WO1996041828A1 - Catalyst, processes and polymer products therefrom - Google Patents
Catalyst, processes and polymer products therefrom Download PDFInfo
- Publication number
- WO1996041828A1 WO1996041828A1 PCT/US1996/008484 US9608484W WO9641828A1 WO 1996041828 A1 WO1996041828 A1 WO 1996041828A1 US 9608484 W US9608484 W US 9608484W WO 9641828 A1 WO9641828 A1 WO 9641828A1
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- WO
- WIPO (PCT)
- Prior art keywords
- aluminum
- cobalt
- catalyst
- ethylene glycol
- polymer
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
Definitions
- This invention relates to a catalyst useful for the preparation of high molecular weight polyester polymers of terephthalic acid and ethylene glycol, to the process for the production of such high molecular weight polyester polymers, to such high molecular weight polyester polymers made by the process using the catalyst, and to products made from such polyester high molecular weight polymers such as fibers, films, and bottles.
- Many commercial processes for the production of high molecular weight polyester polymers of terephthalic acid and ethylene glycol employ an antimony catalyst.
- the use of an antimony catalyst presents some problems when the polymer is melt spun into fibers, i.e., the antimony catalyst residues form deposits around spinneret holes. These deposits must be wiped off from time to time or the filaments will be defective.
- antimony deposits form because antimony is present in the polymer as antimony glycollate, which boils at about the temperature of the spinneret.
- the antimony glycollate vaporizes, and then hydrolyzes, leaving a non-volatile antimony containing deposit at the spinneret.
- a non- antimony containing catalyst is, therefore, a desirable goal.
- High molecular weight polyester polymers of terephthalic acid and ethylene glycol are usually produced by one of three different processes, namely, (1) the direct esterification and then polymerization of pure terephthalic acid and ethylene glycol. (This direct polymerization process is satisfactory only if the ingredients are of high purity.) (2) Transesterification of dimethylterephthalate (DMT) and ethylene glycol to form, what is called in the art, "DMT monomer.” The transesterification usually takes place in the presence of a manganese, zinc, or lithium catalyst.
- DMT dimethylterephthalate
- the DMT monomer is a mixture of ester products (low molecular weight polymer) in which most of the end groups are glycoxyl, and the mixture contains molecules with a degree of polymerization that is 1, 2, or 3.
- the DMT monomer is then further polymerized to high molecular weight polymer often with an antimony catalyst.
- the manganese catalyst used in the transesterification reaction tends to cause undesirable color in the final product unless it is sequestered; so phosphorus compounds, for example, H3PO4, are often added before the DMT monomer is polymerized to sequester the manganese catalyst residue.
- oligomer (3) Reaction of medium purity (polymer grade) terephthalic acid and ethylene glycol to form, what is called in the art, "oligomer.”
- the oligomer mixture contains color forming catalyst residues from the manufacture of terephthalic acid. These catalyst residues include manganese, iron, and molybdenum. These catalyst residues are then sequestered by the addition of a phosphoric compound, for example, H3PO4, and then polymerized (polycondensed) to form high molecular weight polymer.
- the oligomer has a degree of polymerization of about 7, has 500 to 1000 carboxyl end groups per 10 to the 6th power grams of oligomer. Some cyclic materials are present in the oligomer.
- the catalyst of the invention is useful in all three of these processes.
- the catalyst of the invention may be added at the direct esterification step or at the beginning of the polymerization; in the second process described, the catalyst will be added after the DMT monomer is formed and after the manganese catalyst is sequestered (deactivated) ; and in the third process the catalyst will be added after the color-forming metal impurities in the oligomer are deactivated.
- Combinations of metals compounds have been employed in the prior art as catalyst for the preparation of high molecular weight polymers of terephthalic acid and ethylene glycols : see, for example, Nichols U.S. Patent 5,116,311; Engle-Bader et al. U.S. Patent 5,166,938; and Kosky et al. U.S. Patent 4,590,259.
- the present invention is a polymerization catalyst useful for the preparation of high molecular weight polymers of terephthalic acid and ethylene glycol comprising a cobalt salt and an aluminum compound selected from the group consisting of aluminum chloride, aluminum hydroxide, aluminum acetate, and aluminum hydroxychloride dissolved in ethylene glycol, where the mole ratio of aluminum to cobalt is 0.25 to 1 to 16 to 1, and where the mole ratio of chlorine to aluminum is in the range of 0 (no chlorine) to 3 to 1.
- the present invention is also a process for the production of ethylene terephthalate polyester polymer, which comprises combining a polymerization catalyst formed by combining a cobalt salt that is soluble in ethylene glycol and aluminum compound selected from aluminum chloride, aluminum hydroxide, aluminum acetate, and aluminum hydroxychloride in ethylene glycol, where the mole ratio of aluminum to cobalt is 0.25 to 1 to 16 to 1 and a chlorine to aluminum ratio in the range of 0.25 to 3 with (a) terephthalic acid and ethylene glycol, or (b) low molecular weight ethylene terephthalate polymer (also called DMT monomer) , or (c) oligomer, where the concentration of cobalt in the thus formed mixture is in the range of about 10 to 100 parts per million parts of the mixture, and polymerizing the mixture.
- the aluminum to cobalt mole ratio may be in the range of 1 to 1 to 16 to 1 in some circumstances.
- cobalt salts include cobaltous acetate tetrahydrate, cobaltous nitrate, cobaltous chloride, cobalt acetylacetonate, cobalt napthenate, cobalt hydroxide, and cobalt salicyl salicylate.
- the preferred cobalt salts are soluble in ethylene glycol in the 100-10,000 parts per million cobalt range.
- This invention is also a process for the preparation of a catalyst for the preparation of ethylene terephthalate polyester polymer, which comprises heating a cobalt salt and aluminum compound selected from the group consisting of aluminum chloride, aluminum hydroxide, aluminum acetate, and aluminum hydroxychloride in ethylene glycol to a temperature in the range of about 40.to 180 degrees C where the aluminum to cobalt mole ratio is in the range of 0.25 to 1 to 16 to 1.
- a temperature range of about 40 to 180 degrees C is satisfactory: lower temperatures lead to less corrosion of equipment when chloride is present with the aluminum or cobalt salts.
- This invention is also an ethylene terephthalate polyester polymer having a NLRV of at least 12 and containing catalyst residues of cobalt and aluminum; in other words derived from cobalt salt(s) and from aluminum chloride and/or aluminum hydroxychloride.
- the polymer can be in the form of a fiber or film or bottle.
- This invention is also a process for the production of ethylene terephthalate polyester polymer fiber in which there is a reduced need to wipe antimony deposits from the spinneret face which comprises melt spinning a molten mixture of ethylene terephthalate polyester polymer containing catalyst residue of cobalt salt and an aluminum compound selected from the group consistingof aluminum chloride and aluminum hydroxychloride.
- the terephthalic acid (TPA) and ethylene glycol will be fed into a reactor.
- the reaction to form oligomer will proceed without catalyst and is usually conducted at a temperature of about 240 to about 300 degrees C and at a pressure of about 0 to 50 pounds per square inch (0 to 3.5 Kg/sq cm) .
- the reactor will be fed more than an stoichiometric amount of the ethylene glycol, and the excess glycol separated by distillation.
- coloring agents such as carbon black, delustrants, opaquing agents, color, and thermal stabilizers, copolymerization additives such as glycol esters of sodium or other metal dimethyl isophthalate-5- sulfonate, isophthalic acid, trimellitic acid and the like.
- coloring agents such as carbon black, delustrants, opaquing agents, color, and thermal stabilizers
- copolymerization additives such as glycol esters of sodium or other metal dimethyl isophthalate-5- sulfonate, isophthalic acid, trimellitic acid and the like.
- Titanium dioxide is a conventional additive; it serves as a whitening agent and a delustrant.
- Most commercial grades of titanium dioxide that are used in polyester fiber contain antimony compounds which serve as thermal and ultraviolet light stabilizers; so if titanium dioxide is added to the oligomer, the final product will still contain some antimony, and antimony will show up in the analysis of the polymer.
- the antimony in the TiC>2 is chemically bound in the TiC>2 crystal.
- polymer grade TPA and plant grade ethylene glycol contain various amount of metals, for example, iron, titanium, molybdenum, cobalt, and manganese, that tend to give color to the final product, a phosphorus compound, such as orthophosphoric acid, is often added to TPA/glycol slurry that feeds the direct esterfier or to the oligomer line and mixed to sequester these color forming metal impurities.
- the catalyst of the present invention is added to the oligomer stream, and the oligomer is then subjected to polycondensation in the usual manner.
- the catalyst of the present invention is used to prepare polyester polymer from dimethylterephthalate (DMT)
- the DMT and ethylene glycol will be fed into a reactor along with a transesterification catalyst, for example, manganese, zinc, or lithium acetates, or glycollates.
- the reaction that forms DMT monomer is usually conducted at a temperature of about 190 to about 260 degrees C and at a pressure of about 0 to 10 pounds per square inch (0 to 0.7 Kg/ sq cm) .
- Sodium or other metal dimethyl isophthalate-5-sulfonate may be added with the catalyzed glycol to make a copolymer. Methanol will be separated by distillation. To the DMT monomer stream may then be added fillers, coloring agents, such as carbon black, delustrants, opaquing agents, color, and thermal stabilizers, copolymerization additives such as glycol esters of sodium or other metal dimethyl isophthalate-5-sulfonate, isophthalic acid, trimellitic acid and the like. Titanium dioxide is a conventional additive; it serves as a whitening agent and a delustrant.
- titanium dioxide used in polyester fiber contain antimony compounds which serve as thermal and ultraviolet light stabilizers; so if titanium dioxide (TiC ⁇ ) is added to the DMT monomer, the final product will still contain some antimony, and antimony will show up in the analysis of the polymer.
- the antimony in the TiC>2 is chemically bound in the TiC>2 crystal.
- a phosphorus compound such as orthophosphoric acid is then added at this point to (deactivate) sequester the ester exchange catalyst, for example, manganese compound. Then the catalyst of the present invention is added to the stream, and the DMT monomer subjected to polycondensation in the usual manner.
- the terephthalic acid (TPA) and ethylene glycol will be fed into a reactor.
- the reaction to form oligomer will proceed without catalyst and is usually conducted at a temperature of about 240 to about 300 degrees C and at a pressure of about 0 to 50 pounds per square inch gauge (0 to 3.5 Kg/sq cm) .
- the reactor will be fed more than a stoichiometric amount of the ethylene glycol, and the excess ' glycol separated by distillation.
- coloring agents such as carbon black, delustrants, opaquing agents, color, and thermal stabilizers
- copolymerization additives such as glycol esters of sodium or other metal dimethyl isophthalate-5-sulfonate, isophthalic acid, trimellitic acid, and the like.
- Titanium dioxide is a conventional additive; it serves as a whitening agent and a delustrant.
- Most commercial grades of titanium dioxide used in polyester fiber contain antimony compounds which serve as thermal and ultraviolet light stabilizers; so if titanium dioxide is added to the oligomer, the final product will still contain some antimony, and antimony will show up in the analysis of the polymer.
- the antimony in the Ti ⁇ 2 is chemically bound in the TiC-2 crystal.
- the desired catalyst should meet the following criteria: 1. It is preferably soluble in ethylene glycol, but some catalyst may be in slurry form, such as the reaction product of aluminum hydroxide and cobalt hydroxide. 2. It should produce a polymer which, when formed into a yarn, has a color, dyeability, and durability about as good as the yarn made with antimony catalyst. 3. It should be capable of being used in the same equipment that is presently used for antimony catalyst. 4. It should have a reactivity as good as the antimony catalyst. 5. It should not deposit on the spinnerets. 6. It should cost about the same as an antimony catalyst. 7. The catalyst residues should be not be toxic. The catalyst of the invention meets these criteria.
- the catalyst of the invention may be prepared as follows:
- Nalco 8676 aluminum hydroxychloride
- Nalco 8676 is a colloidal suspension in water of aluminum hydroxychloride particles. It is a 10% solution (based on AI2O3) of 20 nanometer particles.)
- Nalco 8187 is aluminum hydroxychloride solution in water having an aluminum content measured as AI2O3 of 22% by weight.
- Nalco 8676 and 8187 were analyzed. The percent solids was determined by drying at 110 degrees C. Nalco 8676 was 21.9 +/- 1.6% solid, and Nalco 8187 was 46.2 +/- 0.39% solid. When calcined at 900 degrees C, Nalco 8676 was 9.75 +/- 0.23% solid, and Nalco 8187 was 22.6 +/- 0.05% solid. The aluminum content of Nalco 8676 was 5.68% by weight, and the chlorine content was 3.77%. The aluminum content of Nalco 8187 was 12.4%, and the chlorine content was 9.3%.)
- NLRV and LRV are measures of relative viscosity, being the ratio at 25 degrees C of the flow times in a capillary viscometer for a solution and for the solvent.
- the solution is 4.75 wt. percent of polymer in solvent.
- the solvent for NLRV is hexafluoroisopropanol.
- the solvent for LRV is hexafluoroisopropanol containing 100 parts per million H2SO4.
- catalyst-free oligomer that was made from pure terephthalic acid and ethylene glycol was combined with 120.4 grams of ethylene glycol and 8.6 grams of ethylene glycol containing the cobalt/aluminum catalyst (#3 in the above table) .
- the amount of catalyst was such that the final polymer contained 14.8 parts per million cobalt, and 54 parts per million aluminum.
- the mixture was stirred at 60 revolutions per minute, heated to 265 degrees C for 30 minutes, to dissolve and remelt the oligomer into the glycol mixture, and then heated to 275 degrees C at a pressure of 120 millimeters of mercury and held at this condition for 20 minutes.
- the temperature was then raised to 280 degrees C, and the vacuum adjusted to 30 millimeters of mercury and held at this condition for 20 minutes.
- the temperature was raised to 285 degrees, and the pressure lowered to about one (+/- 0.5) millimeters of mercury and held until the agitator torque reached 4 pounds per inch (71 Kg/meter) at 60 revolutions per minute.
- the polymerization rate was about the same as that obtained with 200 part per million antimony; the color was close to that obtained from 200 part per million antimony, and the amount of diethylene glycol was somewhat higher than that obtained using 200 parts per million antimony, but still acceptable.
- Dimethyl terephthalate is fed at 84 pounds (38 Kg) per hour to plate 15 of a 20 plate ester exchange distillation column.
- Catalyzed glycol was made by dissolving 590 grams of manganese acetate with 4 waters of hydration, 115 grams of sodium acetate, and 853 grams of antimony glycollate at about 50 degrees C in 1200 pounds (545 Kg) of ethylene glycol.
- This catalyst solution was fed at 210 milliliters/minute to plate 17 of the ester exchange column.
- Virgin glycol was fed to the calandria reboiler at about 70 milliliters/minutes to control the calandria temperature at 231+/ -2 degrees C.
- Glycol boil up in the column was provided by Dowtherm ® heat to the calandria's heat exchanger. Methanol was removed from the top of the column, and methanol reflux was provided to condense the glycol vapor.
- the monomer produced in the calandria was then pumped and filtered through a monomer line to the flasher. 13.8 milliliters/minute of 1% H3PO4 in glycol was added to the monomer line and mixed with the monomer to deactivate the ester exchange manganese catalyst. Then 9.5 milliliters/minute of 5% Ti ⁇ 2 in glycol was injected into the monomer line and mixed with the monomer.
- the monomer was then prepolymerized in a Dowtherm ® -heated flashing vessel operated at 245 degrees C and 90 millimeters of mercury pressure.
- the discharge from the flasher was fed to a Dowtherm ® heated, agitated prepolymerization vessel operated at 275 degrees C and 30 millimeters of mercury pressure.
- the prepolymer from the prepolymerization vessel was then fed to a horizontal screen/wire filming agitated finishing vessel. This vessel was run at 285 degrees C and a pressure to produce 19.7 +/- 0.6 LRV.
- the polymer produced was pumped to a spinning machine where yarn was spun at 290 degrees C, quenched, and steam drawn to produce a 70 denier (78 dtex) 34 filament trilobal cross section yarn. This process and product properties will be compared with product made by use of the catalyst of the invention.
- Dowtherm ® is a registered trademark of the
- the cobalt/aluminum catalyst was prepared separately. 250 grams of cobalt acetate with 4 waters of hydration were dissolved in 180 pounds (82 Kg) of ethylene glycol. 4061 grams of Nalco 8676 was added, and the mixture was heated to 160 degrees C to form a clear purple solution. This catalyst solution was injected into the monomer line at 24 milliliters/minute after the 11.4 milliliters/minute of 1% H3PO4 solution in glycol was added to deactivate the manganese catalyst.
- the catalyst was run the same way as described in the prior paragraph except 2 parts per million on a polymer basis of carboxyl violet was added with the i ⁇ 2 to change the hue color of the fiber.
- Oligomer with about 7 average degrees of polymerization, was made in a commercial direct esterfier reactor. A side stream was pumped to the semi-works' flashing vessel, prepolymerizer, and finishing vessels at 110 pounds (50 Kg) per hour. One item was made with no H3PO4, and one item was made with 14 milliliters/minute of 0.1% H3PO4 that was injected into the oligomer line and mixed with a static mixer to deactivate color forming metal residues. Then 18.8 milliliters/minute of 1% antimony solution in ethylene glycol as the polymerization catalyst and 23 milliliters/minute of 10% Ti ⁇ 2 as the delustrant, was then added to the oligomer line and mixed with a static mixer.
- the polymer was spun through a filtration pack and spinneret to produce a 265 denier (294 dtex) 34 filament draw textured feed yarn, known as partially oriented yarn (POY) .
- This yarn was textured at 700 meters/minute on a Barmag FK-6-900 texturing machine.
- the invention yarn was made in the same equipment, except that, instead of the antimony catalyst, 16 milliliters/minute of a cobalt aluminum catalyst solution was added to the oligomer line after the H3PO4 was injected.
- This catalyst was made by dissolving 250 grams of cobalt acetate with 4 waters of hydration in 180 pounds (82 Kg) of ethylene glycol. Then 4061 grams of Nalco 8676 was added. The mixture was then heated with agitation to 170 degrees C to produce a deep blue solution. The solution's theoretical cobalt level is 0.0725% and aluminum level is 0.263%. Results comparing control and invention produc .
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
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Abstract
Description
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
MX9709309A MX9709309A (en) | 1995-03-25 | 1996-06-04 | Catalyst, processes and polymer products therefrom. |
JP50311297A JP3459261B2 (en) | 1995-06-08 | 1996-06-04 | Catalysts, methods and polymer products obtained therefrom |
EP96919042A EP0830408B1 (en) | 1995-06-08 | 1996-06-04 | Catalyst, processes and polymer products therefrom |
DE69624917T DE69624917T2 (en) | 1995-06-08 | 1996-06-04 | CATALYST, METHOD AND POLYMERS MADE THEREFOR |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/487,767 US5512340A (en) | 1995-06-08 | 1995-06-08 | Catalyst and process for producing polyester |
US08/487,767 | 1995-06-08 | ||
US56904495A | 1995-12-07 | 1995-12-07 | |
US08/569,044 | 1995-12-07 | ||
US08/620,821 | 1996-03-25 | ||
US08/620,821 US5596069A (en) | 1995-06-08 | 1996-03-25 | Catalyst and process for producing catalyst |
Publications (1)
Publication Number | Publication Date |
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WO1996041828A1 true WO1996041828A1 (en) | 1996-12-27 |
Family
ID=27413777
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1996/008484 WO1996041828A1 (en) | 1995-03-25 | 1996-06-04 | Catalyst, processes and polymer products therefrom |
Country Status (9)
Country | Link |
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US (3) | US5596069A (en) |
EP (1) | EP0830408B1 (en) |
JP (1) | JP3459261B2 (en) |
CN (1) | CN1076359C (en) |
CA (1) | CA2222166A1 (en) |
DE (1) | DE69624917T2 (en) |
ES (1) | ES2184872T3 (en) |
PT (1) | PT830408E (en) |
WO (1) | WO1996041828A1 (en) |
Cited By (3)
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US7132383B2 (en) | 2000-09-12 | 2006-11-07 | Toyo Boseki Kabushiki Kaisha | Polymerization catalyst for polyester, polyester produced with the same, and process for producing polyester |
US7144614B2 (en) | 2001-02-23 | 2006-12-05 | Toyo Boseki Kabushiki Kaisha | Polyester polymerization catalyst, polyester produced by using the same, and process for producing polyester |
US7208565B1 (en) | 1999-08-24 | 2007-04-24 | Toyo Boseki Kabushiki Kaisha | Polymerization catalyst for polyesters, polyester produced with the same, and process for production of polyester |
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EP0399797A2 (en) * | 1989-05-25 | 1990-11-28 | Hoechst Celanese Corporation | Process for preparing low color polyarylates |
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DE1545039A1 (en) * | 1963-10-21 | 1969-11-20 | Toyo Rayon Co Ltd | Process for the production of polyesters |
US4590259A (en) * | 1984-11-30 | 1986-05-20 | General Electric Company | High molecular weight linear polyesters and method for their preparation |
US5166311A (en) * | 1989-05-22 | 1992-11-24 | Hoechst Celanese Corporation | Catalyst system and process for preparing high clarity, colorless polyethylene terephthalate |
US5116938A (en) * | 1989-10-23 | 1992-05-26 | Hoechst Celanese Corporation | Process for producing the polyester polyethylene terephthalate (PET) from a lower dialkyl ester of a dicarboxylic acid and a glycol using a specific catalyst system |
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1996
- 1996-03-25 US US08/620,821 patent/US5596069A/en not_active Expired - Fee Related
- 1996-06-04 ES ES96919042T patent/ES2184872T3/en not_active Expired - Lifetime
- 1996-06-04 CN CN96196132A patent/CN1076359C/en not_active Expired - Fee Related
- 1996-06-04 JP JP50311297A patent/JP3459261B2/en not_active Expired - Fee Related
- 1996-06-04 PT PT96919042T patent/PT830408E/en unknown
- 1996-06-04 WO PCT/US1996/008484 patent/WO1996041828A1/en active IP Right Grant
- 1996-06-04 CA CA002222166A patent/CA2222166A1/en not_active Abandoned
- 1996-06-04 EP EP96919042A patent/EP0830408B1/en not_active Expired - Lifetime
- 1996-06-04 DE DE69624917T patent/DE69624917T2/en not_active Expired - Lifetime
- 1996-08-14 US US08/702,419 patent/US5652033A/en not_active Expired - Fee Related
- 1996-08-14 US US08/702,418 patent/US5674801A/en not_active Expired - Fee Related
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FR1426192A (en) * | 1963-10-21 | 1966-01-28 | Toyo Rayon Co Ltd | Process for the preparation of polyesters |
US3533973A (en) * | 1968-11-04 | 1970-10-13 | Fmc Corp | Polyester polycondensation in the presence of a catalytic amount of a trivalent aluminum salt |
EP0234917A2 (en) * | 1986-02-25 | 1987-09-02 | Celanese Corporation | Preparation of gray to blue aromatic polyesters by incorporation of cobalt into the catalyst system |
EP0399797A2 (en) * | 1989-05-25 | 1990-11-28 | Hoechst Celanese Corporation | Process for preparing low color polyarylates |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7208565B1 (en) | 1999-08-24 | 2007-04-24 | Toyo Boseki Kabushiki Kaisha | Polymerization catalyst for polyesters, polyester produced with the same, and process for production of polyester |
US8293862B2 (en) | 1999-08-24 | 2012-10-23 | Toyo Boseki Kabushiki Kaisha | Polyester polymerization catalyst, polyester produced by using the same, and a process for producing polyester |
US7132383B2 (en) | 2000-09-12 | 2006-11-07 | Toyo Boseki Kabushiki Kaisha | Polymerization catalyst for polyester, polyester produced with the same, and process for producing polyester |
US7144614B2 (en) | 2001-02-23 | 2006-12-05 | Toyo Boseki Kabushiki Kaisha | Polyester polymerization catalyst, polyester produced by using the same, and process for producing polyester |
Also Published As
Publication number | Publication date |
---|---|
CN1192758A (en) | 1998-09-09 |
EP0830408B1 (en) | 2002-11-20 |
US5596069A (en) | 1997-01-21 |
US5652033A (en) | 1997-07-29 |
DE69624917D1 (en) | 2003-01-02 |
PT830408E (en) | 2003-02-28 |
ES2184872T3 (en) | 2003-04-16 |
JP3459261B2 (en) | 2003-10-20 |
EP0830408A1 (en) | 1998-03-25 |
US5674801A (en) | 1997-10-07 |
JPH11507694A (en) | 1999-07-06 |
CA2222166A1 (en) | 1996-12-27 |
CN1076359C (en) | 2001-12-19 |
DE69624917T2 (en) | 2003-07-31 |
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