US20020032300A1 - Polyester polycondensation with catalyst and a catalyst enhancer - Google Patents
Polyester polycondensation with catalyst and a catalyst enhancer Download PDFInfo
- Publication number
- US20020032300A1 US20020032300A1 US09/895,990 US89599001A US2002032300A1 US 20020032300 A1 US20020032300 A1 US 20020032300A1 US 89599001 A US89599001 A US 89599001A US 2002032300 A1 US2002032300 A1 US 2002032300A1
- Authority
- US
- United States
- Prior art keywords
- catalyst
- combination
- oxalate
- polyester
- antimony
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0202—Polynuclearity
- B01J2531/0205—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/46—Titanium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
- B01J2531/52—Antimony
-
- 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
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
-
- 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
- C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds thereof
-
- 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
- C08G63/87—Non-metals or inter-compounds thereof
Definitions
- This invention relates to synergistic combinations of titanium containing catalysts and catalyst enhancers of carboxylic acid or oxalic acid or their Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba and ammonium salts that are useful for manufacturing polyesters.
- the synergistic combination of the titanium containing catalysts with a catalyst enhancer such as an oxalic acid, an oxalic acid salt or a carboxylic acid or a carboxylic acid salt provides fast reactions with improved properties such as reduced acetaldehyde content and good color properties for the resulting polyester at substantially reduced catalyst levels.
- Titanyl oxalate compounds have been suggested as catalysts for polycondensation reactions to produce polyesters.
- titanyl oxalate catalysts when used as polycondensation catalysts for polyesters have caused color problems in the resulting polyester.
- Polyesters are obtained by esterification, ester interchange or polycondensation of dibasic acids such as terephthalic acid and isophthalic acid or esters thereof, functional derivatives of acid chlorides and glycols such as ethylene glycol and tetramethylene glycol or oxides thereof and functional derivatives of carbonic acid derivatives.
- dibasic acids such as terephthalic acid and isophthalic acid or esters thereof
- functional derivatives of acid chlorides and glycols such as ethylene glycol and tetramethylene glycol or oxides thereof and functional derivatives of carbonic acid derivatives.
- a single polyester is obtained when one dibasic acid component and glycol component are used.
- Mixed copolyesters can be obtained when at least two or more types of dibasic acid component and glycol component are mixed, esterified or subjected to ester interchange and then subjected to polycondensation.
- an ordered polyester is obtained.
- the term polyester is a general designation for these three types.
- titanyl oxalate compounds for use as polycondensation catalysts for polyesters.
- the titanyl oxalate compounds disclosed include potassium titanyl oxalate, ammonium titanyl oxalate, lithium titanyl oxalate, sodium titanyl oxalate, calcium titanyl oxalate, strontium titanyl oxalate, barium titanyl oxalate, zinc titanyl oxalate and lead titanyl titanate.
- potassium titanyl oxalate include potassium titanyl oxalate, ammonium titanyl oxalate, lithium titanyl oxalate, sodium titanyl oxalate, calcium titanyl oxalate, strontium titanyl oxalate, barium titanyl oxalate, zinc titanyl oxalate and lead titanyl titanate.
- potassium and ammonium titanyl oxalate have actually been used to cat
- EP 0699700 A2 published Mar. 6, 1996 assigned to Hoechst and entitled “Process for production of Thermostable, Color-neutral, Antimony-Free Polyester and Products Manufactured From It” discloses the use as polycondensation catalyst, however only potassium titanyl oxalate and titanium isopropylate were used for such a catalyst, and, while improved color and antimony free polyester are disclosed, cobalt or optical brighteners were also employed.
- Other patents have disclosed potassium titanyl oxalate as a polycondensation catalyst for making polyester such as U.S. Pat. No.
- Titanium based catalysts have shown very high polycondensation activity, however; the resulted polyesters are yellowish color which will limit their applications. Therefore, prior art activity has been directed towards the development of modified titanium catalysts. Titanium compounds are not a good sole catalyst. Ti requires a cocatalysts or modifiers/promoters to form composite catalyst. Titanium compounds in the general formula of Ti(OR) 4 , Ti (III) Ti (IV) y O (3+4y)/2 , RO[Ti(OR) 2 O] n R have been widely claimed by others.
- Cocatalysts or modifiers/promoters such as antimony compounds, tin compounds, zirconium compounds, silicon compounds, cobalt compound, aluminum compounds, alkali metal compounds, rare earth metal compounds, magnesium compounds, germanium compounds, zinc compounds, lanthanide series compounds, phosphorus compounds, halides, sulfur containing compounds, ammonia hydroxide, and amines, have been claimed together with Ti compounds.
- U.S. Pat. No. 6,166, 170, E.I. du Pont de Nemours and Company, issued on Dec. 26, 2000 discloses a catalyst composition of a titanium compound, a complexing agent, and an aqueous solution of hypophosphorous acid or a salt.
- the titanium compound has a general formula, Ti(OR) 4 , combined with a zirconium compound, Zr(OR) 4 .
- the complex agents are hydroxycarboxylic acids, alkanolamines, aminocarboxylic acids and their combinations of two or more.
- the organic compound is Ti(OR) 4 .
- the phosphorus compound is either (RO) x (PO)(OH) 3 ⁇ x or (RO) y (P 2 O 3 )(OH) 4 ⁇ y .
- the amine is a tertiary amine. Aluminum, cobalt, antimony compounds and their combination were claimed as cocatalysts.
- U.S. Pat. No. 6,034,203 E.I. du Pont de Nemours and Company, issued on Mar. 7, 2000, discloses a catalytic process that can be used in oligomerization, polymerization, or depolymerization.
- the catalyst has the formula of M x Ti (III) Ti (IV) y O (x+3+4y)/2 , where M is an alkali metal, such as Li; x and y are numbers greater than or equal to zero wherein if x equals zero, y is a number less than 1 ⁇ 2.
- This patent shows a catalyst solution containing an organic titanate ligand, organic silicates and/or zirconates, and phosphorus compounds.
- Titanium has a formula of Ti(OR) 4 ; silicon and zirconium compounds can be organic ortho silicate and zirconate; phosphorus compound can be an organic phosphonic or phosphinic acid.
- the solvent used was ethylene glycol.
- the catalyst was claimed to be used in fabrication of PET, PEI, PPT, PBT, and etc.
- the base can be selected sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, magnesium hydroxide and ammonia.
- WO 00/71252 Al ACMA Limited, published on Nov. 30, 2000.
- An esterification catalyst composition was disclosed.
- the catalyst contains 1) hydrolysis product of orthoesters and condensed orthoesters of titanium, zirconium or aluminum; 2) an alcohol containing at least two hydroxyl groups; 3) an organophosphorus compound containing at least one P—OH group and a base; 4) a compound of germanium, antimony or tin.
- WO 99/28033 Al Tioxide Specialties, published on Jun. 10, 1999.
- An esterification catalyst composition was disclosed.
- the catalyst contains 1) hydrolysis product of orthoesters and condensed orthoesters of titanium, zirconium or aluminum; 2) an alcohol containing at least two hydroxyl groups; 3) an organophosphorus compound containing at least one P-OH group and a base.
- WO 97/47675 Al Imperial Chemical Industries PLC, published on Dec. 18, 1997 also EP 0906356 jointly with E. I. Du Pont De Nemours & Company Inc.
- a catalyst is disclosed that is obtained by reacting an alkyl titanate or alkyl zirconate, an alcohol, a 2-hydroxy carboxylic acid and a base.
- a cobalt (II) salt, a phosphorus compound, and a sodium compound were claimed as catalyst components.
- a catalyst composition for the preparation of a polyester on copolyester is disclosed.
- the catalyst was composed of 1) a titanium or zirconium based compound, general formula, Ti(OR) 4 or Zr(OR) 4 , the titanium compounds were water-stable; 2) a lanthanide series compound, such as lanthanum, samarium, europium, erbium, terbium, and cerium; 3) a hafnium based compound; 4) a phosphate-forming compound, such as alkali metal phosphates, alkali metal phosphates, alkali hypophosphates, and alkali metal polyphosphates.
- the combination of the above components was claimed.
- titanium oxide acetylacetonate was claimed (in claim 3 , col. 13, lines 52 and 53).
- M is selected from carbon atom, phosphorous atom, sulfur atom, and their mixtures.
- the zinc compound can be zinc oxide, zinc acetate, zinc chloride, zinc hydroxide and their mixtures.
- An antimony compound can be selected from antimony chloride, antimony acetate, antimony oxide and their mixtures.
- a phosphorous compound can be one of the following, Phosphoric acid compounds, phosphite compounds, phosphonic acid compounds, phosphinic acid compound, and their mixtures.
- the composite catalyst consists of a compound of Sb, a compound of Ti, and a compound of Sn.
- a compound of Ti has a general formula of (R 1 O) 4 TiHP(O)(OR 2 ) 2 , and Tin compound, (R 3 ) 2 SnX, where X is selected from sulfur, oxygen, halogen, and a compound containing an ether, a thio or an ester bond.
- potassium titanium oxyoxalate was claimed as shown in claim 9 (col. 10, lines 52 and 53) other metals (such as germanium, zinc, manganese, alkali, and alkali earth) compounds were also claimed. It was disclosed that antioxidant, such as a hindered phenol, was used in the process.
- the present invention is based upon the discovery of a synergistic combination of a titanium containing catalyst and a catalyst enhancer.
- An improved three component enhanced catalyst mixture can be obtained by the addition of second catalyst to either of the above enhanced catalyst mixtures, the second catalyst being a compound containing antimony or germanium.
- enhanced antimony containing catalysts comprising the mixture of an antimony containing catalyst and an enhancer of an oxalic acid or its corresponding Li, Na, K, Rb Cs, Be, Mg, Ca, Sr, Ba or ammonium salt.
- This invention also provides an improved process of producing polyester by the polycondensation of polyester forming reactants in the presence of a catalytically effective amount of a polycondensation catalyst, wherein the improvement comprises utilizing, as the polycondensation catalyst, the synergistic combination of a titanium containing catalyst and the catalyst enhancer described in the preceding paragraph.
- a novel polyester is also provided containing the synergistic combination of a titanium containing catalyst and the catalyst enhancer described in the preceding paragraph.
- the improved process produces an improved polyester having lower acetaldehyde numbers and good color.
- the titanium containing catalyst and catalyst enhancer composition can be used as a polycondensation catalyst in combination with other catalysts to achieve synergistic catalytic activity.
- polyester by polycondensation of polyester forming reactants is well known to those skilled in the polyester art.
- a conventional catalyst for the reaction is antimony oxide.
- the present invention is based upon the discovery of a synergistic relationship between titanium containing catalysts and carboxylic or oxalate catalyst enhancers.
- the catalyst and catalyst enhancer is surprisingly superior in catalyst performance for polycondensation reactions by providing good catalyst activity at reduced catalyst loadings and superior brightness in the resulting polyester.
- Reactants for forming polyesters via a polycondensation reaction are well known to those skilled in the art and disclosed in patents such as U.S. Pat. No. 5,198,530, inventor Kyber, M., et al., U.S. Pat. No. 4,238,593, inventor B. Duh, U.S. Pat. No. 4,356,299, inventor Cholod et al, and U.S. Pat. No. 3,907,754, inventor Tershasy et al, which disclosures are incorporated herein by reference.
- the art is also described in “Comprehensive Polymer Science, Ed. G. C. Eastmond, et al, Pergamon Press, Oxford 1989, vol. 5, pp. 275-315, and by R. E. Wilfong, J. Polym. Science, 54(1961), pp. 385-410.
- a particularly important commercial specie of polyester so produced is polyethylene terephthalate (PET).
- the synergistic catalyst combinations of the present invention are effective for catalyzing esterification and transesterification reactions when used in catalytically effective amounts with reactants known to participate in esterification or transesterification reactions.
- a catalytically effective amount is suitable.
- An improved three component enhanced catalyst composition can be obtained by the addition of second catalyst to enhanced catalyst composition defined above, the second catalyst being a compound containing antimony or germanium.
- Titanyl oxalates include metallic titanyl oxalates of the formula M 2 TiO(C 2 O 4 ) 2 (H 2 O) n wherein each M is independently selected from potassium, lithium, sodium and cesium such as lithium or potassium titanyl oxalate and nonmetallic titanyl oxalates such as ammonium titanyl oxalate.
- Examples of a catalyst enhancer for the titanium oxalate catalysts are a carboxylic acid containing 1 to 26 carbon atoms or its corresponding carboxylic acid salt having an anion selected from the group consisting of Li, Na, K, Rb Cs, Be, Mg, Ca, Sr, Ba and ammonium.
- carboxylic acid includes dicarboxylic acid. Examples of such carboxylic acids or salts are well known and include sodium acetate, sodium propionate, sodium citrate, sodium butyrate, sodium formate, sodium fumarate, malonic acid, potassium acetate, potassium benzoate, succinic acid, glutaric acid, adipic acid, maleic acid. Preferred are potassium acetate, potassium benzoate.
- titanium containing compounds of the formula X m TiY o with X selected from the group consisting of: H, Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba and ammonium, m 0, 1, or 2
- Preferred are acetylacetonate, i-propoxide, bis(2,2,6,6,-t)
- Examples of a catalyst enhancer for said titanium containing compounds are oxalic acids or its corresponding Li, Na, K, Rb Cs, Be, Mg, Ca, Sr, Ba, or ammonium oxalic acid. Preferred are H, Li, Na, K, Ca, Cs, and ammonium.
- antimony containing catalysts that can be added to the synergistic combination of enhanced titanium oxalate or titanium containing catalysts defined above are Sb 2 O 3 , Sb(CH 3 COO) 3 , and Sb 2 (OCH 2 CH 2 O) 3 .
- germanium containing catalysts that can be added to the synergistic combination of enhanced titanium oxalate or titanium containing catalysts defined above are GeO 2 , Ge(OC 2 H 5 ) 4 , Ge[OCH(CH 3 ) 2 ] 4 , Ge(OCH 3 ) 4 . Preferred is GeO 2 .
- antimony containing catalysts that can be enhanced with a carboxylic acid or salt or an oxalic acid or salt are Sb 2 O 3 , Sb(CH 3 COO) 3 , Sb 2 (OCH 2 CH 2 O) 3 .
- Cocatalysts that function in combination with the titanium containing catalyst and the enhancer include antimony triacetate, Sb(CH 3 COO) 3 , antimony glycoxide, Sb 2 (OCH 2 CH 2 O) 3 , antimony oxide. (Sb 2 O 3 ).
- An effective amount for enhancing the catalytic activity of titanyl oxalate catalysts or a titanium containing catalyst is at least about 0.1 part of enhancer per part of titanyl oxalate catalyst. Preferred is from about 0.1 part to about 100 parts enhancer per part of catalyst based upon the total weight of titanium in the catalyst.
- a catalytically effective amount of titanium containing catalyst should be added to the polyester forming reactants, generally at least 0.1 part based upon the weight of titanium. Preferred is from about 1 part to about 40 parts per million of catalyst based on the weight titanium in the catalyst and the weight of the of polyester forming reactants.
- a catalytically effective amount of an antimony containing catalyst should be added to the polyester forming reactants. Preferred is from about 1 part to about 240 parts per million of catalyst based on the weight antimony in the catalyst and the weight of the of polyester forming reactants.
- an effective amount for of an enhancer for the catalytic activity of an antimony containing catalyst is at least about 0.1 part of enhancer per part of antimony containing catalyst based the weight of antimony in said antimony containing catalyst.
- Preferred is from about 0.1 part to about 80 parts enhancer per part of catalyst based upon the total weight of titanium in the catalyst.
- the preferred amount of a antimony or germanium containing catalyst for use in combination with the enhanced titanium oxalate or titanium containing catalyst described above is from about 0.1 parts to about 80 parts based upon the weight of titanium. Preferred is from 1 to 40 parts of antimony or germanium containing catalyst.
- the catalyst and enhancer mixtures of the present invention are used to make polyester typically by first dissolving them in a solvent that is compatible with polyester forming reactants, or preferable in one of the reactants itself, such as ethylene glycol.
- acetaldehyde is an undesirable polymerization by-product.
- Polymerization rate is measured as rate at which intrinsic viscosity (IV) increases during reaction.
- Intrinsic viscosity change is an indication of the degree of polymerization that has occurred during the reaction.
- Catalyst evaluation was performed with a ⁇ fraction (3/16) ⁇ stainless steel, 2 L reactor, fitted with a ball valve at the bottom of the reactor.
- the vessel was equipped with 3 inlet ports, one outlet port, one thermowell port and one pressure transducer port, and was vertically stirred by an electric motor with amperage monitoring.
- the laboratory experimental were all conducted on a 4.0 mole scale, using as polyester forming reactants, BHET and a normal bottle resin autoclave recipe. The experimental catalysts were added at the time of BHET charging.
- BHET Bis(2-hydroxyethyl)terephthalate
- catalyst were added to the reactor and the contents blanketed with nitrogen. The mixtures were heated under reduced pressure with constant stirring. The ethylene glycol (EG) produced during the polymerization was removed and trapped. The polymerization was at 280° C. , under the vacuum of typically around 1 torr. The reaction was terminated when the stirrer torque reached a level, indicated by amperage to the stirrer motor, typical for a polymer of IV ⁇ 0.6. The molten state polymer under nitrogen (containing less than 2 ppm of oxygen) blanket was discharged from the bottom ball valve and quenched into a bucket filled with cold water. 1 ⁇ 4′′ diameter and ⁇ fraction (1/16) ⁇ ′′ thick pellets (for color measurement) were made by filling the molten polymer in a press molder and chilled immediately in cold water.
- EG ethylene glycol
- the solution intrinsic viscosity (IV) was measured by following the ASTM D 4603 method.
- Acetaldehyde (AA) was measured at 150° C. using gas chromatography (GC) equipped with a headspace analyzer.
- the brightness (L*) and yellowness (b*) were determined by the Hunter Lab's instrument and method.
- Example A catalyst ⁇ 180 ppm potassium oxalate ⁇ reaction time 124 mins.
- Example C catalyst ⁇ 6 ppm titanium potassium titanyl oxalate ⁇ reaction time 71 mins.
- Example E catalyst ⁇ 240 ppm antimony from antimony (III) oxide ⁇ reaction time 90 mins.
- Example G catalyst ⁇ 60 ppm germanium from germanium oxide ⁇ reaction time 149.
- the three component catalyst produced more brighter and less yellow polymer than antimony oxide. It is conceivable that the rate for three components can be further enhanced and the amount of acetaldehyde in the resulting polymer can be further reduced by adjusting the composition of the three components.
- the germanium catalyst can be enhanced by potassium oxalate.
Abstract
Description
- REFERENCE TO RELATED APPLICATION
- This application is a continuation-in-part of U.S. patent application Ser. No. 09/747,115, filed Dec. 22, 2000, which claims priority of U.S. Provisional Application No. 60/175,006, filed Jan. 7, 2000, which disclosures are incorporated herein by reference.
- This invention relates to synergistic combinations of titanium containing catalysts and catalyst enhancers of carboxylic acid or oxalic acid or their Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba and ammonium salts that are useful for manufacturing polyesters. The synergistic combination of the titanium containing catalysts with a catalyst enhancer such as an oxalic acid, an oxalic acid salt or a carboxylic acid or a carboxylic acid salt provides fast reactions with improved properties such as reduced acetaldehyde content and good color properties for the resulting polyester at substantially reduced catalyst levels.
- Polycondensation reactions that produce polyesters require an extremely long period of time that is significantly reduced by a suitable catalyst. Various types of catalysts are used to shorten the reaction time. For example, antimony trioxide antimony triacetate and antimony trisglycoxide are generally used as polycondensation catalysts.
- Titanyl oxalate compounds have been suggested as catalysts for polycondensation reactions to produce polyesters. However, titanyl oxalate catalysts when used as polycondensation catalysts for polyesters have caused color problems in the resulting polyester.
- Polyesters are obtained by esterification, ester interchange or polycondensation of dibasic acids such as terephthalic acid and isophthalic acid or esters thereof, functional derivatives of acid chlorides and glycols such as ethylene glycol and tetramethylene glycol or oxides thereof and functional derivatives of carbonic acid derivatives. In this case, a single polyester is obtained when one dibasic acid component and glycol component are used. Mixed copolyesters can be obtained when at least two or more types of dibasic acid component and glycol component are mixed, esterified or subjected to ester interchange and then subjected to polycondensation. When a single polyester or two or more initial polycondensates of a mixed copolyester are subjected to polycondensation, an ordered polyester is obtained. In this invention, the term polyester is a general designation for these three types.
- Prior literature has disclosed titanyl oxalate compounds for use as polycondensation catalysts for polyesters. The titanyl oxalate compounds disclosed include potassium titanyl oxalate, ammonium titanyl oxalate, lithium titanyl oxalate, sodium titanyl oxalate, calcium titanyl oxalate, strontium titanyl oxalate, barium titanyl oxalate, zinc titanyl oxalate and lead titanyl titanate. However, based upon the examples in such literature references, only potassium and ammonium titanyl oxalate have actually been used to catalyze the polyester forming reaction. See for example Japanese Patent Publication 42-13030, published on Jul. 25, 1967. European Patent application EP 0699700 A2 published Mar. 6, 1996 assigned to Hoechst and entitled “Process for production of Thermostable, Color-neutral, Antimony-Free Polyester and Products Manufactured From It” discloses the use as polycondensation catalyst, however only potassium titanyl oxalate and titanium isopropylate were used for such a catalyst, and, while improved color and antimony free polyester are disclosed, cobalt or optical brighteners were also employed. Other patents have disclosed potassium titanyl oxalate as a polycondensation catalyst for making polyester such as U.S. Pat. No. 4,245,086, inventor Keiichi Uno et al., Japanese Patent JP 06128464, Inventor Ishida, M. et al. U.S. Pat. No. 3,951,886, entitled “Process of Producing Polyester Resin” of Hideo, M. et al, at column 3, line 59 to column 4, line 10, contains a disclosure of titanyl oxalate catalysts for polyesters including a listing of many types of titanyl oxalate catalyst. However, only potassium titanyl oxalate and ammonium titanyl oxalate were used in the examples and lithium titanyl oxalate was not even listed among their preferred titanyl oxalate catalysts.
- Titanium based catalysts have shown very high polycondensation activity, however; the resulted polyesters are yellowish color which will limit their applications. Therefore, prior art activity has been directed towards the development of modified titanium catalysts. Titanium compounds are not a good sole catalyst. Ti requires a cocatalysts or modifiers/promoters to form composite catalyst. Titanium compounds in the general formula of Ti(OR)4, Ti(III)Ti(IV) yO(3+4y)/2, RO[Ti(OR)2O]nR have been widely claimed by others. Cocatalysts or modifiers/promoters, such as antimony compounds, tin compounds, zirconium compounds, silicon compounds, cobalt compound, aluminum compounds, alkali metal compounds, rare earth metal compounds, magnesium compounds, germanium compounds, zinc compounds, lanthanide series compounds, phosphorus compounds, halides, sulfur containing compounds, ammonia hydroxide, and amines, have been claimed together with Ti compounds.
- U.S. Pat. No. 6,166, 170, E.I. du Pont de Nemours and Company, issued on Dec. 26, 2000 discloses a catalyst composition of a titanium compound, a complexing agent, and an aqueous solution of hypophosphorous acid or a salt. The titanium compound has a general formula, Ti(OR)4, combined with a zirconium compound, Zr(OR)4. The complex agents are hydroxycarboxylic acids, alkanolamines, aminocarboxylic acids and their combinations of two or more.
- U.S. Pat. No. 6,066,714, E.I. du Pont de Nemours and Company, issued on May 23, 2000, discloses an organic titanium compound, a phosphorus compound, an amine, and a solvent as a catalyst. The organic compound is Ti(OR)4. The phosphorus compound is either (RO)x(PO)(OH)3−x or (RO)y(P2O3)(OH)4−y. The amine is a tertiary amine. Aluminum, cobalt, antimony compounds and their combination were claimed as cocatalysts.
- U.S. Pat. No. 6,034,203, E.I. du Pont de Nemours and Company, issued on Mar. 7, 2000, discloses a catalytic process that can be used in oligomerization, polymerization, or depolymerization. The catalyst has the formula of MxTi(III)Ti(IV) yO(x+3+4y)/2, where M is an alkali metal, such as Li; x and y are numbers greater than or equal to zero wherein if x equals zero, y is a number less than ½.
- U.S. Pat. No. 5,981,690, E.I. du Pont de Nemours and Company, issued on Nov. 9, 1999. This patent shows a catalyst solution containing an organic titanate ligand, organic silicates and/or zirconates, and phosphorus compounds. Titanium has a formula of Ti(OR)4; silicon and zirconium compounds can be organic ortho silicate and zirconate; phosphorus compound can be an organic phosphonic or phosphinic acid. The solvent used was ethylene glycol. The catalyst was claimed to be used in fabrication of PET, PEI, PPT, PBT, and etc.
- U.S. Pat. No. 5,866, 710, Tioxide Specialties Limited, issued on Feb. 2, 1999 (EP 0 812 818 Al, published on Dec. 17, 1999). A process of preparing an ester is disclosed in the presence of a catalyst and a base, the product from orthoesters and condensed orthoesters of zirconium and titanium. The orthoesters have the formula of M(OR)4; the condensed orthoesters, RO[M(OR)2O]R; where M is either zirconium or titanium. This compound can be illustrated as the following,
- M(OR)4, if n=1
- (RO)3MOM(OR)3, if n=2
- (RO)3MOM(OR)2OM(OR)3, if n=3,
- and etc.
- The base can be selected sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, magnesium hydroxide and ammonia.
- WO 00/71252 Al, ACMA Limited, published on Nov. 30, 2000. An esterification catalyst composition was disclosed. The catalyst contains 1) hydrolysis product of orthoesters and condensed orthoesters of titanium, zirconium or aluminum; 2) an alcohol containing at least two hydroxyl groups; 3) an organophosphorus compound containing at least one P—OH group and a base; 4) a compound of germanium, antimony or tin.
- WO 99/28033 Al, Tioxide Specialties, published on Jun. 10, 1999. An esterification catalyst composition was disclosed. The catalyst contains 1) hydrolysis product of orthoesters and condensed orthoesters of titanium, zirconium or aluminum; 2) an alcohol containing at least two hydroxyl groups; 3) an organophosphorus compound containing at least one P-OH group and a base.
- WO 97/47675 Al, Imperial Chemical Industries PLC, published on Dec. 18, 1997 also EP 0906356 jointly with E. I. Du Pont De Nemours & Company Inc. A catalyst is disclosed that is obtained by reacting an alkyl titanate or alkyl zirconate, an alcohol, a 2-hydroxy carboxylic acid and a base. A cobalt (II) salt, a phosphorus compound, and a sodium compound were claimed as catalyst components.
- U.S. Pat. No. 5,874,517, Hoechst Celanese Corporation, issued on Feb. 23, 1999. An improved low acetaldehyde process was disclosed. The process utilized mixed Ti and Sb catalysts, however; potassium titanyl oxalate was suggested as a sole catalyst (col. 6, lines 21 and 22). Potassium titanyl oxalate as a polycondensation catalyst was claimed in claims15 to 20.
- U.S. Pat. No. 5,902,873, General Electric Company, issued on May 11, 1999; (EP 0 909 774 Al, published on Apr. 21, 1999. A catalyst composition for the preparation of a polyester on copolyester is disclosed. The catalyst was composed of 1) a titanium or zirconium based compound, general formula, Ti(OR)4 or Zr(OR)4, the titanium compounds were water-stable; 2) a lanthanide series compound, such as lanthanum, samarium, europium, erbium, terbium, and cerium; 3) a hafnium based compound; 4) a phosphate-forming compound, such as alkali metal phosphates, alkali metal phosphates, alkali hypophosphates, and alkali metal polyphosphates. The combination of the above components was claimed. In particular, titanium oxide acetylacetonate was claimed (in claim 3, col. 13, lines 52 and 53).
- U.S. Pat. No. 6,133,404, National Institute of Technology and Quality, issued on Oct. 17, 2000. A polyester and formation process is disclosed in the presence of a composite catalyst that consists of a titanium compound, a zinc compound, an antimony compound, and a phosphorous compound. This catalyst improved the rate of polyester production and properties of the polymers, in particular, biodegradability of the polymer. The titanium compound has the following general formula,
- Ti(OR)4,
- (RO)4TiHP(O)(OR′)2
- ROTi[OM(O)R″]3,
- where M is selected from carbon atom, phosphorous atom, sulfur atom, and their mixtures.
- The zinc compound can be zinc oxide, zinc acetate, zinc chloride, zinc hydroxide and their mixtures. An antimony compound can be selected from antimony chloride, antimony acetate, antimony oxide and their mixtures. A phosphorous compound can be one of the following, Phosphoric acid compounds, phosphite compounds, phosphonic acid compounds, phosphinic acid compound, and their mixtures.
- U.S. Pat. No. 5,714,570, Korea Institute of Science and Technology, issued on Feb. 3, 1998. A method for the preparation of polyester by use of a composite catalyst was revealed. The composite catalyst consists of a compound of Sb, a compound of Ti, and a compound of Sn. A compound of Ti has a general formula of (R1O)4TiHP(O)(OR2)2, and Tin compound, (R3)2SnX, where X is selected from sulfur, oxygen, halogen, and a compound containing an ether, a thio or an ester bond. In particular, potassium titanium oxyoxalate was claimed as shown in claim 9 (col. 10, lines 52 and 53) other metals (such as germanium, zinc, manganese, alkali, and alkali earth) compounds were also claimed. It was disclosed that antioxidant, such as a hindered phenol, was used in the process.
- U.S. Pat. No. 6,143,837, Sinco Ricerche, S.P.A, issued on Nov. 7, 2000. A process of preparation of polyester resin utilizing Ti compound catalyst was disclosed. The activity of Ti catalysts was shown to be four time higher than S21 catalyst. The titanium compounds can be selected from the group consisting of alkoxides of titanium, acetyl acetonates of titanium, dioxide of titanium, and titanium phosphites. Silica mixed with Ti was used in their examples (but not claimed). A cobalt compound was suggested to be used as a colorants.
- The present invention is based upon the discovery of a synergistic combination of a titanium containing catalyst and a catalyst enhancer. This invention provides a novel catalytic mixture comprising a titanium containing catalyst of the formula XmTiO(C2O4)2(H2O)n, where X is selected from the group consisting of H, Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, and ammonium, m=1 or 2; and a catalyst enhancer comprising oxalic acid or carboxylic acid containing 1 to 26 carbon atoms or their corresponding Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, or ammonium salt. Also provided is a novel enhanced catalyst mixture comprising a titanium compound of the formula XmTiYo with X selected from the group consisting of: H, Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba and ammonium, m=1 or 2, Y is a ligand of the formula CaHbOc, a=0 to 30, b=0 to 60, and c=1 to 10; o=2, 3, 4, and a catalyst enhancer of an oxalic acid or its corresponding Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba or ammonium salt. An improved three component enhanced catalyst mixture can be obtained by the addition of second catalyst to either of the above enhanced catalyst mixtures, the second catalyst being a compound containing antimony or germanium. Also provided are enhanced antimony containing catalysts comprising the mixture of an antimony containing catalyst and an enhancer of an oxalic acid or its corresponding Li, Na, K, Rb Cs, Be, Mg, Ca, Sr, Ba or ammonium salt.
- This invention also provides an improved process of producing polyester by the polycondensation of polyester forming reactants in the presence of a catalytically effective amount of a polycondensation catalyst, wherein the improvement comprises utilizing, as the polycondensation catalyst, the synergistic combination of a titanium containing catalyst and the catalyst enhancer described in the preceding paragraph. A novel polyester is also provided containing the synergistic combination of a titanium containing catalyst and the catalyst enhancer described in the preceding paragraph. The improved process produces an improved polyester having lower acetaldehyde numbers and good color. The titanium containing catalyst and catalyst enhancer composition can be used as a polycondensation catalyst in combination with other catalysts to achieve synergistic catalytic activity.
- The production of polyester by polycondensation of polyester forming reactants is well known to those skilled in the polyester art. A conventional catalyst for the reaction is antimony oxide. The present invention is based upon the discovery of a synergistic relationship between titanium containing catalysts and carboxylic or oxalate catalyst enhancers. The catalyst and catalyst enhancer is surprisingly superior in catalyst performance for polycondensation reactions by providing good catalyst activity at reduced catalyst loadings and superior brightness in the resulting polyester.
- Reactants for forming polyesters via a polycondensation reaction are well known to those skilled in the art and disclosed in patents such as U.S. Pat. No. 5,198,530, inventor Kyber, M., et al., U.S. Pat. No. 4,238,593, inventor B. Duh, U.S. Pat. No. 4,356,299, inventor Cholod et al, and U.S. Pat. No. 3,907,754, inventor Tershasy et al, which disclosures are incorporated herein by reference. The art is also described in “Comprehensive Polymer Science, Ed. G. C. Eastmond, et al, Pergamon Press, Oxford 1989, vol. 5, pp. 275-315, and by R. E. Wilfong, J. Polym. Science, 54(1961), pp. 385-410. A particularly important commercial specie of polyester so produced is polyethylene terephthalate (PET).
- In addition to catalyzing polycondensation reactions, the synergistic catalyst combinations of the present invention are effective for catalyzing esterification and transesterification reactions when used in catalytically effective amounts with reactants known to participate in esterification or transesterification reactions. A catalytically effective amount is suitable.
- An improved three component enhanced catalyst composition can be obtained by the addition of second catalyst to enhanced catalyst composition defined above, the second catalyst being a compound containing antimony or germanium.
- TITANIUM OXALATE CATALYSTS:
- Examples of titanium oxalate catalysts of the formula XmTiO(C2O4)2(H2O)n, where each X is independently selected from the group consisting of H, Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba and ammonium, m=1 or 2 are well known. Titanyl oxalates comprise compounds of the formula: XmTiO(C2O4)2(H2O)n, where X is selected from the group consisting of: H, Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr and Ba, m=1 or 2. Titanyl oxalates include metallic titanyl oxalates of the formula M2TiO(C2O4)2(H2O)n wherein each M is independently selected from potassium, lithium, sodium and cesium such as lithium or potassium titanyl oxalate and nonmetallic titanyl oxalates such as ammonium titanyl oxalate. The titanyl oxalate may be anhydrous (n=0) or contain some water of hydration, i.e. n representing the amount of water of hydration. Preferred are H, Li, Na, K, Ca, Cs and ammonium.
- CARBOXYLIC ACID OR SALT:
- Examples of a catalyst enhancer for the titanium oxalate catalysts are a carboxylic acid containing 1 to 26 carbon atoms or its corresponding carboxylic acid salt having an anion selected from the group consisting of Li, Na, K, Rb Cs, Be, Mg, Ca, Sr, Ba and ammonium. As used herein, “carboxylic acid” includes dicarboxylic acid. Examples of such carboxylic acids or salts are well known and include sodium acetate, sodium propionate, sodium citrate, sodium butyrate, sodium formate, sodium fumarate, malonic acid, potassium acetate, potassium benzoate, succinic acid, glutaric acid, adipic acid, maleic acid. Preferred are potassium acetate, potassium benzoate.
- Titanium Containing Catalysts:
- Examples of titanium containing compounds of the formula XmTiYo with X selected from the group consisting of: H, Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba and ammonium, m=0, 1, or 2, Y is a ligand of the formula CaHbOc, a=0 to 30, b=O to 60, and c=1 to 10; o=2, 3, 4, include: acetylacetonate (a=5, b=7, and c=2); i-propoxide (a=3, b=7, and c=l); butoxide (a=4, b=9, and c=1); bis(2,2,6,6,-tetramethy-3,5-heptanedionato), i.e. a=11, b=19, and c=2. Preferred are acetylacetonate, i-propoxide, bis(2,2,6,6,-tetramethy-3,5-heptanedionato).
- Oxalic Acid or Salt:
- Examples of a catalyst enhancer for said titanium containing compounds are oxalic acids or its corresponding Li, Na, K, Rb Cs, Be, Mg, Ca, Sr, Ba, or ammonium oxalic acid. Preferred are H, Li, Na, K, Ca, Cs, and ammonium.
- Antimony Containing Catalysts:
- Examples of antimony containing catalysts that can be added to the synergistic combination of enhanced titanium oxalate or titanium containing catalysts defined above are Sb2O3, Sb(CH3COO)3, and Sb2(OCH2CH2O)3.
- Germanium Containing Catalysts:
- Examples of germanium containing catalysts that can be added to the synergistic combination of enhanced titanium oxalate or titanium containing catalysts defined above are GeO2, Ge(OC2H5)4, Ge[OCH(CH3)2]4, Ge(OCH3)4. Preferred is GeO2.
- Enhanceable Antimony Containing Catalysts:
- Examples of antimony containing catalysts that can be enhanced with a carboxylic acid or salt or an oxalic acid or salt are Sb2O3, Sb(CH3COO)3, Sb2(OCH2CH2O)3.
- Cocatalyst:
- Cocatalysts that function in combination with the titanium containing catalyst and the enhancer include antimony triacetate, Sb(CH3COO)3, antimony glycoxide, Sb2(OCH2CH2O)3, antimony oxide. (Sb2O3).
- An effective amount for enhancing the catalytic activity of titanyl oxalate catalysts or a titanium containing catalyst is at least about 0.1 part of enhancer per part of titanyl oxalate catalyst. Preferred is from about 0.1 part to about 100 parts enhancer per part of catalyst based upon the total weight of titanium in the catalyst.
- When used in combination with an enhancer, a catalytically effective amount of titanium containing catalyst should be added to the polyester forming reactants, generally at least 0.1 part based upon the weight of titanium. Preferred is from about 1 part to about 40 parts per million of catalyst based on the weight titanium in the catalyst and the weight of the of polyester forming reactants.
- When used in combination with an enhancer, a catalytically effective amount of an antimony containing catalyst should be added to the polyester forming reactants. Preferred is from about 1 part to about 240 parts per million of catalyst based on the weight antimony in the catalyst and the weight of the of polyester forming reactants. For enhancing an antimony containing catalyst, an effective amount for of an enhancer for the catalytic activity of an antimony containing catalyst is at least about 0.1 part of enhancer per part of antimony containing catalyst based the weight of antimony in said antimony containing catalyst. Preferred is from about 0.1 part to about 80 parts enhancer per part of catalyst based upon the total weight of titanium in the catalyst.
- The preferred amount of a antimony or germanium containing catalyst for use in combination with the enhanced titanium oxalate or titanium containing catalyst described above is from about 0.1 parts to about 80 parts based upon the weight of titanium. Preferred is from 1 to 40 parts of antimony or germanium containing catalyst.
- The catalyst and enhancer mixtures of the present invention are used to make polyester typically by first dissolving them in a solvent that is compatible with polyester forming reactants, or preferable in one of the reactants itself, such as ethylene glycol.
- The synergistic performance of the catalyst enhancer in combination with one or more catalysts for a polycondensation reaction for the production of PET resin is shown by the following examples.
- In a polyester polycondensation reaction, acetaldehyde (AA) is an undesirable polymerization by-product. Polymerization rate is measured as rate at which intrinsic viscosity (IV) increases during reaction. Intrinsic viscosity change is an indication of the degree of polymerization that has occurred during the reaction.
- Catalyst evaluation was performed with a {fraction (3/16)} stainless steel, 2 L reactor, fitted with a ball valve at the bottom of the reactor. The vessel was equipped with 3 inlet ports, one outlet port, one thermowell port and one pressure transducer port, and was vertically stirred by an electric motor with amperage monitoring. The laboratory experimental were all conducted on a 4.0 mole scale, using as polyester forming reactants, BHET and a normal bottle resin autoclave recipe. The experimental catalysts were added at the time of BHET charging.
- Bis(2-hydroxyethyl)terephthalate (BHET) and catalyst were added to the reactor and the contents blanketed with nitrogen. The mixtures were heated under reduced pressure with constant stirring. The ethylene glycol (EG) produced during the polymerization was removed and trapped. The polymerization was at 280° C. , under the vacuum of typically around 1 torr. The reaction was terminated when the stirrer torque reached a level, indicated by amperage to the stirrer motor, typical for a polymer of IV ˜0.6. The molten state polymer under nitrogen (containing less than 2 ppm of oxygen) blanket was discharged from the bottom ball valve and quenched into a bucket filled with cold water. ¼″ diameter and {fraction (1/16)}″ thick pellets (for color measurement) were made by filling the molten polymer in a press molder and chilled immediately in cold water.
- The solution intrinsic viscosity (IV) was measured by following the ASTM D 4603 method. Acetaldehyde (AA) was measured at 150° C. using gas chromatography (GC) equipped with a headspace analyzer. The brightness (L*) and yellowness (b*) were determined by the Hunter Lab's instrument and method.
- Twenty-seven examples were performed using the above procedure and various catalysts and catalyst enhancer amounts.
- Example A catalyst−180 ppm potassium oxalate−reaction time=124 mins.
- Example B catalyst−2 ppm titanium from potassium titanyl oxalate−reaction time=118 mins.
- Example C catalyst−6 ppm titanium potassium titanyl oxalate−reaction time=71 mins.
- Example D catalyst−25 ppm antimony from antimony (III) oxide−reaction time=122 mins.
- Example 1 catalyst−2 ppm titanium from potassium titanyl oxalate+90 ppm potassium oxalate−reaction time=111 mins.
- Example 2 catalyst−90 ppm potassium oxalate+25 ppm antimony from antimony (III) oxide−reaction time=120 mins.
- Example 3 catalyst−180 ppm potassium oxalate+50 ppm antimony from antimony (III) oxide−reaction time=130 mins.
- Example 4 catalyst−90 ppm potassium oxalate+100 ppm antimony from antimony (III) oxide−reaction time=112 mins.
- Example 5 catalyst−2 ppm titanium from potassium titanyl oxalate+90 ppm potassium oxalate+25 ppm antimony from antimony (III) oxide−reaction time=105 mins.
- Example E catalyst−240 ppm antimony from antimony (III) oxide−reaction time=90 mins.
- Example F catalyst−240 ppm antimony from antimony (III) oxide−reaction time=100 mins.
- Example 6 catalyst−2 ppm titanium from potassium titanyl oxalate+90 ppm potassium oxalate+25 ppm antimony from antimony (III) oxide−reaction time=73 mins.
- Example 7 catalyst−2 ppm titanium from potassium titanyl oxalate+90 ppm ammonium oxalate+25 ppm antimony from antimony (III) oxide−reaction time=78 mins.
- Example 8 catalyst−2 ppm titanium from ammonium titanyl oxalate+90 ppm potassium oxalate+25 ppm antimony from antimony (III) oxide−reaction time =79 mins.
- Example 9 catalyst−2 ppm titanium from ammonium titanyl oxalate+90 ppm ammonium oxalate+25 ppm antimony from antimony (III) oxide−reaction time=77 mins.
- Example 10 catalyst−2 ppm titanium from potassium titanyl oxalate+90 ppm potassium acetate+25 ppm antimony from antimony (III) oxide−reaction time=81 mins.
- Example 11 catalyst−2 ppm titanium from potassium titanyl oxalate+90 ppm potassium benzoate+25 ppm antimony from antimony (III) oxide−reaction time=72 mins.
- Example 12 catalyst−2 ppm titanium from bis(2,2,6,6-tetramethy-3,5-heptanedionato) oxotitanium+90 ppm potassium oxalate+25 ppm antimony from antimony (III) oxide−reaction time=72 mins.
- Example 13 catalyst−2 ppm titanium from di(i-propoxide)bis(2,2,6,6-tetramethyl-3,5-heptanedionato)titanium+90 ppm potassium oxalate+25 ppm antimony from antimony (III) oxide−reaction time=100 mins.
- Example 14 catalyst−2 ppm titanium from titanium oxide acetylacetonate+90 ppm potassium oxalate+25 ppm antimony from antimony (III) oxide−reaction time=114 mins.
- Example 15 catalyst−2 ppm titanium from potassium titanyl oxalate+90 ppm calcium oxalate+25 ppm antimony from antimony (III) oxide−reaction time=109 mins.
- Example 16 catalyst−2 ppm titanium from potassium titanyl oxalate+45 ppm oxalic acid+25 ppm antimony from antimony (III) oxide−reaction time=108 mins.
- Example 17 catalyst−2 ppm titanium from potassium titanyl oxalate+90 ppm sodium oxalate+25 ppm antimony from antimony (III) oxide−reaction time=108 mins.
- Example 18 catalyst−2 ppm titanium from lithium titanyl oxalate+50 ppm lithium oxalate+25 ppm antimony from antimony (III) oxide−reaction time=102 mins.
- Example G catalyst−60 ppm germanium from germanium oxide−reaction time=149.
- Example 19 catalyst−10 ppm germanium from germanium oxide+90 ppm potassium oxalate−reaction time=130 mins.
- Example 20 catalyst−2 ppm titanium from potassium titanyl oxalate+90 ppm potassium oxalate+7 ppm germanium from germanium oxide−reaction time=123 minutes.
-
AMOUNT POLY TIME AA EXAMPLE (mg) (mins.) IV (ppm) L* b* A 185.5 124 0.252 66.1 80.3 3.6 B 15.4 118 0.583 52.9 76.6 8.3 C 46.5 71 0.583 42.7 78.4 7.1 D 30.8 122 0.230 53.7 na na 1 106.4 111 0.591 52.6 76.6 7.7 2 125.9 120 0.461 24.4 68.3 5.8 3 246.8 130 0.536 46.1 80.4 6.5 4 215.6 112 0.587 38.3 77.6 6.0 5 137.0 105 0.596 42.4 81.4 5.3 B 298.9 90 0.593 34.9 69.9 5.3 F 296.7 100 0.586 34.3 70.0 5.9 6 137.2 73 0.514 26.8 79.6 3.4 7 137.6 78 0.520 32.4 77.3 4.7 8 133.6 79 0.519 33.8 80.4 4.1 9 134.2 77 0.542 19.4 78.6 5.6 10 137.1 81 0.538 22.0 78.3 5.3 11 208.9 72 0.534 18.2 75.5 6.1 12 140.7 72 0.540 19.9 66.4 5.2 13 145.5 100 0.590 45.6 65.7 5.2 14 134.3 114 0.589 42.9 71.9 6.8 15 137.9 109 0.597 42.9 78.3 6.2 16 92.7 108 0.607 39.7 76.2 6.9 17 137.5 108 0.600 43.0 80.8 5.0 18 95.7 102 0.583 37.7 80.4 5.9 G 89.8 149 0.586 43.9 79.9 5.1 19 106.3 130 0.494 41.3 64.9 3.7 20 117.9 123 0.583 42.5 74.1 8.4 - In comparing examples A, B, C and 1, 180 ppm potassium oxalate alone a polymer with a IV of 0.252 after 124 minutes. Using example B as a baseline, mer with a similar IV, 118 minutes were needed for 2 ppm titanium in potassium titanyl oxalate while only 71 minutes were needed for 6 ppm titanium as shown in example C. The addition of potassium oxalate to potassium titanyl oxalate enhanced the rate of polymerization as can be seen in example 1.
- In comparing examples A, D, 2, 3, 4 E and F, 180 ppm potassium oxalate alone produced a polymer with an IV of 0.252 after 124 minutes, 25 ppm of antimony in antimony oxide produced a polymer with an IV of 0.230 after 122 minutes. It is shown in examples 2, 3, and 4 that the addition of potassium oxalate to antimony enhanced the polymerization rate, reduced the amount of acetaldehyde, and also increased the brightness as compared to examples E and F.
- In comparing examples B and 5, using the combination of potassium titanyl oxalate, potassium oxalate, and antimony oxide, the polymerization rate was faster, the acetaldehyde concentration was lower, the resulting polymer was more brighter and less yellow.
- In comparing examples 5, E and F, the three component catalyst produced more brighter and less yellow polymer than antimony oxide. It is conceivable that the rate for three components can be further enhanced and the amount of acetaldehyde in the resulting polymer can be further reduced by adjusting the composition of the three components.
- In comparing examples 6 to 9, replacing potassium with ammonium in three components catalyst reduced the polymerization rate slightly. The resulting polymer by ammonium containing catalyst was slightly more yellow.
- In comparing examples 5, 6, 10 to 14, different ligands such as oxalate, acetate, benzoate, bis 2,2,6,6,-tetramethy-3,5-heptanedionate, i-propoxidate, acetylacetonate have been used. The catalysts containing these ligands polymerized BHET in a comparable rate with oxalate containing catalyst. However, the polymers using catalyst containing ligands rather than oxalate were less bright and more yellow. Therefore, the oxalate embodiment of the present invention is preferred over the ligand containing embodiment of the invention.
- In comparing examples 5, 15 to 18, although catalysts containing H, Li, Na, K, and Ca can polymerize BHET in a similar rate, Li containing catalyst produced the least amount of acetaldehyde in the resulting polymer and are therefore preferred.
- In comparing examples G, 19 and 20, the germanium catalyst can be enhanced by potassium oxalate.
Claims (30)
Priority Applications (17)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/895,990 US6372879B1 (en) | 2000-01-07 | 2001-06-29 | Polyester polycondensation with catalyst and a catalyst enhancer |
EG20020037A EG23090A (en) | 2001-06-29 | 2002-01-14 | Polyester polycondensation with catalyst and ctalyst enhancer |
RU2002100706/04A RU2277969C2 (en) | 2001-06-29 | 2002-01-16 | Polycondensation with utilization of the catalytic agent and the promoter of the catalytic agent for production of polyester |
ARP020100164A AR032252A1 (en) | 2001-06-29 | 2002-01-17 | POLYCHONDENSATION OF POLYESTER WITH CATALYST AND A CATALYTIC IMPROVER. |
TW91100761A TW574251B (en) | 2001-06-29 | 2002-01-18 | Polyester polycondensation with catalyst and a catalyst enhancer |
CNB021023859A CN1223624C (en) | 2001-06-29 | 2002-01-21 | Polyester polycondensation reaction using catalyst and catalytic synergist |
CA002368798A CA2368798A1 (en) | 2001-06-29 | 2002-01-22 | Polyester polycondensation with catalyst and catalyst enhancer |
MYPI20020250A MY127344A (en) | 2001-06-29 | 2002-01-23 | Polyester polycondensation with catalyst and a catalyst enhancer. |
AU13564/02A AU784542B2 (en) | 2001-06-29 | 2002-01-24 | Polyester polycondensation with catalyst and catalyst enhancer |
KR1020020004505A KR100848480B1 (en) | 2001-06-29 | 2002-01-25 | A catalyst combination, a process of producing a polyester using the combination and the polyester produced by the process |
PT02250584T PT1270641E (en) | 2001-06-29 | 2002-01-29 | Polyester polycondensation with catalyst and a catalyst enhancer |
DE60214285T DE60214285T2 (en) | 2001-06-29 | 2002-01-29 | Production of polyesters by polycondensation with a catalyst and a catalytic effect compound |
ES02250584T ES2269608T3 (en) | 2001-06-29 | 2002-01-29 | POLYCHONDENSATION OF POLYESTERS WITH CATALYST AND A CATALYTIC POTENTIATOR. |
EP02250584A EP1270641B1 (en) | 2001-06-29 | 2002-01-29 | Polyester polycondensation with catalyst and a catalyst enhancer |
BR0200448-8A BR0200448A (en) | 2001-06-29 | 2002-02-08 | Combination of catalysts, catalyst, polyester production process, and polyester |
MXPA02001767A MXPA02001767A (en) | 2001-06-29 | 2002-02-19 | Polyester polycondensation with catalyst and a catalyst enhancer. |
JP2002051208A JP4280450B2 (en) | 2001-06-29 | 2002-02-27 | Polyester polycondensation with catalyst and catalyst improver |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US17500600P | 2000-01-07 | 2000-01-07 | |
US09/747,115 US6258925B1 (en) | 2000-01-07 | 2000-12-22 | Polyester polycondensation with titanyl oxalate catalyst and a catalyst enhancer |
US09/895,990 US6372879B1 (en) | 2000-01-07 | 2001-06-29 | Polyester polycondensation with catalyst and a catalyst enhancer |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/747,115 Continuation-In-Part US6258925B1 (en) | 2000-01-07 | 2000-12-22 | Polyester polycondensation with titanyl oxalate catalyst and a catalyst enhancer |
Publications (2)
Publication Number | Publication Date |
---|---|
US20020032300A1 true US20020032300A1 (en) | 2002-03-14 |
US6372879B1 US6372879B1 (en) | 2002-04-16 |
Family
ID=25405424
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/895,990 Expired - Fee Related US6372879B1 (en) | 2000-01-07 | 2001-06-29 | Polyester polycondensation with catalyst and a catalyst enhancer |
Country Status (17)
Country | Link |
---|---|
US (1) | US6372879B1 (en) |
EP (1) | EP1270641B1 (en) |
JP (1) | JP4280450B2 (en) |
KR (1) | KR100848480B1 (en) |
CN (1) | CN1223624C (en) |
AR (1) | AR032252A1 (en) |
AU (1) | AU784542B2 (en) |
BR (1) | BR0200448A (en) |
CA (1) | CA2368798A1 (en) |
DE (1) | DE60214285T2 (en) |
EG (1) | EG23090A (en) |
ES (1) | ES2269608T3 (en) |
MX (1) | MXPA02001767A (en) |
MY (1) | MY127344A (en) |
PT (1) | PT1270641E (en) |
RU (1) | RU2277969C2 (en) |
TW (1) | TW574251B (en) |
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6762275B1 (en) | 2003-05-27 | 2004-07-13 | The Coca-Cola Company | Method to decrease the acetaldehyde content of melt-processed polyesters |
US20050080225A1 (en) * | 2001-11-30 | 2005-04-14 | Brigitta Otto | Method and device for producing highly condensed polyesters in the solid phase |
US20050187374A1 (en) * | 2004-02-20 | 2005-08-25 | Bin Chen | Polyester synthesis with enhanced titanium catalyst composition |
WO2005085318A1 (en) * | 2004-03-04 | 2005-09-15 | Zimmer Ag | Method for producing highly condensed solid-phase polyesters |
US7041350B1 (en) | 2002-08-30 | 2006-05-09 | The Coca-Cola Company | Polyester composition and articles with reduced acetaldehyde content and method using hydrogenation catalyst |
US20060189783A1 (en) * | 2003-01-23 | 2006-08-24 | Stefan Deiss | Method for adding raw materials during the production of polyesters or copolyesters |
US20060287471A1 (en) * | 2005-06-16 | 2006-12-21 | Schreiber Benjamin R | Accelerated acetaldehyde testing of polymers |
US20060287472A1 (en) * | 2005-06-16 | 2006-12-21 | Jernigan Mary T | High intrinsic viscosity melt phase polyester polymers with acceptable acetaldehyde generation rates |
US20070066794A1 (en) * | 2005-09-16 | 2007-03-22 | Jernigan Mary T | Phosphorus containing compounds for reducing acetaldehyde in polyesters polymers |
US20070066792A1 (en) * | 2005-09-16 | 2007-03-22 | Colhoun Frederick L | Late addition to effect compositional modifications in condensation polymers |
US20070066720A1 (en) * | 2005-09-16 | 2007-03-22 | Kenrick Lyle Venett | Method for addition of additives into a polymer melt |
US20070219341A1 (en) * | 2006-03-16 | 2007-09-20 | Lurgi Zimmer Gmbh | Method and device for the crystallization of polyester material |
US20080027207A1 (en) * | 2006-07-28 | 2008-01-31 | Jason Christopher Jenkins | Non-precipitating alkali/alkaline earth metal and aluminum compositions made with mono-ol ether solvents |
US20080027206A1 (en) * | 2006-07-28 | 2008-01-31 | Jason Christopher Jenkins | Multiple feeds of catalyst metals to a polyester production process |
US20080027208A1 (en) * | 2006-07-28 | 2008-01-31 | Donna Rice Quillen | Non-precipitating alkali/alkaline earth metal and aluminum solutions made with polyhydroxyl ether solvents |
US20080027209A1 (en) * | 2006-07-28 | 2008-01-31 | Alan Wayne White | Non-precipitating alkali/alkaline earth metal and aluminum compositions made with organic hydroxyacids |
US20080139727A1 (en) * | 2006-12-08 | 2008-06-12 | Jason Christopher Jenkins | Non-precipitating alkali/alkaline earth metal and aluminum solutions made with diols having at least two primary hydroxyl groups |
US20080293912A1 (en) * | 2007-05-23 | 2008-11-27 | Mary Therese Jernigan | High molecular weight polyester polymers with reduced acetaldehyde |
US7932345B2 (en) | 2005-09-16 | 2011-04-26 | Grupo Petrotemex, S.A. De C.V. | Aluminum containing polyester polymers having low acetaldehyde generation rates |
WO2012136606A1 (en) * | 2011-04-05 | 2012-10-11 | Basf Se | Photo-latent titanium-oxo-chelate catalysts |
US8431202B2 (en) | 2005-09-16 | 2013-04-30 | Grupo Petrotemex, S.A. De C.V. | Aluminum/alkaline or alkali/titanium containing polyesters having improved reheat, color and clarity |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE60019638T2 (en) * | 1999-12-10 | 2005-09-22 | Equipolymers Gmbh | CATALYST SYSTEMS FOR POLYCONDENSATION REACTIONS |
WO2004014982A2 (en) * | 2002-05-09 | 2004-02-19 | Equipolymers Gmbh | Catalyst systems for polycondensation reactions |
US6953768B2 (en) * | 2002-11-26 | 2005-10-11 | Teck Cominco Metals Ltd. | Multi-component catalyst system for the polycondensation manufacture of polyesters |
EP1535946A1 (en) * | 2003-11-28 | 2005-06-01 | Futura Polymers | A process for the preparation of polyethylene terephthalate (PET) |
TW201100460A (en) | 2009-03-18 | 2011-01-01 | Saudi Basic Ind Corp | Process for making thermoplastic polyesters |
KR101385721B1 (en) | 2012-04-13 | 2014-04-15 | 롯데케미칼 주식회사 | Complex metal oxide, and method for preparing polyesters using the same |
EP3448908A1 (en) | 2016-04-28 | 2019-03-06 | SABIC Global Technologies B.V. | Methods of forming dynamic cross-linked polymer compositions using functional monomeric chain extenders under batch process |
US20190119455A1 (en) | 2016-04-28 | 2019-04-25 | Sabic Global Technologies B.V. | Methods of forming dynamic cross-linked polymer compositions using functional, polymeric chain extenders under batch process |
WO2018055603A1 (en) | 2016-09-26 | 2018-03-29 | Sabic Global Technologies B.V. | Networking flame retardant dynamic cross-linked networks |
EP3515977A1 (en) | 2016-09-26 | 2019-07-31 | SABIC Global Technologies B.V. | Dynamic cross-linked networks comprising non-networking flame retardants |
WO2018093853A1 (en) | 2016-11-15 | 2018-05-24 | Sabic Global Technologies B.V. | Methods of forming dynamic cross-linked pollymer compositions using functional chain extenders under batch process |
US20190276590A1 (en) | 2016-11-15 | 2019-09-12 | Sabic Global Technologies B.V. | Methods of forming dynamic cross-linked polymer compositions using functional chain extenders under continuous process |
EP3548540A1 (en) | 2016-11-30 | 2019-10-09 | SABIC Global Technologies B.V. | Improvement of impact properties of dynamically cross-linked networks by using reactive impact modifiers |
TWI596135B (en) * | 2016-12-28 | 2017-08-21 | Far Eastern New Century Corp | Preparation of catalyst, catalyst obtained and and the preparation of polyester applications |
CN109734889B (en) * | 2018-12-27 | 2021-01-05 | 江苏恒力化纤股份有限公司 | Sb in polyester synthesis process2O3Adding method of (1) |
Family Cites Families (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4213030Y1 (en) | 1964-04-01 | 1967-07-24 | ||
JPS5323876B2 (en) | 1973-03-22 | 1978-07-17 | ||
US3907754A (en) | 1974-06-19 | 1975-09-23 | Eastman Kodak Co | Process and catalyst-inhibitor system for preparing synthetic linear polyester |
JPS5826749B2 (en) | 1975-12-27 | 1983-06-04 | 東洋紡績株式会社 | Method for producing N-hydroxyalkyl trimellitic acid imide |
US4238593B1 (en) | 1979-06-12 | 1994-03-22 | Goodyear Tire & Rubber | Method for production of a high molecular weight polyester prepared from a prepolymer polyester having an optional carboxyl content |
JPS5853919A (en) * | 1981-09-25 | 1983-03-30 | Toyobo Co Ltd | Preparation of polyester containing internal particle |
US4356299A (en) | 1982-02-04 | 1982-10-26 | Rohm And Haas Company | Catalyst system for a polyethylene terephthalate polycondensation |
US4780527A (en) | 1987-05-06 | 1988-10-25 | Industrial Technology Research Institute | Preparation of polyesters from terephthalic acid |
DE4137842A1 (en) | 1991-11-16 | 1993-05-19 | Zimmer Ag | METHOD FOR CONTINUOUS POLYCONDENSATION OF TEREPHTHALIC ACID AND 1,4-BIS (HYDROXYMETHYL) -CYCLOHEXANE |
JPH06128464A (en) | 1992-10-20 | 1994-05-10 | Kuraray Co Ltd | Polybutylene terephthalate resin molded product |
US5714570A (en) | 1993-12-09 | 1998-02-03 | Korea Institute Of Science And Technology | Method for the preparation of polyester by use of composite catalyst |
DE4430634A1 (en) | 1994-08-29 | 1996-03-07 | Hoechst Ag | Process for the production of thermally stable, color-neutral, antimony-free polyester and the products which can be produced thereafter |
CN1188446C (en) | 1996-06-11 | 2005-02-09 | 美国杜邦泰津胶片合伙人有限公司 | Polyester article |
GB9612161D0 (en) | 1996-06-11 | 1996-08-14 | Tioxide Specialties Ltd | Esterification process |
US5902873A (en) | 1997-10-17 | 1999-05-11 | General Electric Company | Catalyst composition for the preparation of polyesters, and related processes |
GB9725419D0 (en) | 1997-12-02 | 1998-01-28 | Tioxide Specialties Ltd | Esterification catalysts |
US5874517A (en) | 1997-12-23 | 1999-02-23 | Hoechst Celanese Corporation | Method to reduce regenerated acetaldehyde in pet resin |
US6066714A (en) | 1998-04-17 | 2000-05-23 | E. I. Du Pont De Nemours And Company | Titanium-containing catalyst composition and processes therefor and therewith |
US5981690A (en) | 1998-04-17 | 1999-11-09 | E. I. Du Pont De Nemours And Company | Poly(alkylene arylates) having improved optical properties |
US6376642B1 (en) * | 1998-07-07 | 2002-04-23 | Atofina Chemicals, Inc. | Polyester polycondensation with lithium titanyl oxalate catalyst |
IT1304797B1 (en) | 1998-12-23 | 2001-03-29 | Sinco Ricerche Spa | POLYESTER RESIN PREPARATION PROCEDURE (MG33). |
US6133404A (en) | 1998-12-26 | 2000-10-17 | National Institute Of Technology And Quality | Polyester and formation process thereof |
US6034203A (en) | 1999-04-08 | 2000-03-07 | E. I. Du Pont De Nemours And Company | Catalysis with titanium oxides |
GB9912210D0 (en) | 1999-05-25 | 1999-07-28 | Acma Ltd | Esterification catalysts |
US6166170A (en) | 1999-12-02 | 2000-12-26 | E. I. Du Pont De Nemours And Company | Esterification catalysts and processes therefor and therewith |
US6258925B1 (en) * | 2000-01-07 | 2001-07-10 | Atofina Chemicals, Inc. | Polyester polycondensation with titanyl oxalate catalyst and a catalyst enhancer |
AU771037B2 (en) * | 2000-01-07 | 2004-03-11 | Atofina Chemicals, Inc. | Polyester polycondensation with titanyl oxalate catalyst and a catalyst enhancer |
-
2001
- 2001-06-29 US US09/895,990 patent/US6372879B1/en not_active Expired - Fee Related
-
2002
- 2002-01-14 EG EG20020037A patent/EG23090A/en active
- 2002-01-16 RU RU2002100706/04A patent/RU2277969C2/en not_active IP Right Cessation
- 2002-01-17 AR ARP020100164A patent/AR032252A1/en active IP Right Grant
- 2002-01-18 TW TW91100761A patent/TW574251B/en not_active IP Right Cessation
- 2002-01-21 CN CNB021023859A patent/CN1223624C/en not_active Expired - Fee Related
- 2002-01-22 CA CA002368798A patent/CA2368798A1/en not_active Abandoned
- 2002-01-23 MY MYPI20020250A patent/MY127344A/en unknown
- 2002-01-24 AU AU13564/02A patent/AU784542B2/en not_active Ceased
- 2002-01-25 KR KR1020020004505A patent/KR100848480B1/en not_active IP Right Cessation
- 2002-01-29 PT PT02250584T patent/PT1270641E/en unknown
- 2002-01-29 EP EP02250584A patent/EP1270641B1/en not_active Expired - Lifetime
- 2002-01-29 DE DE60214285T patent/DE60214285T2/en not_active Expired - Fee Related
- 2002-01-29 ES ES02250584T patent/ES2269608T3/en not_active Expired - Lifetime
- 2002-02-08 BR BR0200448-8A patent/BR0200448A/en not_active Application Discontinuation
- 2002-02-19 MX MXPA02001767A patent/MXPA02001767A/en active IP Right Grant
- 2002-02-27 JP JP2002051208A patent/JP4280450B2/en not_active Expired - Fee Related
Cited By (44)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050080225A1 (en) * | 2001-11-30 | 2005-04-14 | Brigitta Otto | Method and device for producing highly condensed polyesters in the solid phase |
US7262263B2 (en) | 2001-11-30 | 2007-08-28 | Brigitta Otto | Method and apparatus for producing solid-state polycondensed polyesters |
US7041350B1 (en) | 2002-08-30 | 2006-05-09 | The Coca-Cola Company | Polyester composition and articles with reduced acetaldehyde content and method using hydrogenation catalyst |
US20060189783A1 (en) * | 2003-01-23 | 2006-08-24 | Stefan Deiss | Method for adding raw materials during the production of polyesters or copolyesters |
US6762275B1 (en) | 2003-05-27 | 2004-07-13 | The Coca-Cola Company | Method to decrease the acetaldehyde content of melt-processed polyesters |
US20050187374A1 (en) * | 2004-02-20 | 2005-08-25 | Bin Chen | Polyester synthesis with enhanced titanium catalyst composition |
US7977448B2 (en) | 2004-03-04 | 2011-07-12 | Lurgi Zimmer Gmbh | Method for producing highly condensed solid-phase polyesters |
WO2005085318A1 (en) * | 2004-03-04 | 2005-09-15 | Zimmer Ag | Method for producing highly condensed solid-phase polyesters |
EA011825B1 (en) * | 2004-03-04 | 2009-06-30 | Лурджи Циммер Гмбх | Method for producing highly-condensed solid-phase polyesters and polyester shaped bodies produced therefrom |
US20070179269A1 (en) * | 2004-03-04 | 2007-08-02 | Brigitta Otto | Method for producing highly condensed solid-phase polyesters |
US20060287471A1 (en) * | 2005-06-16 | 2006-12-21 | Schreiber Benjamin R | Accelerated acetaldehyde testing of polymers |
US8557950B2 (en) | 2005-06-16 | 2013-10-15 | Grupo Petrotemex, S.A. De C.V. | High intrinsic viscosity melt phase polyester polymers with acceptable acetaldehyde generation rates |
US8987408B2 (en) | 2005-06-16 | 2015-03-24 | Grupo Petrotemex, S.A. De C.V. | High intrinsic viscosity melt phase polyester polymers with acceptable acetaldehyde generation rates |
US20060287472A1 (en) * | 2005-06-16 | 2006-12-21 | Jernigan Mary T | High intrinsic viscosity melt phase polyester polymers with acceptable acetaldehyde generation rates |
US20100048783A1 (en) * | 2005-09-16 | 2010-02-25 | Eastman Chemical Company | Phosphorus containing compounds for reducing acetaldehyde in polyesters polymers |
US7799891B2 (en) | 2005-09-16 | 2010-09-21 | Eastman Chemical Company | Phosphorus containing compounds for reducing acetaldehyde in polyesters polymers |
US9267007B2 (en) | 2005-09-16 | 2016-02-23 | Grupo Petrotemex, S.A. De C.V. | Method for addition of additives into a polymer melt |
US20070066794A1 (en) * | 2005-09-16 | 2007-03-22 | Jernigan Mary T | Phosphorus containing compounds for reducing acetaldehyde in polyesters polymers |
US8791187B2 (en) | 2005-09-16 | 2014-07-29 | Grupo Petrotemex, S.A. De C.V. | Aluminum/alkyline or alkali/titanium containing polyesters having improved reheat, color and clarity |
US20070066792A1 (en) * | 2005-09-16 | 2007-03-22 | Colhoun Frederick L | Late addition to effect compositional modifications in condensation polymers |
US8431202B2 (en) | 2005-09-16 | 2013-04-30 | Grupo Petrotemex, S.A. De C.V. | Aluminum/alkaline or alkali/titanium containing polyesters having improved reheat, color and clarity |
US7655746B2 (en) | 2005-09-16 | 2010-02-02 | Eastman Chemical Company | Phosphorus containing compounds for reducing acetaldehyde in polyesters polymers |
US20070066720A1 (en) * | 2005-09-16 | 2007-03-22 | Kenrick Lyle Venett | Method for addition of additives into a polymer melt |
US7932345B2 (en) | 2005-09-16 | 2011-04-26 | Grupo Petrotemex, S.A. De C.V. | Aluminum containing polyester polymers having low acetaldehyde generation rates |
US7838596B2 (en) | 2005-09-16 | 2010-11-23 | Eastman Chemical Company | Late addition to effect compositional modifications in condensation polymers |
US20070219341A1 (en) * | 2006-03-16 | 2007-09-20 | Lurgi Zimmer Gmbh | Method and device for the crystallization of polyester material |
US8063176B2 (en) | 2006-03-16 | 2011-11-22 | Lurgi Zimmer Gmbh | Method and device for the crystallization of polyester material |
US7745368B2 (en) * | 2006-07-28 | 2010-06-29 | Eastman Chemical Company | Non-precipitating alkali/alkaline earth metal and aluminum compositions made with organic hydroxyacids |
US7709593B2 (en) | 2006-07-28 | 2010-05-04 | Eastman Chemical Company | Multiple feeds of catalyst metals to a polyester production process |
US7709595B2 (en) | 2006-07-28 | 2010-05-04 | Eastman Chemical Company | Non-precipitating alkali/alkaline earth metal and aluminum solutions made with polyhydroxyl ether solvents |
US20080027206A1 (en) * | 2006-07-28 | 2008-01-31 | Jason Christopher Jenkins | Multiple feeds of catalyst metals to a polyester production process |
US20080027208A1 (en) * | 2006-07-28 | 2008-01-31 | Donna Rice Quillen | Non-precipitating alkali/alkaline earth metal and aluminum solutions made with polyhydroxyl ether solvents |
US20080027209A1 (en) * | 2006-07-28 | 2008-01-31 | Alan Wayne White | Non-precipitating alkali/alkaline earth metal and aluminum compositions made with organic hydroxyacids |
US20080027207A1 (en) * | 2006-07-28 | 2008-01-31 | Jason Christopher Jenkins | Non-precipitating alkali/alkaline earth metal and aluminum compositions made with mono-ol ether solvents |
US20080139727A1 (en) * | 2006-12-08 | 2008-06-12 | Jason Christopher Jenkins | Non-precipitating alkali/alkaline earth metal and aluminum solutions made with diols having at least two primary hydroxyl groups |
US8563677B2 (en) | 2006-12-08 | 2013-10-22 | Grupo Petrotemex, S.A. De C.V. | Non-precipitating alkali/alkaline earth metal and aluminum solutions made with diols having at least two primary hydroxyl groups |
US8748559B2 (en) | 2007-05-23 | 2014-06-10 | Grupo Petrotemex, S.A. De C.V. | High molecular weight polyester polymers with reduced acetaldehyde |
US20080293912A1 (en) * | 2007-05-23 | 2008-11-27 | Mary Therese Jernigan | High molecular weight polyester polymers with reduced acetaldehyde |
US8207289B2 (en) | 2007-05-23 | 2012-06-26 | Grupo Petrotemex, S.A. De C.V. | High molecular weight polyester polymers with reduced acetaldehyde |
CN103596684A (en) * | 2011-04-05 | 2014-02-19 | 巴斯夫欧洲公司 | Photo-latent titanium-oxo-chelate catalysts |
WO2012136606A1 (en) * | 2011-04-05 | 2012-10-11 | Basf Se | Photo-latent titanium-oxo-chelate catalysts |
RU2610090C2 (en) * | 2011-04-05 | 2017-02-07 | Басф Се | Photo-latent titanium-oxo-chelate catalysts |
US9809727B2 (en) | 2011-04-05 | 2017-11-07 | Basf Se | Photo-latent titanium-oxo-chelate catalysts |
RU2610090C9 (en) * | 2011-04-05 | 2018-04-26 | Басф Се | Photo-latent titanium-oxo-chelate catalysts |
Also Published As
Publication number | Publication date |
---|---|
MXPA02001767A (en) | 2003-01-23 |
CN1393482A (en) | 2003-01-29 |
DE60214285D1 (en) | 2006-10-12 |
JP2003026789A (en) | 2003-01-29 |
MY127344A (en) | 2006-11-30 |
PT1270641E (en) | 2006-12-29 |
TW574251B (en) | 2004-02-01 |
KR20030003661A (en) | 2003-01-10 |
EP1270641A3 (en) | 2003-04-23 |
AU1356402A (en) | 2003-01-02 |
CA2368798A1 (en) | 2002-12-29 |
EP1270641A2 (en) | 2003-01-02 |
AR032252A1 (en) | 2003-10-29 |
ES2269608T3 (en) | 2007-04-01 |
KR100848480B1 (en) | 2008-07-28 |
US6372879B1 (en) | 2002-04-16 |
JP4280450B2 (en) | 2009-06-17 |
RU2277969C2 (en) | 2006-06-20 |
AU784542B2 (en) | 2006-04-27 |
CN1223624C (en) | 2005-10-19 |
BR0200448A (en) | 2003-04-29 |
DE60214285T2 (en) | 2007-09-20 |
EG23090A (en) | 2004-03-31 |
EP1270641B1 (en) | 2006-08-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6372879B1 (en) | Polyester polycondensation with catalyst and a catalyst enhancer | |
KR100840089B1 (en) | Metal-containing composition and process therewith | |
KR20010052255A (en) | Catalytic Composition Comprising a Titanium Compound, an Amine and a Phosphorus Compound, Preparation and Use Thereof | |
EP0909774B1 (en) | Catalyst composition for the preparation of polyesters and related processes | |
US6043335A (en) | Phosphate-containing catalyst composition for the preparation of polyesters, and related processes | |
WO2005082527A1 (en) | Polyester synthesis with enhanced titanium catalyst composition | |
KR100758517B1 (en) | Polyester polycondensation with titanyl oxalate catalyst and a catalyst enhancer | |
CN1297374A (en) | Catalyst composition comprising titanium compound, phosphorus compound and solubility promoter, preparation and use thereof | |
EP1771247A1 (en) | Composition comprising titanium and aluminum and polyester production | |
EP1159330B1 (en) | Catalyst composition for the preparation of polyesters | |
US7709409B2 (en) | Mixed catalytic composition | |
AU771037B2 (en) | Polyester polycondensation with titanyl oxalate catalyst and a catalyst enhancer | |
WO2022258518A1 (en) | Titanium catalyst for the polyester manufacturing process | |
KR20010052254A (en) | Catalyst Composition Comprising a Titanium Compound, a Phosphorus Compound and a Solubility Promoter, Preparation and Use Thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: ATOFINA CHEMICALS, INC., PENNSYLVANIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:DOWLING, CONOR M.;CHEN, BIN;SESHADRI, SRI R.;REEL/FRAME:012193/0960;SIGNING DATES FROM 20010823 TO 20010824 |
|
RF | Reissue application filed |
Effective date: 20030224 |
|
AS | Assignment |
Owner name: ARKEMA INC., PENNSYLVANIA Free format text: CHANGE OF NAME;ASSIGNOR:ATOFINA CHEMICALS, INC.;REEL/FRAME:015394/0628 Effective date: 20041004 |
|
FPAY | Fee payment |
Year of fee payment: 4 |
|
REMI | Maintenance fee reminder mailed | ||
LAPS | Lapse for failure to pay maintenance fees | ||
STCH | Information on status: patent discontinuation |
Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362 |
|
FP | Lapsed due to failure to pay maintenance fee |
Effective date: 20100416 |