Catalyst for polyester production, process for producing polyester using the catalyst, polyester obtained by the process, and uses of the polyester

• US 6,346,070 B1
• Filed: 12/22/1999
• Issued: 02/12/2002
• Est. Priority Date: 12/25/1998
• Status: Expired due to Term

• Current Assignee: Mitsui Chemicals Incorporated (Mitsui Chemicals)
• Original Assignee: Mitsui Chemicals Incorporated (Mitsui Chemicals)
• Inventors: Hori, Hideshi, Shimizu, Akiyoshi, Noda, Seiji, Onogi, Takayuki, Miyazoe, Satoru, Tsugawa, Michio, Ehara, Fujito, Toyota, Kazuo, Ohmatsuzawa, Takeshi, Fukutani, Kenzaburou, Sakai, Masayuki, Imuta, Junichi, Nakamachi, Koji, Hiraoka, Shoji
• Primary Examiner(s): Acquah, Samuel A.
• Application Number:
  US09/470,664
• Time in Patent Office: 783 Days
• Field of Search: 528/274, 528/277, 528/279, 528/280, 528/281, 528/282, 528/283, 528/285, 528/286, 528/308, 528/308.1, 528/308.3, 524/779, 524/780, 524/783, 524/781, 524/784, 524/785, 524/786, 524/788, 524/789
• US Class Current: 528/279
• CPC Class Codes: C08G 63/183 Terephthalic acids
• CPC Class Codes: C08G 63/82 characterised by the catalyst used
• CPC Class Codes: C08G 63/85 Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof C08G63/823 takes precedence
• CPC Class Codes: C08G 63/88 Post-polymerisation treatment

Abstract

The present invention provides a catalyst for polyester production capable of producing a polyester with high catalytic activity and a process for producing a polyester using the catalyst. The catalyst for polyester production comprises a solid titanium compound which is obtained by dehydro-drying a hydrolyzate obtained by hydrolysis of a titanium halide and which has a molar ratio (OH/Ti) of a hydroxyl group (OH) to titanium (Ti) exceeding 0.09 and less than 4. The present invention also provides a method to obtain a polyester having a small increase of the acetaldehyde content during the molding. This method comprises bringing a polyester, which is obtained by the use of a titanium compound catalyst and in which the reaction has been completed, into contact with a phosphoric ester aqueous solution or the like having a concentration of not less than 10 ppm in terms of phosphorus atom. The present invention further provides a polyester having excellent transparency and tint and molded products of the polyester such as a blow molded article, a film, a sheet and a fiber. The polyester is obtained by polycondensing an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol or an ester-forming derivative thereof in the presence of a catalyst for polyester production which comprises a polycondensation catalyst component comprising a solid titanium compound and a co-catalyst component comprising a magnesium compound. This polyester has a titanium content of 1 to 100 ppm, a magnesium content of 1 to 200 ppm and a weight ratio (Mg/Ti) of magnesium to titanium of not less than 0.01.

Claims

1. A catalyst useful for polyester production, comprising:

(I) a polycondensation catalyst component comprising a solid titanium compound (I-c) obtained by dehydro-drying hydrolyzed titanium halide, and

(II) a co-catalyst component comprising a magnesium compound.

3. The catalyst according to claim 1, wherein the compound of said element other than titanium is a compound of at least one element selected from the group consisting of beryllium, magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, copper, zinc, boron, aluminum, gallium, silicon, germanium, tin, antimony and phosphorus, or a precursor of said compound.

15. The catalyst according to any one of claims 1, 2, 3, 4, 5, 6, 7, 8, or 9, wherein the co-catalyst component (II) is selected from the group consisting of magnesium acetate and magnesium carbonate.

17. The catalyst according to any one of claims 1, 2, 3, 4, 5, 6, 7, 8, or 9, wherein the weight ratio of magnesium from the magnesium compound (II) to polycondensation catalyst component (I) to is in the range of from 0.06 to 10.

2. A catalyst useful for polyester production, comprising:

(I) a polycondensation catalyst component comprising a solid titanium compound (I-d) obtained by dehydro-drying hydrolyzed mixture of (i) titanium halide and (ii) a compound of at least one element other than titanium or a precursor of said compound, and

(II) a co-catalyst component comprising a magnesium compound.

16. The catalyst according to any one of claims 2, 6, or 8, wherein the molar ratio of the element other than titanium in compound (ii) to titanium in the titanium halide (i) is in the range of from 1/50 to 50/1.

4. A catalyst useful for polyester production, comprising:

(I) a polycondensation catalyst component comprising a solid titanium compound (I-e) obtained by bringing a titanium halide into contact with water to hydrolyze the titanium halide and thereby obtain an acid solution containing a hydrolyzate of the titanium halide, rendering the solution basic by addition of base, then adjusting pH of the solution to 2 to 6 by addition of acid, and dehydro-drying the resulting precipitate; and

(II) a cocatalyst component comprising a magnesium compound.

5. A catalyst useful for polyester production, comprising:

(I) a polycondensation catalyst component comprising a solid titanium compound (I-f) obtained by bringing a titanium halide into contact with water to hydrolyze the titanium halide and thereby obtaining an acid solution containing a hydrolyzate of the titanium halide, and adding a base to the solution to adjust the pH to from 2 to 6, and dehydro-drying the resulting basic solution of hydrolyzed titanium halide, and

(II) a cocatalyst component comprising a magnesium compound.

6. A catalyst useful for polyester production, comprising:

(I) a polycondensation catalyst component comprising a solid titanium compound (I-g) obtained by bringing a mixture of (i) titanium halide and (ii) a compound of an element other than titanium or a precursor of said compound, into contact with water to hydrolyze the titanium halide and thereby obtain an acid solution containing a hydrolyzate of the titanium halide, rendering the solution basic addition of base, then adjusting pH of the solution to 2 to 6 by the addition of acid, and dehydro-drying the resulting precipitate; and

(II) a cocatalyst component comprising a magnesium compound.

7. The catalyst according to claim 6, wherein the compound of said element other than titanium is a compound of at least one element selected from the group consisting of beryllium, magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, copper, zinc, boron, aluminum, gallium, silicon, germanium, tin, antimony and phosphorus, or a precursor of said compound.

8. A catalyst useful for polyester production, comprising

a polycondensation catalyst component comprising a solid titanium compound (I-h) obtained by bringing a mixture of (i) titanium halide and (ii) a compound of an element other than titanium or a precursor of said compound, into contact with water to hydrolyze the titanium halide and thereby obtain an acid solution containing a hydrolyzate of the titanium halide, rendering the solution basic by addition of base, then adjusting pH of the solution to 2 to 6 by the addition of acid, and dehydro-drying the resulting precipitate;

and

(II) a cocatalyst component comprising a magnesium compound.

9. The catalyst according to claim 8, wherein the compound of said element other than titanium is a compound of at least one element selected from the group consisting of beryllium, magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, copper, zinc, boron, aluminum, gallium, silicon, germanium, tin, antimony and phosphorus, or a precursor of said compound.

10. A polyester (P-5) which is obtained by polycondensing an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic diol or an ester-forming derivative thereof, in the presence of:

(I) a polycondensation catalyst component comprising a solid titanium compound (I-c) obtained by dehydro-drying hydrolyzed titanium halide, and

(II) a co-catalyst component comprising a magnesium compound, said polyester being characterized by satisfying the following relationship;

11. The polyester (P-5) according to claim 10, wherein said polycondensation catalyst component (I) is obtained by dehydro-drying a hydrolyzed mixture of (i) titanium halide and (ii) a compound of at least one element other than titanium or a precursor of said compound.

12. The polyester (P-5) according to claim 11, wherein the compound of said element other than titanium is a compound of at least one element selected from the group consisting of beryllium, magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, copper, zinc, boron, aluminum, gallium, silicon, germanium, tin, antimony and phosphorus, or a precursor of said compound.

13. The polyester (P-5) according to any one of claims 10, 11, or 12, wherein the titanium atom content in said polycondensation catalyst is in the range of 1 to 100 ppm, the magnesium atom content is in the range of 1 to 200 ppm, and the weight ratio (Mg/Ti) of the magnesium atom to the titanium atom is not less than 0.01.

14. The polyester (P-5) according to any one of claims 10, 11, or 12, which is a polyethylene terephthalate.

18. The polyester (P-5) according to claim 10, wherein

19. The polyester (P-5) according to claim 10 or claim 18, having an intrinsic viscosity X in the range of from 0.50 to 1.50 dl/g;

and a density of from 1.37 to 1.44 g/cm³.

20. The polyester according to claim 10, having a titanium atom content in the range of from 1 to 100 ppm and a magnesium atom content in the range of from 1 to 200 ppm, and a weight ratio Mg/Ti in the range of from 0.06 to 10.