# US 9,751,981 B2 · Manufacturing method of organic zinc catalyst and manufacturing method of polyalkylene carbonate resin

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- Number: US 9,751,981 B2
- Document ID: US9751981B2
- Status: Granted
- Kind: B2
- Application number: 14/917,219
- Filed: 2014-10-30
- Published: 2016-07-07
- Granted: 2017-09-05
- Earliest claimed: 2013-10-30
- Assignees: LG Chem, Ltd.
- Applicants: LG Chem, Ltd.
- Inventors: Sung-Kyoung Kim; Seung Young Park; Hyun Ju Cho
- Web page: https://patentgrep.com/patent/US9751981B2

## CPC

- C08G 64/34: and cyclic ethers
- B01J 31/12: containing organo-metallic compounds or metal hydrides
- C07C 51/412: {by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part}
- B01J 31/2239: {Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands}
- C08K 5/0091: {Complexes with metal-heteroatom-bonds}
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)

## Abstract

The present invention relates to a manufacturing method of an organic zinc catalyst having more uniform and finer particle size and showing a more improved activity in a polymerization process for manufacturing a polyalkylene carbonate resin, and a manufacturing method of the polyalkylene carbonate resin using the organic zinc catalyst obtained by the manufacturing method of the organic zinc catalyst, the manufacturing method of an organic zinc catalyst including: forming a zinc dicarboxylate-based catalyst by reacting a zinc precursor with C3-C20 dicarboxylic acid, wherein the reaction step is performed under a condition in which the number of moles of the dicarboxylic acid is more than that of the zinc precursor in a reaction system, throughout the entire reaction step.

## Claims

### Claim 1

A manufacturing method of an organic zinc catalyst comprising:
forming a zinc dicarboxylate-based catalyst by reacting a zinc precursor with C3-C20 dicarboxylic acid,
wherein the reaction step is performed under a condition in which the number of moles of the dicarboxylic acid is more than that of the zinc precursor in a reaction system, throughout the entire reaction steps, and
wherein the reaction step is performed in a liquid medium, and is performed by separately adding a solution or a dispersion liquid containing the zinc precursor to a solution or a dispersion liquid containing the dicarboxylic acid two or more times.

### Claim 2 (depends on 1)

The manufacturing method of claim 1, wherein:
the dicarboxylic acid has a molar ratio of 1.05 to 1.5 relative to 1 mol of the zinc precursor.

### Claim 3 (depends on 1)

The manufacturing method of claim 1, wherein:
the zinc precursor includes a zinc compound selected from the group consisting of zinc oxide, zinc sulfate (ZnSO4), zinc chlorate (Zn(ClO3)2), zinc nitrate (Zn(NO3)2), zinc acetate (Zn(OAc)2, and zinc hydroxide.

### Claim 4 (depends on 1)

The manufacturing method of claim 1, wherein:
the C3-C20 dicarboxylic acid includes an aliphatic dicarboxylic acid selected from the group consisting of a malonic acid, a glutaric acid, a succinic acid, and an adipic acid, or an aromatic dicarboxylic acid selected from the group consisting of a terephthalic acid, an isophthalic acid, a homophthalic acid, and a phenylglutaric acid.

### Claim 5 (depends on 1)

The manufacturing method of claim 1, wherein:
the reaction step is performed by adding the solution or the dispersion liquid containing the zinc precursor to the solution or the dispersion liquid containing the dicarboxylic acid at an equal time interval with an amount at which the total used amount of the zinc precursor is divided into two to ten parts.

### Claim 6 (depends on 1)

The manufacturing method of claim 1, wherein:
the reaction step is performed by dropping the solution or the dispersion liquid containing the zinc precursor in droplet forms onto the solution or the dispersion liquid containing the dicarboxylic acid.

### Claim 7 (depends on 1)

The manufacturing method of claim 1, wherein:
the liquid medium includes at least one solvent selected from the group consisting of toluene, hexane, DMF, ethanol and water.

### Claim 8 (depends on 1)

The manufacturing method of claim 1, wherein:
the organic zinc catalyst in a particle shape having an average particle size of 0.8 μm or less and a particle size standard deviation of 0.2 μm or less is manufactured.

### Claim 9 (depends on 1)

The manufacturing method of claim 1, wherein:
the organic zinc catalyst having a surface area of 1.8 m2/g or more is manufactured.

### Claim 10 (depends on 1)

The manufacturing method of claim 1, wherein:
the reaction step is performed at a temperature of 50 to 130° C. for 1 to 10 hours.

### Claim 11 (depends on 1)

A manufacturing method of a polyalkylene carbonate resin comprising:
polymerizing an epoxide and a monomer including carbon dioxide in the presence of the organic zinc catalyst manufactured by the method of claim 1.

### Claim 12 (depends on 11)

The manufacturing method of claim 11, wherein:
the manufacturing method is performed in an organic solvent by solution polymerization.