Manufacturing method of polyalkylene carbonate resin

Abstract

The present invention relates to a manufacturing method of a polyalkylene carbonate resin capable of suppressing agglomeration among catalyst particles during polymerization to maintain an excellent catalytic activity in a polymerization process, wherein the manufacturing method of a polyalkylene carbonate resin may include polymerizing epoxide and a monomer including carbon dioxide in the presence of a zinc dicarboxylate-based organic zinc catalyst and a dispersant, and the dispersant may include at least one selected from the group consisting of C1-C10 alkyl acrylate, C1-C10 alkyl methacrylate, C1-C20 monocarboxylic acid having an oxo group in a molecular structure, and a polyether-based polymer having C2-C6 alkylene oxide repeating units.

Claims

1. A manufacturing method of a polyalkylene carbonate resin comprising: polymerizing epoxide and a monomer including carbon dioxide in the presence of a zinc dicarboxylate-based organic zinc catalyst and a dispersant, wherein the dispersant includes at least one selected from the group consisting of C1-C10 alkyl acrylate, C1-C10 alkyl methacrylate, C1-C20 monocarboxylic acid having an oxo group in a molecular structure, and a polyether-based polymer having C2-C6 alkylene oxide repeating units.

2. The manufacturing method of claim 1, wherein: the dispersant includes at least one selected from the group consisting of hexyl methacrylate, 3,5-dioxohexanoic acid, 3,5,7-trioxo-dodecanoic acid, and a propylene oxide (PO)-ethylene oxide (EO) block copolymer.

3. The manufacturing method of claim 1, wherein: the zinc dicarboxylate-based organic zinc catalyst is a catalyst obtained by reacting a zinc precursor with C3-C20 aliphatic dicarboxylic acid or C8-C40 aromatic dicarboxylic acid.

4. The manufacturing method of claim 3, wherein: the aliphatic dicarboxylic acid or the aromatic dicarboxylic acid includes a dicarboxylic acid selected from the group consisting of malonic acid, glutaric acid, succinic acid, adipic acid, terephthalic acid, isophthalic acid, homophthalic acid and phenylglutaric acid.

5. The manufacturing method of claim 3, wherein: the zinc precursor includes zinc oxide, zinc hydroxide, zinc acetate (Zn(O.sub.2CCH.sub.3).sub.2), zinc nitrate (Zn(NO.sub.3).sub.2) or zinc sulfate (ZnSO.sub.4).

6. The manufacturing method of claim 3, wherein: the aliphatic dicarboxylic acid or the aromatic dicarboxylic acid is used and reacted at 1.0 to 1.5 molar ratio relative to 1 mol of the zinc precursor.

7. The manufacturing method of claim 1, wherein: the zinc dicarboxylate-based organic zinc catalyst is used for the polymerization, as a particle shape in which an average particle size is 0.3 to 1.0 μm, and a particle size standard deviation is 0.3 μm or less.

8. The manufacturing method of claim 1, wherein: the manufacturing method is performed in an organic solvent by solution polymerization.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

(1) Hereinafter, preferable Examples of the present invention will be provided for better understanding of the present invention.

(2) However, the following Examples are provided only for illustration of the present invention, and should not be construed as limiting the present invention by the examples.

Manufacture Example 1: Manufacture of Organic Zinc Catalyst

(3) 6.6 g (0.05 mol) of a glutaric acid and 0.1 mL of acetic acid were added to 100 mL of toluene in a 250 mL size round bottom flask, and dispersed under reflux.

(4) Then, the mixture was heated at a temperature of 55° C. for 30 minutes, and 4.1 g (0.05 mol) of ZnO was added to 50 mL of toluene, and dispersed. The obtained product was added to the glutaric acid dispersion, and stirred for 3 hours.

(5) Next, the mixture was heated at 110° C. for 4 hours.

(6) A white solid was produced, filtered and washed with acetone/ethanol, and dried in a vacuum oven at 130° C.

(7) According to the above-described method, the organic zinc catalyst of Manufacture Example 1 was manufactured, and a chemical structure thereof was confirmed.

(8) Further, the organic zinc catalyst of Manufacture Example 1 was confirmed by SEM analysis. As a result, it was confirmed that the organic zinc catalyst of Manufacture Example 1 had an average particle size of about 0.6 μm and a particle size standard deviation of about 0.18 μm.

Example 1

(9) First, 0.4 g of the catalyst of Manufacture Example 1, 10 mg of a dispersant (hexyl methacrylate) and 8.52 g of dichloromethane (methylene chloride) were added to a high-pressure reactor in a glove box, and 8.9 g of ethylene oxide was added thereto.

(10) Then, the mixture was pressed in the reactor by a pressure of 30 bar using carbon dioxide.

(11) The polymerization reaction was performed at 70° C. for 3 hours.

(12) After the reaction was completed, unreacted carbon dioxide and ethylene oxide were removed together with dichloromethane which is a solvent.

(13) In order to measure an amount of the manufactured polyethylene carbonate, the remaining solid was completely dried and quantified.

(14) An activity and a yield of the catalyst according to the polymerization results were shown in Table 1 below.

Example 2

(15) Polyethylene carbonate of Example 2 was manufactured in the same manner as Example 1 except for using 10 mg of 3,5,7-trioxo-dodecanoic acid instead of using the hexyl methacrylate as the dispersant in Example 1.

(16) In order to measure an amount of the manufactured polyethylene carbonate, the remaining solid was completely dried and quantified.

(17) An activity and a yield of the catalyst according to the polymerization results were shown in Table 1 below.

Example 3

(18) Polyethylene carbonate of Example 3 was manufactured in the same manner as Example 1 except for using 10 mg of 3,5-dioxohexanoic acid instead of using the hexyl methacrylate as the dispersant in Example 1.

(19) In order to measure an amount of the manufactured polyethylene carbonate, the remaining solid was completely dried and quantified.

(20) An activity and a yield of the catalyst according to the polymerization results were shown in Table 1 below.

Example 4

(21) Polyethylene carbonate of Example 4 was manufactured in the same manner as Example 1 except for using 10 mg of propylene oxide (PO)-ethylene oxide (EO) block copolymer (Mw: 8000; Sigma-Aldrich Co., Ltd.) instead of using the hexyl methacrylate as the dispersant in Example 1.

(22) In order to measure an amount of the manufactured polyethylene carbonate, the remaining solid was completely dried and quantified.

(23) An activity and a yield of the catalyst according to the polymerization results were shown in Table 1 below.

Comparative Example 1

(24) Polyethylene carbonate of Comparative Example 1 was manufactured in the same manner as Example 1 except for not using a dispersant.

(25) In order to measure an amount of the manufactured polyethylene carbonate, the remaining solid was completely dried and quantified.

(26) An activity and a yield of the catalyst according to the polymerization results were shown in Table 1 below.

Comparative Example 2

(27) Polyethylene carbonate of Comparative Example 2 was manufactured in the same manner as Example 1 except for using 10 mg of propionic acid instead of using the hexyl methacrylate as the dispersant in Example 1.

(28) In order to measure an amount of the manufactured polyethylene carbonate, the remaining solid was completely dried and quantified.

(29) An activity and a yield of the catalyst according to the polymerization results were shown in Table 1 below.

(30) TABLE-US-00001 TABLE 1 Activity of catalyst Kinds of dispersant in Yield (g-polymer/g- polymerization (g) catalyst) Example 1 Hexyl methacrylate, 17.3 43.3 Example 2 3,5,7-trioxo-dodecanoic acid 16.6 41.5 Example 3 3,5-dioxohexanoic acid 15.8 39.5 Example 4 PO-EO block copolymer 16.2 40.5 Comparative None 13.5 33.8 Example 1 Comparative Propionic acid 8.9 22.3 Example 2

(31) Referring to Table 1 above, it was confirmed that even though Examples 1 to 4 used the same catalyst as Comparative Examples 1 and 2, an excellent activity was maintained and expressed during polymerization, and polyethylene carbonate was capable of being manufactured in an excellent yield.

(32) It is thought that due to the use of the specific dispersant, agglomeration among the catalyst particles is effectively suppressed in the polymerization process, and as a result, an excellent catalyst activity is not inhibited during the polymerization process.

(33) On the contrary, it is thought that the propionic acid used in Comparative Example 2 does not effectively suppress agglomeration among the catalyst particles during the polymerization, and as a result, relative deterioration of the catalytic activity is significantly shown in Comparative Example 2.