Economical method of preparing a resin composition including polyalkylene carbonate with improved thermal stability and processability

Patent metadata

Field	Value
Publication number	US-10829635-B2
Application number	US-201715769648-A
Country	US
Kind code	B2
Filing date	Mar 8, 2017
Priority date	Mar 11, 2016
Publication date	Nov 10, 2020
Grant date	Nov 10, 2020

Abstract

The present disclosure relates to an economical method of preparing a resin composition including a polyalkylene carbonate with improved thermal stability and processability. More specifically, the method of preparing a resin composition includes the steps of polymerizing carbon dioxide and an epoxide compound in the presence of a zinc-based catalyst and a solvent, recovering monomers, removing the catalyst and recovering raw materials, solution-blending with a thermostable resin to improve the thermal stability and processability, and removing the solvent and byproducts from the reaction mixture by using an agitated flash drum and an extrusion or kneader-type devolatilizer.

First claim

What is claimed is:

1. A method of preparing a resin composition containing a polyalkylene carbonate, comprising the steps of:
(a) polymerizing a polyalkylene carbonate using a zinc-based catalyst, a solvent, carbon dioxide, and an epoxide compound;
(b) recovering unreacted residual monomers from a polymerization solution obtained after the step (a) which contains the polyalkylene carbonate, unreacted residual monomers, a catalyst residue, the solvent, and cyclic alkylene carbonate-based byproducts;
(c) removing the catalyst residue from the polymerization solution obtained after the step (b) and recovering raw materials of the catalyst;
(d) solution-blending by mixing the polymerization solution obtained after the step (c) which contains the polyalkylene carbonate, the solvent, and the cyclic alkylene carbonate-based byproducts with a thermostable blending resin to prepare a resin composition containing the polyalkylene carbonate;
(e) recovering the solvent from the resin composition containing the polyalkylene carbonate; and
(f) removing the cyclic alkylene carbonate-based byproducts from the resin composition containing the polyalkylene carbonate.

2. The method of claim 1 ,
wherein the step (a) of polymerizing further comprises controlling the molecular weight of the polyalkylene carbonate resin obtained by polymerization by controlling the moisture content in the reaction mixture before initiation of the polymerization reaction to 10 to 1000 ppm.

3. The method of claim 1 ,
wherein the step (b) of recovering unreacted residual monomers comprises removing the unreacted residual monomers from the polymerization solution by using a venting method, a simple flash drum, a falling film evaporator, a thin film evaporator, or a combination thereof.

4. The method of claim 1 ,
wherein the step (c) of removing the catalyst residue comprises removing the catalyst residue from the polymerization solution by a method using an ion exchange resin, a filtration method selected from the group consisting of a metal filter, a polymer filter, and a centrifuge, or a combination thereof.

5. The method of claim 1 ,
wherein the step (c) of recovering raw materials of the catalyst comprises removing the catalyst residue from the polymerization solution by using an ion exchange resin, precipitating the raw materials of the catalyst on the surface of the ion exchange resin, and recovering the raw materials of the catalyst by using water, or recovering the catalyst from the polymerization solution by using a metal filter, a polymer filter, or a centrifuge, passing through an ion exchange resin to precipitate the raw materials of the catalyst on the surface of the ion exchange resin, and recovering the raw materials of the catalyst by using water.

6. The method of claim 1 ,
wherein the step (d) of solution-blending comprises preparing a resin composition containing the polyalkylene carbonate by adding the thermostable blending resin dissolved in the solvent into the polymerization solution containing the polyalkylene carbonate by using a stirrer mixer, a tank reactor, or an extruder to make the weight ratio of the polyalkylene carbonate to the thermostable blending resin of 99:1 to 10:90, and then solution-blending.

7. The method of claim 1 ,
wherein the blending resin comprises at least one selected from the group consisting of polylactide, polymethyl methacrylate, and cellulose acetate.

8. The method of claim 1 ,
wherein the step (e) of recovering the solvent comprises recovering the solvent in a content of at least 60 wt% in the polymerization solution by volatilizing the solvent while extruding or kneading the polymerization solution through a co-extrusion or kneading method using a twin-screw extrusion devolatilizer or a kneader-type devolatilizer at a temperature of 40° C. to 150° C. and atmospheric pressure to a vacuum.

9. The method of claim 1 ,
wherein the step (f) of removing the byproducts comprises removing the byproducts and the remaining solvent from the polymerization solution using an extrusion devolatilizer or a kneader-type devolatilizer at a temperature of 120° C. to 200° C. and a degree of vacuum of 1 Torr to 500 Torr.

10. The method of claim 1 ,
wherein after the step (f) of removing the byproducts, the method further comprises the step (g) of obtaining the resin composition containing the polyalkylene carbonate in the form of pellets through a pelletizing process and a drying process of the resin composition containing the polyalkylene carbonate in which byproducts were removed.

11. The method of claim 10 ,
wherein after the step of obtaining the resin composition containing the polyalkylene carbonate in the form of pellets, the method comprises the step of further compounding and pelletizing the pelletized resin composition containing the polyalkylene carbonate with the thermostable compounding resin.

12. The method of claim 1 ,
wherein a final resin composition comprises the polyalkylene carbonate having a metal content of the catalyst of less than 300 ppm, a solvent content of 0.5 wt% or less, and a cyclic alkylene carbonate byproducts content of 2 wt% or less.

13. The method of claim 1 ,
wherein the steps of polymerizing to removing the byproducts are carried out by a continuous or batch type of process.

14. The method of claim 1 ,
wherein the zinc-based catalyst is a zinc dicarboxylate-based catalyst prepared by reacting a zinc-based precursor with a C3 to C20 dicarboxylic acid.

15. The method of claim 1 ,
wherein the epoxide compound is at least one selected from the group consisting of: a C2 to C20 alkylene oxide substituted or unsubstituted with a halogen or a C1 to C5 alkyl group;
a C4 to C20 cycloalkylene oxide substituted or unsubstituted with a halogen or a C1 to C5 alkyl group; and a C8 to C20 styrene oxide substituted or unsubstituted with a halogen or a C1 to C5 alkyl group, and
the solvent is at least one selected from the group consisting of methylene chloride, 1,2-dichloroethane, n-methyl pyrrolidone, dimethylsulfoxide, 1,4-dioxane, and 1,3-dioxolane.

16. The method of claim 1 ,
wherein a molar ratio of the epoxide compound to the zinc-based catalyst is 50:1 to 400:1 in the polymerization step, and the polymerization is carried out at a polymerization temperature of 50 to 90° C. and a polymerization pressure of 15 to 50 bar for 1 to 60 hours.

Assignees

• Lg Chemical Ltd

Inventors

• Lee Jun Wye
• Park Seung Young
• Lee Jin Woo
• Cho Hyun Ju
• Sohn Jung Min
• Kim Yoon Jung
• Seong Bo Hyun
• Jung Taek Jun
• Cho Yun Ki
• An Yong Hee
• Kim Sung-Kyoung
• Kim Hyun Min

Classifications

• C08J3/09

  in organic liquids · CPC title

• C08G2261/712

  Catalyst removal · CPC title

• C08G2261/416

  zinc-based, e.g. Rieke reactions · CPC title

• C08G64/40

  Post-polymerisation treatment · CPC title

• C08G64/34 Primary

  and cyclic ethers · CPC title