymerization. .

【Canggu Port 8】

The method of claim 1, wherein the method for producing a polyalkylene carbonate resin is carried out by solution polymerization in an organic solvent.