Preparation method of organic zinc catalyst and poly(alkylene carbonate) resin

• US 10,047,032 B2
• Filed: 06/09/2015
• Issued: 08/14/2018
• Est. Priority Date: 06/13/2014
• Status: Active Grant

• Current Assignee: LG Chem Limited (LG Corporation)
• Original Assignee: LG Chem Limited (LG Corporation)
• Inventors: Kim, Sung Kyoung, Kang, Seong Kyun, Lee, Jun Wye, Park, Seung Young, Choi, Hyeon
• Primary Examiner(s): EGWIM, KELECHI CHIDI
• Application Number:
  US14/734,856
• Publication Number:
  US 20150361023A1
• Time in Patent Office: 1,162 Days
• Field of Search: 528414, 524792
• CPC Class Codes: B01J 2231/14 Other (co) polymerisation, e.g. of lactides or epoxides
• CPC Class Codes: B01J 2531/26 Zinc
• CPC Class Codes: B01J 31/2239 Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
• CPC Class Codes: B01J 35/23 in a colloidal state
• CPC Class Codes: B01J 35/40 characterised by dimensions, e.g. grain size in a colloidal state B01J35/23; crystallite size B01J35/77
• CPC Class Codes: B01J 37/0203 the impregnation liquid containing organic compounds
• CPC Class Codes: B01J 37/0209 involving a reaction between the support and a fluid
• CPC Class Codes: C07C 51/418 Preparation of metal complexes containing carboxylic acid moieties
• CPC Class Codes: C07C 55/12 Glutaric acid
• CPC Class Codes: C08G 64/34 and cyclic ethers

Abstract

The present invention relates to a preparation method of an organic zinc catalyst capable of preparing an organic zinc catalyst having a finer and more uniform particle size and more improved activity during a polymerization process for preparing a poly(alkylene carbonate) resin, and a preparation method of a poly(alkylene carbonate) resin using the organic zinc catalyst. The preparation method of an organic zinc catalyst includes reacting a zinc precursor and a dicarboxylic acid in the presence of a dispersant to form a zinc dicarboxylate-based catalyst, wherein a reaction step is performed under a condition at which the number of moles of the dicarboxylic acid present in a reaction system is larger than that of the zinc precursor throughout the entire reaction step.

Claims

1. A preparation method of an organic zinc catalyst, the preparation method comprising:

providing a zinc precursor surface-treated with a dispersant; and

reacting the surface-treated zinc precursor with a dicarboxylic acid having 3 to 20 carbon atoms to form a zinc dicarboxylate-based catalyst,

wherein the reaction step is performed under a condition at which the number of moles of the dicarboxylic acid present in a reaction system is larger than that of the zinc precursor throughout the entire reaction step,

wherein the dispersant is an anionic surfactant.

2. The preparation method of claim 1, wherein the dispersant is an alkyl phenol ethoxylated phosphate ester represented by the following Chemical Formula 1:

3. The preparation method of claim 1, wherein the zinc precursor surface treated by the dispersant is formed by mixing the zinc precursor with the dispersant in a solvent.

4. The preparation method of claim 3, wherein the dispersant is mixed at a content of 0.01 to 10 wt % with respect to the zinc precursor.

5. The preparation method of claim 1, wherein the dicarboxylic acid is used in a ratio of 1.05 to 1.5 moles based on 1 mole of the zinc precursor.

6. The preparation 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.

7. The preparation method of claim 1, wherein the dicarboxylic acid having 3 to 20 carbon atoms includes an aliphatic dicarboxylic acid selected from the group consisting of malonic acid, glutaric acid, succinic acid, and adipic acid, or an aromatic dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid, homophthalic acid, and phenyl glutaric acid.

8. The preparation method of claim 1, wherein the reaction step is performed in a liquid medium,

while adding a solution or dispersion containing the zinc precursor in portions 2 times or more to a solution or dispersion containing the dicarboxylic acid.

9. The preparation method of claim 8, wherein the reaction step is performed while adding a solution or dispersion containing the zinc precursor at an amount obtained by dividing the entire use amount of the zinc precursor into 2 to 10 to the solution or dispersion containing the dicarboxylic acid at the same time interval.

10. The preparation method of claim 8, wherein the reaction step is performed while dripping the solution or dispersion containing the zinc precursor in a droplet form into the solution or dispersion containing the dicarboxylic acid.

11. The preparation method of claim 8, wherein the liquid medium includes one or more kinds of solvents selected from the group consisting of toluene, hexane, dimethylformamide, ethanol, and water.

12. The preparation method of claim 1, wherein the organic zinc catalyst is in a form of particles having an average particle size of 0.5 μ

m or less.

13. The preparation method of claim 1, wherein the organic zinc catalyst having a surface area of 1.8 m²/g or more is prepared.