Organozinc-supported catalyst, method for producing the same, and method for preparing polyalkylene carbonate resin using catalyst

• US 10,640,610 B2
• Filed: 03/17/2017
• Issued: 05/05/2020
• Est. Priority Date: 03/24/2016
• Status: Active Grant

• Current Assignee: LG Chem Limited (LG Corporation)
• Original Assignee: LG Chem Limited (LG Corporation)
• Inventors: Lee, Jun Wye, Lee, Il Ha, Park, Seung Young, Kim, Ki-Hwan, Kim, Sung-Kyoung
• Primary Examiner(s): Fang, Shane
• Application Number:
  US15/768,319
• Publication Number:
  US 20190010283A1
• Time in Patent Office: 1,145 Days
• CPC Class Codes: B01J 23/06 of zinc, cadmium or mercury
• CPC Class Codes: B01J 31/12 containing organo-metallic compounds or metal hydrides
• CPC Class Codes: B01J 35/00 Catalysts, in general, characterised by their form or physical properties
• CPC Class Codes: B01J 35/30 characterised by their physical properties
• CPC Class Codes: C07F 3/06 Zinc compounds
• CPC Class Codes: C08G 64/20 General preparatory processes
• CPC Class Codes: C08G 64/34 and cyclic ethers

Abstract

The present invention relates to an organozinc-supported catalyst, a method for producing the same, and a method for preparing a polyalkylene carbonate resin using the catalyst. The organozinc-supported catalyst provided by the present invention includes a zinc dicarboxylate-based catalyst supported on a zinc compound layer formed on at least a portion of a support surface, and can be used repeatedly or continuously while exhibiting improved selectivity in the polymerization process for preparing a polyalkylene carbonate resin.

Claims

1. An organozinc-supported catalyst comprising:

a support;

a zinc compound layer formed on at least a portion of the surface of the support; and

a zinc dicarboxylate-based catalyst supported on the zinc compound layer,

wherein the zinc compound layer has a thickness of 10 to 1000 nm.

2. The organozinc-supported catalyst of claim 1, wherein the support has a needle-like shape, a plate-like shape, or a spherical shape.

3. The organozinc-supported catalyst of claim 1, wherein the support is at least one selected from the group consisting of silica (SiO₂), zirconium oxide (ZrO₂), aluminum oxide (Al₂O₃), magnesium chloride (MgCl₂), calcium chloride (CaCl₂), magnesium oxide (MgO), titanium oxide (TiO₂), boron oxide (B₂O₃), calcium oxide (CaO), barium oxide (BaO), thorium oxide (ThO₂), stainless steel, and silicon carbide (SiC).

4. The organozinc-supported catalyst of claim 1, wherein the zinc compound is at least one selected from the group consisting of zinc oxide (ZnO), zinc sulfate (ZnSO₄), zinc chlorate (Zn(ClO₃)₂), zinc nitrate (Zn(NO₃)₂), zinc acetate (Zn(OAc)₂), and zinc hydroxide (Zn(OH)₂).

5. The organozinc-supported catalyst of claim 1, wherein the zinc compound layer has a structure in which zinc compounds in the form of a nano-rod, a nano-hair, a nano-fiber, a nano-pillar, or a nano-wire are clustered.

6. The organozinc-supported catalyst of claim 1, wherein the zinc dicarboxylate-based catalyst is at least one selected from the group consisting of a zinc malonate-based catalyst, a zinc glutarate-based catalyst, a zinc succinate-based catalyst, a zinc adipate-based catalyst, a zinc terephthalate-based catalyst, a zinc isophthalate-based catalyst, a zinc homophthalate-based catalyst, and a zinc phenylglutarate-based catalyst.

7. The organozinc-supported catalyst of claim 1, wherein the zinc dicarboxylate-based catalyst is supported on the surface of the zinc compound layer in a flake shape.

8. The organozinc-supported catalyst of claim 1, wherein the zinc dicarboxylate-based catalyst forms a thin film having a thickness of 10 to 500 nm.

9. A method for producing an organozinc-supported catalyst according to claim 4, the method comprising:

treating a support with a zinc compound to form a zinc compound layer on at least a portion of the surface of the support; and

reacting the zinc compound with a dicarboxylic acid to support a zinc dicarboxylate-based catalyst on the zinc compound layer.

10. The method of claim 9, wherein the treating the zinc compound is performed by a method of depositing the zinc compound on the surface of the support.

11. The method of claim 9, wherein the treating the zinc compound is performed such that the zinc compound layer has a thickness of 10 to 1000 nm.

12. The method of claim 9, wherein the reacting the zinc compound with the dicarboxylic acid is performed in the presence of at least one solvent selected from the group consisting of toluene, hexane, dimethylformamide, acetone, methanol, ethanol, and water.

13. The method of claim 12, wherein the solvent is added in an amount of 2 to 1000 mol relative to 1 mole of the dicarboxylic acid.

14. The method of claim 9, the reacting the zinc compound with the carboxylic acid is performed for 1 hour to 10 hours at a temperature of 40 to 130°

C.

15. The method of claim 9, wherein the reacting the zinc compound with the dicarboxylic acid is performed on the surface of the zinc compound layer.

16. A method for preparing a polyalkylene carbonate resin, the method comprising polymerizing a monomer including an epoxide and carbon dioxide in the presence of an organozinc-supported catalyst according to claim 4.

17. The method of claim 16, wherein the polymerizing the monomer is performed by a solution polymerization in an organic solvent.

18. The method of claim 17, wherein the solvent is added in a weight of 0.1 to 100 times relative to the weight of the epoxide.

19. The method of claim 17, wherein the solution polymerization is performed for 1 hour to 60 hours at a temperature of 50 to 90°

C. and a pressure of 15 to 50 bar.