Continuous Process for Manufacturing Aliphatic Polycarbonates from Carbon Dioxide and Epoxides

• US 20110054145A1
• Filed: 09/02/2010
• Published: 03/03/2011
• Est. Priority Date: 09/03/2009
• Status: Active Grant

• Current Assignee: SK Innovation Company Limited
• Original Assignee: SK Energy Co Ltd (SK Innovation Company Limited)
• Inventors: Kim, Gyungrok, Lee, Seongjun, Chang, Byoungmu, Sudevan, Sujith, Yoo, Jieun, Choi, Sun, Shin, Daeho, Kim, Hongdae, Lee, Jangjae, Jeong, Jisu, Lee, Jaeho, Ok, Myungahn, Moon, Gwangbin, Park, Mingyoo
• Granted Patent: US 8,546,514 B2
• Time in Patent Office: Days
• US Class Current: 528/395
• CPC Class Codes: C08G 64/34 and cyclic ethers

Abstract

Disclosed is a continuous process for manufacturing aliphatic polycarbonate by polymerizing carbon dioxide and one or more epoxide compound in the presence of catalyst, in which carbon dioxide, one or more epoxide compound, and the catalyst are continuously supplied to polymerization reactor to produce aliphatic polycarbonate, separate unreacted carbon dioxide and epoxide compound and recycle them as raw materials.

Claims

1. A continuous process for manufacturing aliphatic polycarbonate, comprising:

continuously polymerizing by supplying carbon dioxide, one or more epoxide compound and organometallic catalyst to reactor and manufacturing aliphatic polycarbonate; and

separating unreacted carbon dioxide and epoxide compound.

2. The process for continuously manufacturing aliphatic polycarbonate of claim 1, wherein the unreacted carbon dioxide and epoxide are separated and recycled to use as raw materials.

3. The process for continuously manufacturing aliphatic polycarbonate of claim 2, wherein the epoxide compound is a reactant and a reaction solvent as well.

4. The process for continuously manufacturing aliphatic polycarbonate of claim 3, wherein a polar solvent as the reaction solvent is further included in addition to the epoxide compound.

5. The process for continuously manufacturing aliphatic polycarbonate of claim 2, wherein, after polymerizing the aliphatic polycarbonate, the polymer solution is supplied to catalyst separator to separate the catalyst.

6. The process for continuously manufacturing aliphatic polycarbonate of claim 5, wherein an ion exchange process is used for separating the catalyst.

7. The process for continuously manufacturing aliphatic polycarbonate of claim 1, wherein, after prepolymerization is performed by continuously supplying carbon dioxide, one or more epoxide compound, and catalyst to prepolymerizaiton reactor, aliphatic polycarbonate is continuously manufactured by continuously supplying the prepolymerized solution into polymerization reactor.

8. The process for continuously manufacturing aliphatic polycarbonate of claim 7, wherein prepolymerization is performed at 10˜

49 kg/cm²g and 0˜

100°

C. and polymerization is performed at 10˜

49 kg/cm²g and 40˜

100°

C.

9. The process for continuously manufacturing aliphatic polycarbonate of claim 1, wherein a part of the epoxide compound is supplied to the polymerization reactor outlet to adjust 5˜

30 wt % of the concentration of the polymer solution.

10. The process for continuously manufacturing aliphatic polycarbonate of claim 9, wherein the unreacted carbon dioxide and epoxide compound are separated from the polymer in several phase separators to separate the unreacted epoxide compound and carbon dioxide into vapor phase, and concentrate aliphatic polycarbonate into polymer melt.

11. The process for continuously manufacturing aliphatic polycarbonate of claim 9, wherein the recycling process is performed by supplying the separated carbon dioxide and epoxide compound to a separation column to separate the carbon dioxide and epoxide compound respectively and then reuse them as the raw material.

12. The process for continuously manufacturing aliphatic polycarbonate of claim 10, wherein separation of the unreacted carbon dioxide and epoxide compound includes a low-pressure separation performed at 0˜

5 kg/cm²g and 40˜

200°

C. after an intermediate pressure separation performed at 0˜

10 kg/cm²g and 40˜

200°

C.

13. The process for continuously manufacturing aliphatic polycarbonate of claim 9, wherein the epoxide compound is one or more from the group consisting of substituted or unsubstituted (C2-C10) alkylene oxide with a halogen or an alkoxy;

substituted or unsubstituted (C4-C20) cycloalkylene oxide with a halogen or an alkoxy; and

substituted or unsubstituted (C8-C20) styrene oxide with a halogen, an alkoxy, an alkyl, or an aryl.

14. The process for continuously manufacturing aliphatic polycarbonate of claim 9, wherein carbon dioxide and epoxide compound are mixed and maintained in full liquid phase, to supply to the prepolymerization reactor or the polymerization reactor.

15. The process for continuously manufacturing aliphatic polycarbonate of claim 9, wherein the organic metal catalyst is a complex compound represented by the following Chemical Formula 1:

[L¹L²L³L⁴M]⁻

[X¹ . . . H . . . X²]⁻

_aZ⁻

_b 

 

[Chemical Formula 1]

[where,

M is a cobalt III or a chrome III;

L¹ to L⁴ is an anionic X-type ligand, L¹ to L⁴ may be independently same or different to each other, and may be connected each other to be a bidentate, a tridentate, or a tetradentate ligand, one or more of L¹ to L⁴ include a quaternary ammonium cation, the total number of ammonium cations included in L¹ to L⁴ is 1+a+b, and a complex compound is overall neutral;

A or b is an integer; and

Ligand without the ligand including the quaternay ammonium cation of L¹ to L⁴, or X¹ and X² are independently a halogen anion or HCO₃⁻

, C1 to C20 carboxy anion, C6 to C20 aryloxy anion with or without one or more of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom, and a phosphorus atom;

C1 to C20 alkoxy anion;

C1 to C20 carbonate anion;

C1 to C20 alkylsulfonate anion;

C1 to C20 amide anion;

C1 to C20 carbamate anion, and Z is BF₄⁻

, ClO₄⁻

, NO₃⁻

or PF₆⁻

]

16. The process for continuously manufacturing aliphatic polycarbonate of claim 15, wherein the catalyst is selected from the group consisting of the following Chemical Formula 2 to Chemical Formula 8:

17. The process for continuously manufacturing aliphatic polycarbonate of claim 15, wherein organometallic catalyst is maintained in liquid phase after mixing with the mole ratio of the epoxide compound or other polar solvents such as acetone, propylene carbonate, ethylene carbonate, dichloromethane, chloroform, methyl acetate, ethyl acetate, aceonitrile, tetrahydrofurane, dioxane, etc.:

the organometallic catalyst of 10,000;

1˜

200,000;

1.

18. The continuous process for manufacturing aliphatic polycarbonate of claim 17, wherein organometallic catalyst solution is 0.1˜

5 wt % to the total content of the epoxide compound and carbon dioxide.