Method for preparing organic zinc catalyst, organic zinc catalyst prepared by the method and method for preparing polyalkylene carbonate resin using the catalyst

Patent metadata

Field	Value
Publication number	US-2019329230-A1
Application number	US-201816469421-A
Country	US
Kind code	A1
Filing date	Aug 28, 2018
Priority date	Aug 28, 2017
Publication date	Oct 31, 2019
Grant date	—

Abstract

The disclosed relates to a method for preparing an organic zinc catalyst used in the synthesis of a polyalkylene carbonate resin, an organic zinc catalyst provided therefrom, and a method for preparing a polyalkylene carbonate resin using the catalyst. The organic zinc catalyst according to the present disclosure includes a predetermined amount of Zr on the surface through a simple process, and thus can exhibit improved catalytic activity as compared to a conventional catalyst in the polymerization process for preparing a polyalkylene carbonate resin.

First claim

1 . A method for preparing an organic zinc catalyst, comprising:
reacting a zinc precursor with a dicarboxylic acid having 3 to 20 carbon atoms and a zirconium-based co-catalyst, wherein the zirconium-based co-catalyst is Zr-metal organic framework (MOF) containing zirconium or a Zr precursor.

2 . The method for preparing an organic zinc catalyst of claim 1 , wherein the Zr-metal organic framework is at least one selected from the group consisting of UiO-66 (zirconium 1,4-dicarboxybenzene MOF), UiO-66-NH 2 , UiO-67, UiO-68, and Nu-1000.

3 . The method for preparing an organic zinc catalyst of claim 1 , wherein the Zr precursor is at least one selected from the group consisting of ZrSO 4 , zirconium acetate, zirconium iodide, zirconium fluoride, zirconium chloride, zirconium acetylacetonate, zirconium butoxide, zirconium propoxide, and ZrO 2 .

4 . The method for preparing an organic zinc catalyst of claim 1 ,
wherein the zirconium-based co-catalyst is used at a molar ratio of 0.1 mmol to 0.5 mol based on 1 mol of the zinc precursor.

5 . The method for preparing an organic zinc catalyst of claim 1 , which is used for the synthesis of a polyalkylene carbonate resin.

6 . The method for preparing an organic zinc catalyst of claim 1 ,
wherein the zinc precursor includes at least one compound selected from the group consisting of zinc oxide (ZnO), zinc sulfate (ZnSO 4 ), zinc chlorate (Zn(ClO 3 ) 2 ), zinc nitrate (Zn(NO 3 ) 2 ), zinc acetate (Zn(OAc) 2 ), and zinc hydroxide (Zn(OH) 2 ), and wherein the dicarboxylic acid having 3 to 20 carbon atoms includes at least one compound selected from the group consisting of a malonic acid, a glutaric acid, a succinic acid, an adipic acid, a terephthalic acid, an isophthalic acid, a homophthalic acid, and a phenylglutaric acid.

7 . The method for preparing an organic zinc catalyst of claim 1 ,
wherein the reaction is carried out in the presence of at least one solvent selected from the group consisting of toluene, hexane, dimethylformamide, ethanol, and water.

8 . An organic zinc catalyst comprising:
a zinc dicarboxylate-based compound; and a zirconium element supported or substituted on the surface of the zinc dicarboxylate-based compound, wherein the zinc zirconium element is obtained derived from any one of a zirconium-based co-catalyst which is a Zr-metal organic framework (MOF) containing zirconium or a Zr precursor.

9 . The organic zinc catalyst of claim 8 , wherein the Zr-metal organic framework is at least one selected from the group consisting of UiO-66 (zirconium 1,4-dicarboxybenzene MOF), UiO-66-NH 2 , UiO-66-NH 3+ , UiO-67, UiO-68, and Nu-1000.

10 . The organic zinc catalyst of claim 8 , wherein the Zr precursor is at least one selected from the group consisting of ZrSO 4 , zirconium acetate, zirconium iodide, zirconium fluoride, zirconium chloride, zirconium acetylacetonate, zirconium butoxide, zirconium propoxide, and ZrO 2 .

11 . The organic zinc catalyst of claim 8 , which is used for the synthesis of a polyalkylene carbonate resin.

12 . The organic zinc catalyst of claim 8 , wherein the content of the zirconium element on the surface of the zinc dicarboxylate-based compound is 0.01 to 5% by weight, based on the total weight of the ratio of the entire elements constituting the organic zinc catalyst.

13 . The organic zinc catalyst of claim 8 , wherein
the zinc dicarboxylate-based compound is a reaction product of a zinc precursor and a dicarboxylic acid having 3 to 20 carbon atoms, wherein the zinc precursor includes at least one compound selected from the group consisting of zinc oxide (ZnO), zinc sulfate (ZnSO 4 ), zinc chlorate (Zn(ClO 3 ) 2 ), zinc nitrate (Zn(NO 3 ) 2 ), zinc acetate (Zn(OAc) 2 ), and zinc hydroxide (Zn(OH) 2 ), and wherein the dicarboxylic acid having 3 to 20 carbon atoms includes at least one compound selected from the group consisting of a malonic acid, a glutaric acid, a succinic acid, an adipic acid, a terephthalic acid, an isophthalic acid, a homophthalic acid, and a phenylglutaric acid.

14 . A method for preparing a polyalkylene carbonate resin, comprising
polymerizing a monomer containing an epoxide and carbon dioxide in the presence of the organic zinc catalyst of claim 8 .

15 . The method for preparing an organic zinc catalyst of claim 1 ,
wherein the zirconium-based co-catalyst is used in an amount of 0.1 to 100 parts by weight based on 100 parts by weight of the zinc precursor.

Assignees

• Lg Chemical Ltd

Inventors

• Bang Jungup
• Park Kyosung
• Park Seung Young
• Hwang Gyo Hyun
• Choi Byung Hee
• Kim Sung-Kyoung
• Bang Yongju

Classifications

• C08G64/34

  and cyclic ethers · CPC title

• B01J31/04 Primary

  containing carboxylic acids or their salts {(B01J31/0277 - B01J31/0298 take precedence; multi-metal carboxylate complexes like Pd (II) acetate, i.e. Pd3 (OAc) 6 or Cr(II)acetate, i.e. Cr2(OAc)4 B01J31/2226)} · 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

• B01J2531/26

  Zinc · CPC title

• B01J37/04 Primary

  Mixing {(B01J37/0009, B01J37/0018 take precedence)} · CPC title