Organic zinc catalyst, and manufacturing method thereof and manufacturing method of polyalkylene carbonate resin using the same (as amended)

Patent metadata

Field	Value
Publication number	US-10047196-B2
Application number	US-201415034696-A
Country	US
Kind code	B2
Filing date	Nov 18, 2014
Priority date	Nov 18, 2013
Publication date	Aug 14, 2018
Grant date	Aug 14, 2018

Abstract

The present disclosure relates to an organic zinc catalyst suppressing agglomeration among catalyst particles during a manufacturing method to have more uniform and finer particle size, thereby showing a more improved activity in a polymerization process for manufacturing a polyalkylene carbonate resin, a manufacturing method thereof, and a manufacturing method of a polyalkylene carbonate resin using the same, wherein the organic zinc catalyst is a zinc dicarboxylate-based organic zinc catalyst used for a reaction in which a polyalkylene carbonate resin is manufactured from carbon dioxide and epoxide and includes a monocarboxylic acid-derived moiety having a C3-C15 aliphatic hydrocarbon group (provided that at least one oxygen or carbonyl group is included or not included in the aliphatic hydrocarbon group) that is bonded to an end of at least one side of the zinc dicarboxylate-based organic zinc catalyst.

First claim

What is claimed is:

1. An organic zinc catalyst which is a zinc dicarboxylate-based organic zinc catalyst used for a reaction in which a polyalkylene carbonate resin is manufactured from carbon dioxide and epoxide, the organic zinc catalyst comprising:
a moiety having a C4-C15 aliphatic hydrocarbon group (R) bonded to an end of at least one side of the zinc dicarboxylate-based organic zinc catalyst,
wherein the moiety having a C4-C15 aliphatic hydrocarbon group (R) is derived from a monocarboxylic acid (R—COOH),
wherein the moiety having a C4-C15 aliphatic hydrocarbon group (R) optionally inlcudes at least one oxygen or carbonyl group,
wherein the organic zinc catalyst has a particle shape having an average particle size of 0.2 to 0.9 μm and a particle size standard deviation of 0.05 to 0.3 μm, and
wherein the monocarboxylic acid-derived moiety is bonded at 0.2 to 0.5 molar ratio relative to 1 mol of a dicarboxylate-derived moiety of the organic zinc catalyst.

2. The organic zinc catalyst of claim 1 , wherein: the zinc dicarboxylate-based organic zinc catalyst is a catalyst in which zinc is bonded to C3-C20 aliphatic dicarboxylate or C8-C40 aromatic dicarboxylate.

3. The organic zinc catalyst of claim 1 , wherein: the zinc dicarboxylate-based organic zinc catalyst is a zinc glutarate-based catalyst.

4. The organic zinc catalyst of claim 1 , wherein: the monocarboxylic acid includes at least one selected from the group consisting of valeric acid, lauric acid, 3,5-dioxohexanoic acid, 3,5,7-trioxo-dodecanoic acid, acetoacetic acid, levulinic acid, 4-oxo-4H-1-benzopyran-2-carboxylic acid, and 5-hydroxy-4-oxo-4H-pyran-2-carboxylic acid.

5. A manufacturing method of the organic zinc catalyst of claim 1 comprising:
reacting a zinc precursor, a dicarboxylic acid, and a monocarboxylic acid having a C4-C15 aliphatic hydrocarbon group with or without at least one oxygen or carbonyl group,
wherein the monocarboxylic acid-derived moiety is bonded at 0.2 to 0.5 molar ratio relative to 1 mol of a dicarboxylate-derived moiety of the organic zinc catalyst.

6. The manufacturing method of claim 5 , wherein:
the reaction step includes reacting the zinc precursor with the dicarboxylic acid, and
further reacting with the monocarboxylic acid.

7. The manufacturing method of claim 5 , wherein:
the zinc precursor includes a compound selected from the group consisting of zinc oxide, zinc hydroxide, zinc acetate (Zn(O 2 CCH 3 ) 2 ), zinc nitrate (Zn(NO 3 ) 2 ) and zinc sulfate (ZnSO 4 ).

8. The manufacturing method of claim 6 , wherein:
the reaction step with the dicarboxylic acid is performed at a temperature of 40 to 90° C. for 0.5 to 10 hours, and the reaction step of the monocarboxylic acid is performed at a temperature of 80 to 150° C. for 1 to 20 hours.

9. The manufacturing method of claim 5 , wherein:
the monocarboxylic acid is used at 0.1 to 0.5 molar ratio relative to 1 mol of the dicarboxylic acid.

10. The manufacturing method of claim 5 , wherein:
the dicarboxylic acid is used at 1.0 to 1.5 molar ratio relative to 1 mol of the zinc precursor.

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

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

Assignees

• Lg Chemical Ltd

Inventors

• Kim Sung-Kyoung
• Park Seung Young
• Cho Hyun Ju

Classifications

• B01J2531/26

  Zinc · CPC title

• B01J31/1691

  Coordination polymers, e.g. metal-organic frameworks [MOF] (preparation of metal complexes containing carboxylic acid moieties C07C51/418; MOF's per se C07F) · CPC title

• B01J31/2239

  Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands · CPC title

• C08K5/56

  Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond · CPC title

• C08G64/34 Primary

  and cyclic ethers · CPC title