KR102039206B1 - Organic zinc catalyst, its preparation method, and method for preparing poly(alkylene carbonate) using the same - Google Patents

Organic zinc catalyst, its preparation method, and method for preparing poly(alkylene carbonate) using the same Download PDF

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KR102039206B1
KR102039206B1 KR1020150185336A KR20150185336A KR102039206B1 KR 102039206 B1 KR102039206 B1 KR 102039206B1 KR 1020150185336 A KR1020150185336 A KR 1020150185336A KR 20150185336 A KR20150185336 A KR 20150185336A KR 102039206 B1 KR102039206 B1 KR 102039206B1
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zinc
catalyst
shell
organic
organic zinc
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KR20170075544A (en
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방정업
황교현
송철옥
방용주
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주식회사 엘지화학
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/122—Metal aryl or alkyl compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/32—General preparatory processes using carbon dioxide
    • C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
    • B01J2531/26—Zinc

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Abstract

The present invention relates to an organic zinc catalyst, a method for producing the same, and a method for producing a polyalkylene carbonate using the same.

Description

Organic zinc catalyst, preparation method thereof and polyalkylene carbonate production method using the same {ORGANIC ZINC CATALYST, ITS PREPARATION METHOD, AND METHOD FOR PREPARING POLY (ALKYLENE CARBONATE) USING THE SAME}

The present invention relates to an organic zinc catalyst, a method for producing the same, and a method for producing a polyalkylene carbonate using the same.

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 the increase of greenhouse gases such as carbon dioxide in the atmosphere and freon and 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 copolymerization reaction 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 viewpoint of using carbon dioxide as a carbon resource. It is becoming. In particular, in recent years, polyalkylene carbonate by polymerization of the carbon dioxide and epoxide has gained much attention as a kind of biodegradable resin.

Accordingly, there is a continuous demand for development of a catalyst capable of producing polyalkylene carbonate more efficiently.

United States Patent Application Publication No. 4960862

The present invention is to provide an organic zinc catalyst, a method for producing the same and a method for producing a polyalkylene carbonate using the same.

Herein is zinc oxide core; A silicon oxide first shell provided on the core and having a thickness of 10 nm or more and 20 nm or less; And a second shell provided on the first shell and having a zinc carboxylate.

In addition, the present specification comprises the steps of forming a silicon oxide first shell having a thickness of 10nm or more and 20nm or less on the zinc oxide core; And forming a second shell having zinc carboxylate on the first shell to produce core-shell particles.

In addition, in the presence of the organic zinc catalyst, it provides a method for producing a polyalkylene carbonate comprising the step of polymerizing a monomer comprising epoxide and carbon dioxide.

Organic zinc catalyst according to one embodiment of the present specification has the advantage of easy separation after use.

In an exemplary embodiment of the present specification, the amount of carboxylate used to make the organic zinc catalyst can be reduced.

1 is a TEM image (left) of a ZnO @ SiO 2 particle prepared in Comparative Example 1 and a TEM image (right) in which ZnO is selectively dissolved by acid treatment.
FIG. 2 is a projection electron microscope (TEM) image (left) of ZnO @ SiO 2 particles prepared in Example 1 and a TEM image (right) in which ZnO is selectively dissolved by acid treatment.
3 is a TEM image (left) of a ZnO @ SiO 2 particle prepared in Comparative Example 2 and a TEM image (right) in which ZnO is selectively dissolved by acid treatment.
4 is a scanning electron microscope (SEM) image of the organic zinc catalyst prepared in Comparative Example 1. FIG.
5 is a scanning electron microscope (SEM) image of the organic zinc catalyst prepared in Example 1. FIG.
6 is a scanning electron microscope (SEM) image of the organic zinc catalyst prepared in Comparative Example 2.
7 is an XRD measurement graph of each of the organic zinc catalysts prepared in Example 1 and Comparative Examples 1-2.

Hereinafter, the present specification will be described in detail.

Herein is zinc oxide core; A silicon oxide first shell provided on the core; And a second shell provided on the first shell and having a zinc carboxylate.

The organic zinc catalyst is a heterogeneous catalyst, and the heterogeneous catalyst refers to a material that changes a reaction rate by using a material different from the reactant as a catalyst such as a gas-solid catalyst or a liquid-solid catalyst.

The organic zinc catalyst may be a catalyst for synthesizing polyalkylene carbonate. Specifically, the organic zinc catalyst may be a catalyst for polymerizing monomers including epoxide and carbon dioxide.

The average diameter of the organic zinc catalyst may be 1 μm or more and 2 μm or less.

The individual diameter of the organic zinc catalyst may be 100 nm or more and 4 μm or less.

In the present specification, the diameter of the particle refers to the length of the longest line segment between two points on the circumference of the particle.

The thickness of the first shell may be 10 nm or more and 20 nm or less. In this case, when forming the second shell, the zinc oxide core and the carboxylic acid may react to form zinc carboxylate, and after the second shell is formed to a predetermined thickness or more, the zinc oxide core may not function as a catalyst.

The carboxylate (Carboxylate) is a carboxylic acid is H + dissociated carboxylate ion (-COO -) from the carboxyl group (-COOH) of (carboxylic acid) containing at least one carboxyl group and the salt is a metal coupling (M (RCOO) n, wherein M is a metal and n is an integer of 1 or more). In particular, the zinc carboxylate is carboxylate ion (-COO -) means a salt of zinc and a combination.

The zinc carboxylate is 2 or more carboxylate anion (-COO -) may include.

The zinc carboxylate may include two or more carboxylate anions by dissociating H + from the carboxyl group (—COOH) of the compound including two or more carboxyl groups.

The zinc carboxylate may include two carboxylate anions by dissociating H + from the carboxyl group (-COOH) of the compound including two carboxyl groups.

The zinc carboxylate may include at least one of those containing at least one of aliphatic zinc dicarboxylate having 3 to 20 carbon atoms and aromatic zinc dicarboxylate having 8 to 40 carbon atoms.

The aliphatic dicarboxylate having 3 to 20 carbon atoms may be glutarate, malonate, succinate, or adipate.

The aromatic dicarboxylate having 8 to 40 carbon atoms may be terephthalate, isophthalate, homophthalate or phenylglutarate.

The second shell may include zinc glutarate.

Herein is a step of forming a silicon oxide first shell having a thickness of more than 10nm 20nm on the zinc oxide core; And forming a second shell having zinc carboxylate on the first shell to produce core-shell particles.

In the above-described method for producing an organic zinc catalyst, the above-described bar for the organic zinc catalyst can be cited.

The forming of the first shell may include forming a silicon oxide first shell on the zinc oxide core using a silicon oxide precursor.

If the silicon oxide precursor shell can be formed using the silicon oxide precursor is not particularly limited, for example, the silicon oxide precursor is triethoxysilane (TEOS) and tetramethyl orthosilicate (TMOS) It may include at least one.

The forming of the second shell may include reacting the zinc oxide core with the carboxylic acid to form the second shell on the first shell.

The carboxylic acid means a compound including a carboxyl group, and the carboxylic acid used in the forming of the second shell may be a compound including two or more carboxyl groups.

The zinc carboxylate may include at least one of those containing at least one of aliphatic zinc dicarboxylate having 3 to 20 carbon atoms and aromatic zinc dicarboxylate having 8 to 40 carbon atoms.

In the presence of the organic zinc catalyst, it provides a method for producing a polyalkylene carbonate comprising the step of polymerizing a monomer comprising epoxide and carbon dioxide.

The molar ratio of the organic zinc catalyst to the epoxide may be 1:50 or more and 1: 1000. Specifically, the molar ratio of the organic zinc catalyst to the epoxide may be 1:70 or more and 1: 600, and more specifically, 1:80 or more and 1: 300. In this case, there is an advantage of showing sufficient catalytic activity during solution polymerization, by-products, or less back-biting of the resin due to heating in the presence of a 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 to be obtained can be easily controlled.

The temperature of the solution polymerization may be 50 ° C or more and 100 ° C or less, and specifically, 70 to 90 ° C.

The pressure of the solution polymerization may be 15 bar or more and 50 bar or less, and specifically, 20 bar or more and 40 bar or less.

The solution polymerization time may be polymerized for 1 hour to 60 hours, and specifically, may be polymerized for 3 hours to 40 hours.

In this solution polymerization, solvents include methylene chloride, ethylene dichloride, trichloroethane, tetrachloroethane, chloroform, acetonitrile, propionitrile, dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide , Nitromethane, 1,4-dioxane, hexane, toluene, tetrahydrofuran, methylethylketone, methylamineketone, methyl isobutyl ketone, acetone, cyclohexanone, trichloroethylene, methyl acetate, vinyl acetate, ethyl acetate, At least one selected from the group consisting of propyl acetate, butyrolactone, caprolactone, nitropropane, benzene, styrene, xylene and methyl propasol can be used. Among these, by using methylene chloride or ethylene dichloride as a solvent, a polymerization reaction can be advanced more effectively.

Based on 1 part by weight of the epoxide, the content of the solvent may be 0.5 parts by weight or more and 100 parts by weight, and specifically 1 part by weight or more and 10 parts by weight. In this case, the solvent can act as the reaction medium and maintain the proper reaction concentration of the epoxide.

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, hexene oxide, octene oxide, decene oxide, dodecene oxide, tetradecene oxide, hexadecene oxide, octadecene oxide, butadiene monooxide, 1, 2-epoxy-7-octene, epifluorohydrin, epichlorohydrin, epibromohydrin, isopropyl glycidyl ether, butyl glycidyl ether, t-butyl glycidyl ether, 2-ethylhexyl Glycidyl ether, allyl glycidyl ether, cyclopentene oxide, cyclohexene oxide, cyclooctene oxide, cyclododecene oxide, alpha-pinene oxide, 2,3-epoxynorbornene, limonene oxide, dieldrin, 2, 3-epoxypropylbenzene, styrene oxide, phenylpropylene oxide, stilbene oxide, chlorostilbene Oxides, dichlorostilbene oxide, 1,2-epoxy-3-phenoxypropane, benzyloxymethyl oxirane, glycidyl-methylphenyl ether, chlorophenyl-2,3-epoxypropyl ether, epoxypropyl methoxyphenyl ether, Biphenyl glycidyl ether, glycidyl naphthyl ether, and the like. Most typically, ethylene oxide is used as the epoxide.

Hereinafter, the present specification will be described in more detail with reference to Examples. However, the following examples are merely to illustrate the present specification, but not to limit the present specification.

EXAMPLE

Example 1

SiO 2 Shell  ZnO @ SiO with a thickness of 10 nm-20 nm 2 Synthesis of Particles

A solution was prepared by stirring 24 mmol of ZnO particles (average diameter: 160 nm) at room temperature using 20 ml of IPA (Isopropyl Alcohol) and 4 ml H 2 O as a solvent. 1 ml of ammonia solution and 4.8 mmol of TEOS were added to the solution and allowed to react with stirring for 2 hours. Then separate the precipitate using a centrifuge. After washing twice with ethanol and dried at 70 ℃ oven to obtain ZnO @ SiO 2 particles.

Organic Zinc Catalyst Synthesis

In a 100 ml round bottom flask at room temperature, 50 ml of toluene was added, 20 mmol of glutaric acid was added, and the solution was heated. 17mmol of SiO 2 coated ZnO @ SiO 2 particles having a thickness of 10 nm to 20 nm or more were added to the solution heated to 55 ° C., and the mixture was allowed to react with stirring for 24 hours and then cooled to room temperature. At this time, through the reaction, ZnO of ZnO @ SiO 2 particles is reacted with glutaric acid to form zinc glutarate (ZnGA) on the silica of ZnO @ SiO 2 particles.

The precipitate was recovered using a centrifuge, washed three times or more with acetone, and dried in a vacuum oven at 70 ° C. to obtain an organic zinc catalyst.

Comparative Example 1

SiO 2 Shell  ZnO @ SiO> 20 nm thick 2 Synthesis of Particles

A solution was prepared by stirring 14.4 mmol of ZnO particles (average diameter: 160 nm) at room temperature using IPA 20 ml and 4 ml H 2 O as a solvent. 1 ml of ammonia solution and 4.8 mmol of TEOS were added to the solution and allowed to react with stirring for 2 hours. Then separate the precipitate using a centrifuge. After washing twice with ethanol and dried in 70 ℃ oven to obtain ZnO @ SiO 2 particles.

Organic Zinc Catalyst Synthesis

An organic zinc catalyst was prepared in the same manner as in Example 1, except that ZnO @ SiO 2 particles coated with SiO 2 having a thickness greater than 20 nm were used as the method of Comparative Example 1.

Comparative Example 2

SiO 2 Shell  ZnO @ SiO <10 nm thick 2 Synthesis of Particles

A solution was prepared by stirring 24 mmol of ZnO particles (average diameter: 160 nm) at room temperature using 23 ml of IPA and 1 ml H 2 O as a solvent. 1 ml of ammonia solution and 4.8 mmol of TEOS were added to the solution and allowed to react with stirring for 2 hours. Then separate the precipitate using a centrifuge. After washing twice with ethanol and dried at 70 ℃ oven to obtain ZnO @ SiO 2 particles.

Organic Zinc Catalyst Synthesis

Through the same manner as in, except that the method ZnO @ SiO 2 particles, the thickness of the coating is less than 10nm SiO 2 in the above-described Comparative Example 2 Example 1 was prepared in the organic zinc catalyst.

Experimental Example 1

The ZnO @ SiO 2 particles prepared in Example 1 and Comparative Examples 1-2 were photographed by TEM, respectively.

In Figures 1 to 3, the left side is a TEM image of each ZnO @ SiO 2 particles prepared in Example 1 and Comparative Examples 1-2, the right side is ZnO by acid treatment to measure the formation and thickness of the SiO 2 shell It is a selectively melted TEM image.

SEM photographs of the respective organic zinc catalysts prepared in Example 1 and Comparative Examples 1-2 are shown in FIGS. 4 to 6. It can be seen that the particles of the organic zinc catalyst prepared in Example 1 are larger than Comparative Examples 1 and 2. Because of the large size of the organic zinc catalyst particles, it is relatively easy to separate after use of the catalyst, and easy to recycle again.

The average diameters of the organic zinc catalysts prepared in Example 1 and Comparative Example 1-2 were 1.5 μm, 700 nm, and 500 nm, respectively.

Experimental Example 2

XRD results of the respective organic zinc catalysts prepared in Example 1 and Comparative Examples 1-2 are shown in FIG. 7. Through XRD peak, it is possible to confirm wt% of ZnO remaining after ZnGA synthesis.

In Comparative Example 2 using a SiO 2 shell having a thickness less than 10 nm, 0.4 wt% remained, so that most of ZnO participated in the reaction, whereas Example 1 and a comparison using a SiO 2 shell having a thickness of 10-20 nm and more than 20 nm were compared. In the case of Example 1, it can be seen that 35 wt% and 72 wt% of ZnO remain, respectively.

Since ZnO and glutaric acid participate in the reaction at the same molar ratio during ZnGA synthesis, after ZnGA is synthesized by reacting ZnO and glutaric acid, XRD data is confirmed to infer the participation rate of glutaric acid according to the content of unreacted ZnO. can do.

Therefore, it can be seen that the amount of glutaric acid (GA) is reduced in comparison with Comparative Example 2 (thickness of the SiO 2 shell: less than 10 nm) in Example 1 through wt% of ZnO remaining after ZnGA synthesis.

Experimental Example 3

0.4 g of catalyst and 8.5 g of dichloromethane are placed in a high temperature high pressure reactor. 8.5 g of ethylene oxide (EO) was added to the reactor, and CO 2 was added to the reactor under a pressure of 30 bar (about 10 g). After the reaction was carried out at 70 ℃ for 3 hours to determine the activity of the amount of polymer formed is shown in Table 1 below.

Thickness of SiO 2 shell Catalytic activity (g-polymer / g-catalyst) Example 1 10-20nm 14 Comparative Example 1 More than 20nm 9 Comparative Example 2 Less than 10nm 11

Table 1 shows that Example 1 having a suitable thickness of SiO 2 particles has a higher catalytic activity than Comparative Examples 1 and 2.

Claims (12)

Zinc oxide cores;
A silicon oxide first shell provided on the core and having a thickness of 10 nm or more and 20 nm or less; And
An organic zinc catalyst provided on the first shell and comprising a second shell having zinc carboxylate,
The organic zinc catalyst is an organic zinc catalyst is a catalyst for the synthesis of polyalkylene carbonate. The organic zinc catalyst of claim 1, wherein the zinc carboxylate is zinc dicarboxylate. The organic zinc catalyst of claim 1, wherein the zinc carboxylate comprises at least one of aliphatic zinc dicarboxylate having 3 to 20 carbon atoms and aromatic zinc dicarboxylate having 8 to 40 carbon atoms. The organic zinc catalyst of claim 1, wherein the second shell comprises zinc glutarate. The organic zinc catalyst of Claim 1 whose average diameter of the said organic zinc catalyst is 1 micrometer or more and 2 micrometers or less. delete Forming a silicon oxide first shell having a thickness of 10 nm or more and 20 nm or less on the zinc oxide core; And
Forming a second shell having zinc carboxylate on the first shell to produce core-shell particles,
The organic zinc catalyst is a method for producing an organic zinc catalyst is a catalyst for the synthesis of polyalkylene carbonate. The method of claim 7, wherein the forming of the first shell comprises forming a silicon oxide first shell on the zinc oxide core using a silicon oxide precursor. The method of claim 7, wherein the forming of the second shell comprises reacting the zinc oxide core with a carboxylic acid to form zinc carboxylate on the first shell. The method of claim 7, wherein the zinc carboxylate comprises at least one of those containing at least one of aliphatic zinc dicarboxylate having 3 to 20 carbon atoms and aromatic zinc dicarboxylate having 8 to 40 carbon atoms. Method for preparing an organic zinc catalyst. A process for producing a polyalkylene carbonate comprising polymerizing a monomer comprising epoxide and carbon dioxide in the presence of an organic zinc catalyst according to any one of claims 1 to 5. The method of claim 11, wherein the polymerization step is performed by solution polymerization in an organic solvent.
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US4960862A (en) 1989-03-31 1990-10-02 Air Products And Chemicals, Inc. Regeneration of metallo-organic catalyst for carbon dioxide-epoxide copolymerization
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