Complex metal oxide, and method of preparing polyester using the same

Patent metadata

Field	Value
Publication number	US-9243105-B2
Application number	US-201314391804-A
Country	US
Kind code	B2
Filing date	Apr 10, 2013
Priority date	Apr 13, 2012
Publication date	Jan 26, 2016
Grant date	Jan 26, 2016

Abstract

Disclosed herein are a novel complex metal oxide catalyst, and a method of preparing polyester using the same. The metal-bound compound of the present invention has a higher catalytic activity as compared to an antimony catalyst and existing titanium catalysts to be easily synthesized and stabilized, have a sufficient polymerization activity even with a small amount, and be used as an environmentally friendly catalyst for polyester polymerization. In addition, when preparing polyester by using the complex metal oxide of the present invention, since catalytic activity caused by phosphorus (P) which is a thermal stabilizer used to decrease pyrolysis at the time of hot-melting and molding is not deteriorated, an excessive amount of phosphorus may be used as compared to the related art, such that pyrolysis less occurs, whereby the yellowing phenomenon may be decreased and high viscosity may be maintained. Therefore, the complex metal oxide may be usefully applied to the preparation of polyester having good physical properties, in particular, polyethylene terephthalate.

First claim

What is claimed is:

1. A complex metal oxide used as a catalyst for polyester polymerization, comprising:
one metal (M) selected from the group consisting of magnesium (Mg), zinc (Zn), copper (Cu), manganese (Mn), calcium (Ca), iron (Fe), titanium (Ti), and aluminum (Al).

2. The complex metal oxide of claim 1 , comprising titanium alkoxide represented by the following Chemical Formula 1, aluminum alkoxide represented by the following Chemical Formula 2, and a coprecipitate of a metal alkoxide represented by the following Chemical Formula 3:
Ti(OR 1 ) 4   [Chemical Formula 1]

Al(OR 2 ) 3   [Chemical Formula 2]

M(OR 3 ) 2   [Chemical Formula 3]

wherein, in Chemical Formulas 1, 2, and 3, R 1 , R 2 , and R 3 are each independently, identically or differently, a hydrogen atom, C 1 to C 20 alkyl, C 2 to C 20 alkenyl, C 3 to C 20 cycloalkyl, C 6 to C 20 aryl, C 1 to C 20 alkylsilyl, C 7 to C 20 arylalkyl, or C 7 to C 20 alkylaryl, and
wherein, in Chemical Formula 3, M is one metal selected from the group consisting of Mg, Zn, Cu, Mn, Ca, and Fe.

3. The complex metal oxide of claim 2 , wherein R 1 , R 2 , and R 3 are each independently, identically or differently, a hydrogen atom or C 1 to C 4 alkyl, and wherein M is Mg.

4. The complex metal oxide of claim 1 , wherein the complex is represented by the following Chemical Formula 4 or the following Chemical Formula 5:

wherein, in Chemical Formula 5, n is an integer of 2 to 20.

5. A method of preparing polyester, comprising:
polymerizing a dicarboxylic acid component including terephthalic acid and a glycol component in the presence of a complex metal oxide including one metal (M) selected from the group consisting of magnesium (Mg), zinc (Zn), copper (Cu), manganese (Mn), calcium (Ca), iron (Fe), titanium (Ti), and aluminum (Al).

6. The method of claim 5 , wherein the metal (M) is magnesium (Mg).

7. The method of claim 5 , wherein the complex metal oxide comprises titanium alkoxide represented by the following Chemical Formula 1, aluminum alkoxide represented by the following Chemical Formula 2, and a coprecipitate of a metal alkoxide represented by the following Chemical Formula 3:
Ti(OR 1 ) 4   [Chemical Formula 1]

Al(OR 2 ) 3   [Chemical Formula 2]

M(OR 3 ) 2   [Chemical Formula 3]

wherein, in Chemical Formulas 1, 2, and 3, R 1 , R 2 , and R 3 are each independently, identically or differently, a hydrogen atom, C 1 to C 20 alkyl, C 2 to C 20 alkenyl, C 3 to C 20 cycloalkyl, C 6 to C 20 aryl, C 1 to C 20 alkylsilyl, C 7 to C 20 arylalkyl, or C 7 to C 20 alkylaryl, and
wherein in Chemical Formula 3, M is one selected from the group consisting of Mg, Zn, Cu, Mn, Ca, and Fe.

8. The method of claim 7 , wherein the complex metal oxide is added so that the titanium (Ti), aluminum (Al), and metal (M) elements contained in the complex metal oxide have a total content of 5 to 200 ppm based on a weight of the polyester.

9. The method of claim 5 , wherein the polymerizing of the dicarboxylic acid component including the terephthalic acid and the glycol component comprises:
esterifying the dicarboxylic acid component including the terephthalic acid and the glycol component; and
polycondensing a reaction product produced by the esterification reaction.

10. The method of claim 9 , wherein the polycondensing of the reaction product produced by the esterification reaction is performed by injecting a phosphoric compound having a concentration of 20 to 200 ppm based on a content of phosphorus (P) element based on the polyester.

11. The method of claim 10 , wherein the polycondensing of the reaction product produced by the esterification reaction is performed by injecting a phosphoric compound having a concentration of 40 to 180 ppm based on a content of phosphorus (P) element based on the polyester.

12. The method of claim 10 , wherein the phosphoric compound at least one compound selected from the group consisting of trimethyl phosphate ((CH 3 O) 3 PO), triethyl phosphate ((C 2 H 5 O) 3 PO), triphenyl phosphate ((PhO) 3 PO), and phosphoric acid ((H 3 PO 4 )).

13. The method of claim 9 , wherein the complex metal oxide is injected into the polycondensation.

14. The method of claim 13 , wherein the complex metal oxide is further injected into the esterification reaction.

15. The method of claim 9 , wherein the esterifying of the dicarboxylic acid component including the terephthalic acid or an ester-forming derivative thereof, and the glycol component is performed at a temperature of 200 to 300° C. for 2 to 6 hours.

16. The method of claim 9 , wherein the polycondensing of the reaction product produced by the esterification reaction is performed at a temperature of 200 to 300° C., under a pressure of 0.1 to 1 torr, for 1 to 5 hours.

17. The method of claim 5 , wherein the polymerizing is performed by liquid phase polymerization or solid phase polymerization.

18. The method of claim 17 , wherein the polyester is formed by liquid phase polymerization and has an intrinsic viscosity (IV) of 0.60 to 0.65 dl/g,
wherein the intrinsic viscosity (IV) is measured by mixing 60 g of phenol with 40 g of 1,1,2,2-tetrachloro-ethanol to form a solvent mixture and dissolving 0.4 g of the polyester in the solvent mixture at a temperature of 30° C.

19. The method of claim 17 , wherein the polyester is formed by solid phase polymerization and has an intrinsic viscosity (IV) of 0.70 to 0.87 dl/g.

20. The method of claim 5 , wherein the polyester is used for a food packing material, a bottle, a film, or a fibrous plastic.

21. The method of claim 5 , wherein the polyester is polyethylene terephthalate.

Assignees

• Lotte Chemical Corp

Inventors

• Yang Young Keun
• Yoon Seung Woong
• Hwang Yong Taek
• Lim Kyung Ho
• Bae Jong Ho

Classifications

• C08G63/181

  Acids containing aromatic rings · CPC title

• C08G63/80

  Solid-state polycondensation · CPC title

• C08G63/183

  Terephthalic acids · CPC title

• C08G63/85 Primary

  Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof {(C08G63/823 takes precedence)} · CPC title

• C08G63/82 Primary

  characterised by the catalyst used · CPC title