WO2007117028A1 - ポリエチレンテレフタレートの製造方法 - Google Patents
ポリエチレンテレフタレートの製造方法 Download PDFInfo
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- WO2007117028A1 WO2007117028A1 PCT/JP2007/058016 JP2007058016W WO2007117028A1 WO 2007117028 A1 WO2007117028 A1 WO 2007117028A1 JP 2007058016 W JP2007058016 W JP 2007058016W WO 2007117028 A1 WO2007117028 A1 WO 2007117028A1
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- Prior art keywords
- polyethylene terephthalate
- polycondensation
- solid phase
- esterification reaction
- polycondensed
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- 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
- C08G63/80—Solid-state polycondensation
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- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- 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
-
- 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
-
- 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
Definitions
- the present invention relates to a method for producing polyethylene terephthalate, which can obtain a molded article having a low content of acetaldehyde and a low content of cyclic trimer without causing deterioration of hue.
- Acetaldehyde may cause offensive odors and off-flavors, or may alter the flavor of the contents, and may adversely affect the use of polyethylene terephthalate molded products.
- Polyethylene terephthalate is widely used in the form of fibers, vinylomes, sheets, bottles, cups, or trays because of its excellent mechanical and chemical properties.
- Such polyethylene terephthalate can usually be produced from an aromatic dicarboxylic acid such as terephthalic acid and an aliphatic diol such as ethylene dallicol. Specifically, first, a low-order condensate (ester low polymer) is formed by an esterification reaction of an aromatic dicarboxylic acid and an aliphatic diol, and then this low-order condensate is removed in the presence of a polycondensation catalyst. Manufactured by a glycol reaction (melt polycondensation). If necessary, solid state polycondensation is further performed after melt polycondensation to further increase the molecular weight. '
- an antimony compound and a germanium compound have been conventionally used as a polycondensation catalyst.
- polyethylene and terephthalate produced using an antimony compound as a polycondensation catalyst were inferior to polyethylene terephthalate produced using a germanium compound as a polycondensation catalyst in terms of transparency and heat resistance.
- Polyethylene obtained especially for beverage bottle applications and food packaging materials It is also desired to reduce the acetonitrile content in terephthalate. 'Furthermore, antimony compounds have some health concerns.
- germanium compounds have no hygiene concerns, and polyethylene terephthalate molded products produced using germanium compounds as polycondensation catalysts have good transparency, content of acetoaldehyde and content of oligomers. There are few. However, since the germanium compound is expensive, there is a problem that the production cost of polyethylene terephthalate increases. In recent years, aluminum compounds have been proposed as polycondensation catalysts for polyethylene terephthalate. However, organoaluminum compounds are not as expensive as germanium compounds, but they are relatively expensive, and some water-soluble aluminum salts are known to be neurotoxic, leaving hygiene concerns.
- a titanium compound also has an action of promoting a polycondensation reaction of an ester, and titanium alkoxide, titanium tetrachloride, titanyl oxalate, or orthotitanic acid is known as a polycondensation catalyst.
- titanium alkoxide, titanium tetrachloride, titanyl oxalate, or orthotitanic acid is known as a polycondensation catalyst.
- the content of the acetoaldehyde in the polyethylene terephthalate chip and its molded product is lower than that of the polyethylene terephthalate obtained by using the germanium compound as the polycondensation catalyst.
- the oligomer content was high.
- the main component of the oligomer is a cyclic trimer of ethylene terephthalate, which is sometimes abbreviated as Cy-3.
- Oligomers present in polyethylene terephthalate chips or oligomers produced during polyethylene terephthalate molding adhere to and contaminate the rollers of drawing equipment and rollers of heat treatment equipment as white powder.
- the oligomer becomes a powdery foreign substance and contaminates the staining solution.
- film is formed, it is made of fiber.
- problems such as contamination of various equipment rollers and product defects such as so-called dropout on magnetic tape.
- it becomes white powder contaminates the molding die, or adheres to the surface of the molded product, so that a molded product with a normal appearance cannot be obtained.
- the oligomer generated during the stretching process and the heat process adheres to the mold and the like, and there is another problem that the transparency of the molded product is significantly impaired by the transfer.
- Patent Document 1 and Patent Document 2 propose a method for reducing the oligomer content by a solid phase polycondensation method in which polyethylene terephthalate is heat-treated in a high vacuum state below its melting point.
- Patent Document 3 proposes a method for reducing the oligomer content by a solid phase polycondensation method in which polyethylene terephthalate is heat-treated in an inert gas atmosphere at a temperature below the melting point.
- the oligomer content When the oligomer content is reduced by this method, it has the effect of reducing the amount of white powder generated for polyethylene terephthalate having a relatively high oligomer content in the polyethylene terephthalate. However, if the polyethylene terephthalate content in polyethylene terephthalate is relatively low, the amount of white powder generated may be increased if the amount of white powder generated cannot be reduced.
- Patent Document 4 states that by treating the polyethylene terephthalate after solid-phase polycondensation with water, the amount of acetate aldehyde and oligomer produced at the time of molding can be reduced.
- the polycondensation catalyst is an antimony compound other than a germanium compound, When it is a ruminium compound or a titanium compound, it has no effect.
- Patent Document 6 and Patent Document 7 propose a method of adding an alkali metal salt or an alkaline earth metal salt as a method for reducing the content of acetonitrile and / or oligomer in polyethylene terephthalate moldings.
- This method alone, the acetoaldehyde content in polyethylene terephthalate moldings is considerably higher than that of polyethylene terephthalate using a germanium compound as a catalyst.
- Patent Document 1 Japanese Patent Application Laid-Open No. Sho 4 8-10 10 4 6 2
- Patent Document 2 Japanese Patent Application Laid-Open No. 5 1-04 8 5 0 5
- Patent Document 3 Japanese Patent Laid-Open No. Sho 5 5-1 8 9 3 3 1
- Patent Document 4 Japanese Patent Laid-Open No. 3-4 7 8 30
- Patent Document 5 US Patent No. 5 0.1 7'6 80
- Patent Document 6 International Publication No. 0 5Z0 2 3 90 0 Pamphlet
- Patent Document 7 Japanese Patent Laid-Open No. 2 00 4-0 1 0 6 5 7
- Patent Document 8 International Publication No. 0 3/0 0 8 4 7 9 Pamphlet
- An object of the present invention is to provide a method for producing a polyethylene terephthalate that is suitable for solving the problems of the prior art as described above and for obtaining a molded article having a low content of alkyl aldehyde. is there. (Means for solving problems)
- An object of the present invention is to provide a polyethylene terephthalate having a good hue with a small amount of acetonitrile and a small amount of oligomer.
- the present inventors have intensively studied to solve the above-mentioned problems. Using specific compounds containing a titanium atom and a phosphorus atom, the conditions of the melt polycondensation are examined in detail, and the number of carboxyl ends and the intrinsic viscosity are determined. The present invention was completed by finding that the problem can be solved by obtaining a strictly controlled polyethylene terephthalate and subjecting it to solid phase polycondensation.
- an object of the present invention is a method for producing polyethylene terephthalate, in which a compound represented by the following general formula (I) is used as a polycondensation catalyst to perform melt polycondensation, and the intrinsic viscosity is 0.4 8 to 0 5 3 d L / g, a process to obtain molten polycondensed polyethylene terephthalate having a terminal carboxyl number of 14 to 2 2 mm o 1 / kg, and then the intrinsic viscosity of the molten polycondensed polyethylene terephthalate by solid phase polycondensation
- a method for producing polyethylene terephthalate including a step of obtaining a solid phase polycondensed polyethylene terephthalate from 0.70 to 0.86 d LZg.
- a metal salt containing at least one kind of atom selected from the group consisting of sodium, potassium and cesium in any step in the polyethylene terephthalate production process.
- the present invention is a method for producing polyethylene terephthalate under specific conditions using a titanium compound that is less expensive than a germanium compound and less hygienic as compared with an antimony compound and a aluminum compound as a polycondensation catalyst.
- a polyethylene terephthalate capable of producing a molded article having a low alkyl aldehyde content and a low oligomer content equivalent to polyethylene terephthalate using a germanium compound as a polycondensation catalyst. . (Best Mode for Carrying Out the Invention)
- the polyethylene terephthalate in the production method of the present invention is polyethylene terephthalate whose main repeating unit is an ethylene terephthalate unit.
- main means that the content is 80 mol% or more and 100 mol% or less in the repeating units constituting polyethylene terephthalate. Therefore, in the polyethylene terephthalate of the present invention, the remaining 0 to 20 mol% may be copolymerized with a copolymer component other than the ethylene terephthalate component.
- the other copolymerization components are unsubstituted or substituted isophthalic acid, naphthalene dicarboxylic acid norevonic acid, dipheny / resicanoreponic acid, dipheninore terdicarboxylic acid, diphenylsulephone dicarboxylic acid, diphenoxyethanedicarboxylic acid, succinic acid Acid, adipic acid, sebacic acid, zelaic acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid, trimellitic acid, pyromellitic acid, or their lower alkyl esters, their lower aryl esters or these Ester-forming derivatives of these acid halides, trimethylene glycol, 1,2 propanediol, tetramethylene glycol, neopentyl glycol, hexamethylene glycol, decane methylene glycol, dodecamethylene glycol Ko.
- Mono-ole, 1,4-cyclohexanedimethano Mono-ole, Diethylene glycolate, Triethylene glycolate, Tetraethylene glycolate, Polyethylene Lenguli Cornole, Dipropylene Glicone, Tripropylene Glycol, Tetrapropylene Glycol, Polypropylene Glycol, Di (Tetramethylene) Glycol, Tri (Tetramethylene) Glycol, Polytetramethylene Dalicol, Pentaerythritol, or Mention may be made of 2,2-bis (4-hydroxyhydroxy) propane.
- a compound represented by the following formula (I) it is necessary to use a compound represented by the following formula (I) as a polycondensation catalyst. Furthermore, it is preferable to use a polycondensation catalyst such that the titanium atom concentration is 1 to 50 ppm with respect to the polyethylene terephthalate obtained after solid phase polycondensation.
- the compound serving as the polycondensation catalyst can be produced, for example, by heating a titanium compound and a phosphorus compound using darcol as a solvent. In that case, the compound that becomes the polycondensation catalyst is obtained as a precipitate in the glycol.
- the two R i groups in general formula (I) are each independently an alkyl group derived from a titanium compound or an alkyl group derived from a phosphorus compound, and an alkyl group having 3 to 6 carbon atoms. Is preferred.
- Titanium compounds used in the production of the polycondensation catalyst include titanium tetroxide, titanium tetrisopropoxide, titanium tetrannormal hydroxide, titanium tetraethoxide, titanium tetramethoxide, titante traxacetyl cetate "" one complex, Titanium tetrakis (2,4 monohexanato) complex, titanium tetrakis (3,5 monoheptane diato) complex, titanium dimethoxybisacetylacetonate complex, Titanium jetoxy bisacetyl etherate complex, Titanium diisopropoxy bisacetyl etherate complex, Titanium dinormalpropoxy bisacetyl acetate toner complex, Titanium dibutoxy bisacetyl acetate toner complex, Titanium dihydroxy bisglycolate, Titanium dihydrate Mouth Kishibis lactate, Titanium dihydroxybis (2-Hydroxyp oral pionate), Titanium lactate, Titanium oc
- V compounds include monoethyl phosphate, monopropyl phosphate, monoptinorephosphate, monohexinorephosphate, monooctinorephosphate, monodecide. Mono-anoleyl phosphates or monophenyl phosphates such as norephosphate, monolaurinophosphate, monooleyl phosphate, or monotetradecyl phosphate are preferred. These phosphorus compounds may be used in a mixture. For example, a combination of a mixture of monoalkinophosphate and monophenolate phosphate can be preferably mentioned. In particular, it is particularly preferable that the ratio of monoalkyl phosphate is 90 mol% or more and 100 mol% or less.
- the glycols used as a solvent in the production of the polycondensation catalyst of the general formula (I) include ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol, and hexamethylene glycol. Or cyclohexanedimethanol.
- Dalicol used in the production of polycondensation catalyst is polyethylene polyethylene produced using the polycondensation catalyst. It is preferable to use the same darlicol as the glycol used as the raw material for the phthalate.
- the polycondensation catalyst used in the present invention is a method in which a titanium compound, a phosphorus compound, and a glycol are mixed and heated at the same time, or a solution of each of the titanium compound and the phosphorus compound is prepared, and then they are used. It can be produced by mixing and heating a glycol solution. Of these, the latter method is preferred.
- the reaction temperature for producing the polycondensation catalyst is carried out at room temperature, the reaction may not proceed sufficiently, or the reaction may take excessive time. Accordingly, the reaction is usually preferably carried out at a reaction temperature of 50 ° C. to 200 ° C., and the reaction time is preferably completed in 1 minute to 4 hours.
- the reaction temperature when ethylene darlicol is used as the daricol is preferably 50 ° C to 150 ° C, and the reaction temperature when hexamethylenedaricol is used is 100 ° C (:
- the reaction time when using these glycols is more preferably in the range of 30 minutes to 2 hours When the reaction temperature is too high or the reaction time is too long. This is not preferable because the produced polycondensation catalyst deteriorates.
- the molar ratio of the phosphorus atom to the titanium atom is 1.5 or more and less than 2.5. It is preferably 1.7 or more and less than 2.3.
- the molar ratio is less than 1.5, the physical properties of the polyethylene terephthalate may deteriorate due to the presence of a large amount of unreacted titanium compound.
- the molar ratio is 2.5 or more, the presence of a large amount of unreacted phosphorus compound may slow the polymerization rate of polyethylene terephthalate and may deteriorate the physical properties of polyethylene terephthalate.
- the liquid containing the polycondensation catalyst used in the present invention as a precipitate obtained by such an operation may be used as it is as a catalyst for producing polyethylene terephthalate without solid-liquid separation.
- centrifugation treatment Alternatively, after separating the precipitate and the solvent by filtration, the separated precipitate may be purified and used as a polycondensation catalyst.
- a specific purification method there can be mentioned a method of recrystallization using acetone, methyl alcohol, or a mixed solvent of methyl alcohol and water.
- the polycondensation catalyst used in the present invention can be easily separated from darcol using a filter, its chemical structure and titanium atom content in the polycondensation catalyst are analyzed by solid-state NMR and XMA metal analysis after separation. Can be analyzed. On the other hand, since the unreacted titanium compound and phosphorus compound are soluble in glycol, the unreacted rate can be determined by analyzing the titanium atom concentration or phosphorus atom concentration in the filtrate components.
- the polycondensation catalyst should be used so that the polyethylene atom terephthalate obtained after solid-phase polycondensation has a titanium atom concentration of 1 to 50 ppm. Is preferred. Further, it is preferably used as a polycondensation catalyst in an amount of 5 to 25 ppm in terms of titanium atom concentration in the finally obtained solid phase polycondensation polyethylene terephthalate, and used in an amount of 6 to 20 ppm. More preferably.
- a polycondensation catalyst in an amount in the range of 5 to 25 ppm when performing an operation of adding a compound containing at least one atom among sodium, potassium and cesium described later.
- the polycondensation catalyst is used in an amount of 50 ppm or more, the polymerization rate of liquid phase polycondensation or solid phase polycondensation may be too fast, and the polyethylene terephthalate may be strongly colored.
- the polycondensation catalyst is used at less than 1 ppm, the polymerization rate of liquid phase polycondensation or solid phase polycondensation may be too slow or the polycondensation reaction may not proceed at all.
- the metal atom other than the titanium atom is preferably 1 O ppm or less, more preferably 5 ppm or less in terms of metal atom concentration.
- the polycondensation catalyst may be present during the polycondensation reaction. For this reason, the addition of the polycondensation catalyst is performed in the melt polycondensation process, that is, the raw material slurry preparation process, It may be carried out in any of the esterification reaction step, liquid phase polycondensation step and other steps. Further, the entire amount of the polycondensation catalyst may be added to the reactor all at once, or may be added to the reactor in several batches.
- the polyethylene terephthalate production method of the present invention will be described in more detail for each step.
- polyethylene terephthalate in the present invention will be described in detail.
- polycondensation catalyst polyethylene terephthalate can be produced mainly by polycondensation of terephthalic acid or its ester-forming derivative and ethylene dalycol.
- an ester-forming derivative thereof can be used mainly using terephthalic acid.
- the ester-forming derivative represents a lower alkyl ester, a lower aryl ester or an acid halide.
- terephthalic acid or an ester-forming derivative thereof is 80 mol% or more and 10'0 mol% or less, preferably 90 mol% or more and LOO mol% with respect to 100 mol% of the aromatic dicarboxylic acid component.
- Ethylene glycol is used in an amount of 80 mol% or more and 100 mol% or less, preferably 90 mol% or more and 100 mol% or less with respect to 100 mol% of the aliphatic glycol component.
- Ethylene glycol is used in an amount of 80 mol% or more and 100 mol% or less, preferably 90 mol% or more and 100 mol% or less with respect to 100 mol% of the aliphatic glycol component.
- an example of producing polyethylene terephthalate using terephthalic acid and ethylene glycol will be described in detail.
- terephthalic acid and ethylene glycolate are esterified. Specifically, a slurry containing terephthalic acid and ethylene glycol is prepared. This slurry contains preferably 1.2 to 1.8 moles, more preferably 1.3 to 1.6 monoethylene ethylene glycolate per mole of terephthalic acid. This slurry is continuously supplied to the esterification reaction step.
- ethylene glycol a part of the ethylene glycol recovered by distillation from the reactor in the esterification reaction step and liquid phase polycondensation step described later may be used. (Esterification reaction process)
- the reactants are not circulated in the esterification reactor in a single stage, or two or more esterification reactors are connected in series and the reactants are circulated in the same manner.
- the method of implementation is preferred. In both cases, water is generated by the esterification reaction under conditions where ethylene glycol is refluxed, and is removed from the esterification reactor by a rectification column.
- the reaction conditions for carrying out the esterification continuously in a single stage while allowing the reactants to self-circulate are usually a reaction temperature of 240 to 230 ° C, and a reaction pressure of normal to 0.3 MPa. It is preferable to carry out under the following conditions.
- the esterification reaction temperature may be initially in a low temperature range within this range, but the final esterification reaction temperature is preferably between 25 ° C and 279 ° C. 6 5 to 2 7 6 ° C is more preferable, and 2 7 3 to 2 75 ° C is most preferable.
- the final esterification reaction temperature represents the reaction temperature at the end of the esterification reaction step.
- the molar ratio of ethylene glycol / terephthalic acid used is preferably 1.2 to 1.8, and more preferably 1.3 to 1.6. preferable.
- ethylene glycol or terephthalic acid that is added during the esterification reaction is included.
- the molar ratio is preferably within the range.
- the intrinsic viscosity value and end point of the melt polycondensed polyethylene terephthalate described later can be obtained. It becomes easy to control the value of the terminal carboxyl number within a predetermined range.
- the esterification reaction rate is usually 90% or more, preferably 90% or more and 100% or less, more preferably 95% or more and 100%. /. In the following, it is more preferable to carry out the reaction until it becomes 97% or more and 100% or less.
- the terminal carboxyl number of polyethylene terephthalate obtained by the melt polycondensation reaction can be controlled by adjusting the reaction temperature during the esterification reaction and the reflux ratio of ethylene dalycol. If these conditions are not met, the intrinsic viscosity may not increase in the subsequent liquid phase polycondensation step.
- an esterification reaction product (ethylene terephthalate oligomer) of terephthalic acid and ethylene glycol is obtained.
- the degree of polymerization of this ethylene terephthalate oligomer is preferably 3 to 12, more preferably 4 to 10, and most preferably 6 to 10.
- the ethylene terephthalate oligomer obtained in the esterification reaction step as described above is then supplied to a polycondensation (liquid phase polycondensation) step.
- the degree of polymerization of ethylene terephthalate oligomer is controlled by adjusting the esterification reaction rate by adjusting the ethylene glycol / terephthalic acid molar ratio, esterification reaction time, reaction pressure and reaction time as appropriate. can do. If the degree of polymerization of the ethylene terephthalate oligomer is deviated, the intrinsic viscosity may not increase in the subsequent liquid phase polycondensation step.
- the ethylene terephthalate oligomer obtained in the esterification reaction step is reduced in pressure and above the melting point of polyethylene terephthalate.
- Polycondensation is carried out by heating to a temperature below the decomposition temperature of the rate (usually 2400 to 2800C). This polycondensation reaction is preferably carried out while distilling off unreacted ethylene glycol and ethylene glycol generated by polycondensation outside the reactor.
- the liquid phase polycondensation step may be performed in one tank or may be performed in a plurality of tanks.
- the polycondensation reaction in the first tank has a reaction temperature of 245 to 290, preferably 2600 to 280 ° C, and a reaction pressure of 1 0 0 to 1 1? &, Preferably 5 0 to 2 k Pa.
- the polycondensation reaction is performed at a reaction temperature of 2 65 to 300 ° C., preferably 2 70 to 2 90 ° C., and a reaction pressure is usually 1 to 0 0 to: L 0 Pa
- the reaction is performed under conditions of 500 to 30 Pa.
- the intrinsic viscosity of the obtained melt polycondensed polyethylene terephthalate is controlled to be within the following range.
- the reaction time in the polycondensation step is preferably 240 minutes or less, more preferably 200 minutes or less, as the residence time in the polycondensation reaction tank. In this way, polyethylene terephthalate can be produced using the polycondensation catalyst described above.
- Polyethylene terephthalate obtained in this polycondensation step is usually extruded in a molten state, cooled, and then cut to obtain granular (chip-like) polyethylene terephthalate.
- the polyethylene terephthalate obtained should have an intrinsic viscosity IV of 0.48 to 0.53 dL / g and a terminal carboxyl number of 14 to 22 mm o 1 kg.
- the intrinsic viscosity falls within the range of 0.48 to 0.52 d LZ g and the terminal carboxyl number falls within the range of 17 to 2 2 mm o 1 / kg.
- the intrinsic viscosity of polyethylene terephthalate is preferably as high as possible.
- the intrinsic viscosity exceeds the upper limit of the above range, there will be a problem that the amount of polyethylene terephthalate after solid phase polycondensation and the amount of acetate aldehyde in the polyethylene terephthalate molded product is large.
- the content of acetonitrile in the polyethylene terephthalate molded product is large. If the number of terminal carboxyls exceeds the upper limit of the above range, the cyclic trimer content increases.
- a phosphorus stabilizer such as trimethyl phosphate may be added at any stage in the production of polyethylene terephthalate, if necessary.
- an antioxidant an ultraviolet absorber, a flame retardant, a fluorescent brightener, a decoloring agent, a color-tuning agent, an antifoaming agent or other additives may be added to the polyethylene terephthalate.
- azo compounds in the production stage of polyethylene terephthalate, azo compounds, triphenylmethane compounds, quinoline compounds, anthraquinone compounds, or phthalocyanines
- Organic blue pigments of compounds, inorganic blue pigments, or other color matching agents can also be added to the reactor.
- the polyethylene terephthalate obtained in the liquid phase polycondensation step needs to be further supplied to the solid phase polycondensation.
- the granular polyethylene terephthalate to be supplied to the solid phase polycondensation step is preliminarily crystallized by heating to a temperature lower than the temperature for solid phase polycondensation, and then supplied to the solid phase polycondensation step. Also good.
- This precrystallization step involves heating the granular polyethylene terephthalate in a dry state, usually from 120 to 200 ° C, preferably from 130 to 180 ° C for 1 minute to 4 hours. Can be done.
- pre-crystallization is performed by using granular polyethylene terephthalate in a water vapor atmosphere, in a water vapor-containing inert gas atmosphere, in an inert gas atmosphere, in a water vapor-containing air atmosphere, or in the flow of these gases. It can also be carried out by heating at a temperature of ⁇ 200 ° C for 1 minute or longer.
- the heating time is preferably 1 minute to 20 hours, more preferably 30 minutes to 10 hours, and most preferably 1 hour to 8 hours.
- Pre-crystallized polyethylene terephthalate has a crystallinity of 20 It is desirable to be 50%.
- the so-called solid phase polycondensation reaction of polyethylene terephthalate does not proceed by this precrystallization treatment, and the intrinsic viscosity of the precrystallized polyethylene terephthalate is the limit of polyethylene terephthalate after liquid phase polycondensation. It is almost the same as the viscosity.
- the difference between the intrinsic viscosity of the pre-crystallized polyethylene terephthalate and the intrinsic viscosity of the polyethylene terephthalate before pre-crystallization is usually not more than 0.06 d LZ g.
- the density of the complete crystal state and the density of the completely amorphous state are 1.5 0 1 g _ cm 3 and 1. 3 3 5 g Z cm 3 respectively. Therefore, the crystallinity can be calculated by measuring the specific gravity of the obtained polyethylene terephthalate sample with a density gradient pipe or the like.
- the solid phase polycondensation step consists of at least one stage, and the reaction temperature is 190 to 230 ° C, preferably 1955-225 ° C, more preferably 200-22-2. 5 ° C.
- Oxidation is carried out in an atmosphere of nitrogen, argon, carbon dioxide, or other inert gas under a reaction pressure of 200 kPa to lkPa, preferably from normal pressure to 10 kPa. Since decomposition
- the granular polyethylene terephthalate that has been subjected to such a solid phase polycondensation step may be subjected to water treatment if necessary.
- This water treatment is performed by converting the granular polyethylene terephthalate to water, water vapor, water vapor-containing This is done by contact with activated gas or air containing steam.
- the granular polyethylene terephthalate thus obtained should have an intrinsic viscosity IV of 0.70 to 0.86 d LZ g.
- the polyethylene terephthalate after the solid phase polycondensation preferably has a terminal carboxyl number of less than 15 mm o 1 / kg.
- the number of terminal carboxyls is more preferably 0 to less than 15 mm o 1 / kg, even more preferably 5 to 12 mm o 1 / kg.
- Polyethylene terephthalate including esterification reaction step, liquid phase polycondensation step, and solid phase polycondensation step as described above This manufacturing process can be carried out by any of the patch type, semi-continuous type and continuous type.
- the intrinsic viscosity of polyethylene terephthalate after solid-phase polycondensation is less than 0-70 dL / g, the strength of the polyethylene terephthalate molded product obtained by melt-molding polyethylene terephthalate will be insufficient, bottles, etc. For applications that require high transparency, the appearance may be whitened. On the other hand, if the intrinsic viscosity exceeds 0.86 dLZ g, the toughness of the polyethylene terephthalate molded article is lost, and the brittleness and the crystallization speed may be reduced.
- the cyclic trimer content may increase, which is not preferable.
- the above-mentioned intrinsic viscosity and molten polycondensed polyethylene It is important to carry out the process in an inert gas atmosphere within the above temperature range and pressure range.
- a compound containing at least one atom of sodium, potassium, and cesium in polyethylene terephthalate before molding is added at a concentration of these metal atoms of 2 in polyethylene terephthalate. It is preferably added to contain ⁇ 25 ppm.
- Metal salts other than sodium, potassium, and cesium have little effect on reducing the amount of acetonitrile. Even when sodium salt, potassium salt, or cesium salt is used, if the metal atom concentration in polyethylene terephthalate is less than 2 ppm, there is almost no effect of reducing the amount of acetate aldehyde, and more than 25 ppm. When is added, molding abnormalities such as foreign matters are generated in polyethylene terephthalate molded products.
- the amount of metal salt added at the time of addition is contained in polyethylene terephthalate as it is. Therefore, considering this point, 2 to 25 in the obtained polyethylene terephthalate.
- the amount added during production can be calculated so as to include ppm.
- at least one atom of the above-mentioned sodium, potassium, and cesium in the polyethylene terephthalate at least one metal salt selected from the group consisting of acetate, carbonate, and sulfate is used. It is preferable to add.
- acetate is preferable, that is, it is preferable to use sodium acetate, potassium acetate, or cesium acetate.
- the solution containing the metal salt can be used without limitation as long as it is a liquid that can dissolve the metal salt at an appropriate concentration, but an aqueous solution is preferable because of its high solubility and easy availability of the solvent.
- the contacting method can be adopted in either a batch type or a continuous type. In the case of a batch system, a method in which a solution of these metal salts and poly (ethylene terephthalate) after solid-phase polycondensation are put into a processing apparatus and brought into contact with each other can be mentioned.
- a method of continuously supplying an aqueous solution of these metal salts in a countercurrent or a parallel flow and contacting with polyethylene terephthalate or a method of spraying a solution onto polyethylene terephthalate can be mentioned. Further, the method of drying at an appropriate temperature after adhering an aqueous solution of these metal salts is most excellent.
- acetonitrile in polyethylene terephthalate obtained by solid phase polycondensation is obtained.
- the content is less than 15 ppm, and the cyclic trimer content can be 0.4% by weight or less.
- the acetonitrile content is preferably 8 ppm or less, more preferably 6 ppm or less.
- polyethylene terephthalate includes polyethylene terephthalate immediately after contact with the solution containing the above metal salt, and then a polyethylene terephthalate molded product obtained by a method such as injection molding. . (Other)
- the polyethylene terephthalate obtained by the production method of the present invention is excellent in hue and transparency, has a low content of acyl aldehyde, and a low content of Cy-3. It is useful as a molding material for beverages. Before producing the molded body, it is preferable to sufficiently dry the polyethylene terephthalate, and the temperature is 120 to 180 ° C. in an air atmosphere, an inert gas atmosphere, or an inert gas flow. It is preferable to do so.
- test tubular molded body Prepare an appropriate mold of polyethylene terephthalate obtained by the production method of the present invention, and mold it at a molding temperature of 300 ° C, outer diameter of 28 mm, inner diameter of 19 mm, length of 13 6 mm, weight 5 6 g of test tubular molded body can be obtained.
- Its detailed shape is generally a hollow cylindrical shape, with one end closed in a nearly hemispherical shape.
- the test aldehyde content in the test tubular molded body may be less than 13 ppm and the cyclic trimer content may be 0.4% by weight or less. This is the same level as a molded article of polyethylene terephthalate under the same conditions obtained by using a conventional germanium compound under the optimum conditions.
- a polyethylene terephthalate is produced by using as a catalyst a titanium compound that is less expensive than a germanium compound and less sanitary than an antimony compound or an aluminum compound.
- the polyethylene terephthalate can produce molded articles with a low aldehyde content and low cyclic tridentate content, equivalent to polyethylene terephthalate using a germanium compound as a polycondensation catalyst. . This fact has great industrial significance.
- a polyethylene terephthalate sample was pulverized and precisely weighed, then dissolved in benzyl alcohol and subjected to neutralization titration with potassium hydroxide. The titration value was converted into a value per unit weight of polyethylene terephthalate to calculate the number of terminal carboxyls.
- a polyethylene terephthalate sample was freeze-ground and charged into a vial, and held at 150 ° C. ⁇ 60 minutes. After that, the gas in the vial was analyzed with a Hitachi headspace gas chromatography, and the AA content was calculated.
- the dried polycondensation catalyst slurry sample was set on a scanning electron microscope (SEM, Hitachi Instrument Service S570). Quantitative analysis is performed with an energy dispersive X-ray microanalyzer (XMA, Horiba EMA X—700) connected to SEM. The phosphorus atom concentration was calculated.
- SEM scanning electron microscope
- XMA energy dispersive X-ray microanalyzer
- the catalyst metal concentration in polyethylene terephthalate is determined by heating and melting a granular sample on an aluminum plate, and then creating a molded product with a flat surface using a compression press.
- X-ray fluorescence equipment Riviere Denki Kogyo 3 2 7 0 E type
- Polyethylene terephthalate sample was pulverized with a powder machine, weighed in a fixed amount, once dissolved with a small amount of hexafluoroisopropanol / formaldehyde solution, and diluted to a constant concentration (SO g ZL) with formaldehyde . Thereafter, this solution was subjected to gel chromatography (GPC, WALCs AL CZG PC2244 type), and the peak of the component appearing in the low molecular weight region was detected. On the other hand, Cy-3 in polyethylene terephthalate was quantified based on a calibration curve obtained from a standard sample of cyclic trimer (Cy-3).
- a sample of the esterification reaction product obtained by the esterification process is sampled by Maurice et al.
- the amount of carboxyl end groups was measured by [An al. Chim. A cta, 2 2, p 3 6 3 (1 9 6 0)].
- a sample of the esterification reaction product was dissolved in hexafluoroisopropanol, and the amount of terminal hydroxyl group was determined by using 13 C-NMR for this solution. Furthermore, the number average molecular weight was calculated from the amounts of both terminal groups, and converted to the degree of polymerization.
- T BMB P catalyst solution As a result of separating and purifying fine precipitates in the solution from various parts of the solution and conducting various analyses, the fine precipitates are compounds represented by the general formula (I). Was a compound having a normal butyl group.
- the degree of polymerization of the ethylene terephthalate oligomer produced was about 5-9.
- Ethylene terephthalate oligomer obtained by this esterification reaction 45 parts by mass were sequentially transferred to a polycondensation reaction tank, and 4 parts by mass of the TBMBP catalyst solution prepared in Reference Example 1 was added as a polycondensation catalyst per unit time. While maintaining the reaction temperature in the polycondensation reaction tank at 27.65 ° C and the reaction pressure at 6 OPa, it is in a molten state while removing water and ethylene glycol generated in the polycondensation reaction from the polycondensation reaction tank. The polycondensation reaction was carried out. At this time, the residence time in the polycondensation reaction tank was 180 minutes.
- This polyethylene terephthalate (melt polycondensed polyethylene terephthalate) has an IV of 0.4 9 2 d L g and a terminal carboxyl number of f up to 1 mmol / js g.
- This melt polycondensed polyethylene terephthalate was crystallized and dried at 160 ° C. for 5 hours under nitrogen flow. Subsequently, the crystallized polyethylene terephthalate was put into a tumbler type solid-phase polycondensation apparatus, and a solid-phase polycondensation reaction was carried out for 2 hours at 2 25 ° C under a reduced pressure of ⁇ 0.13 kPa.
- a preform was molded by the following method. Polyethylene terephthalate (5 kg) was dried using a shelf-type dryer for 5 hours or more at a temperature of 160 ° C., normal pressure, and nitrogen flow.
- Dry polyethylene terephthalate was injected with an injection molding machine (FN-2200 model, manufactured by Nissei Plastic Industry Co., Ltd.), cylinder temperature 3 0 0 ° C, screw rotation speed 1 60 rpm, primary pressure time 3.0 Second, mold temperature 10 ° C, cycle 30 seconds, cylindrical test tube molded body with outer diameter 28 mm, inner diameter 19 mm, length 13 36 mm, weight 56 g was injection molded . Since this test tubular molded body is molded into a bottle, a bottle is obtained. This test tubular molded body is called a molded preform.
- FN-2200 model manufactured by Nissei Plastic Industry Co., Ltd.
- a series of polyethylene terephthalate (melt polycondensed polyethylene terephthalate, solid phase polycondensed polyethylene terephthalate) and molded preform intrinsic viscosity, terminal carboxyl number, Ti atom content, P atom Tables 1 and 2 show the content, K atom content, and other qualities.
- Example 1 the esterification reaction temperature was changed to 2 7 3.5 ° C, and the IV of the melt polycondensed polyethylene terephthalate was 0.4 8 9 d L / g, and the number of terminal carboxyls was 19 mm o
- a polycondensation reaction was carried out in the same manner as in Example 1 except that the amount was 1 / kg ′.
- Tables 1 and 2 show the quality of the obtained melt polycondensed polyethylene terephthalate, solid phase polycondensed polyethylene terephthalate, and molded preform.
- Example 1 the esterification reaction temperature was changed to 2 7 3.0 ° C, and the IV of the melt polycondensed polyethylene terephthalate was 0.4 8 3 d L / g, and the terminal carboxyl number was 2 2 mmo 1 / A polycondensation reaction was carried out in the same manner as in Example 1 except that kg was used. Tables 1 and 2 show the quality of the obtained melt polycondensed polyethylene terephthalate, solid phase polycondensed polyethylene terephthalate, and molded preform.
- Example 1 the esterification reaction temperature was changed to 273.5 ° C and the melt polycondensation temperature was changed to 277.5 ° C, so that the IV of the melt polycondensed polyethylene terephthalate was 0.5 0.5 0.
- a polycondensation reaction was carried out in the same manner as in Example 1 except that d L / g and the number of terminal carboxyls were 18 mmo 1 / kg.
- Tables 1 and 2 show the quality of the obtained melt polycondensed polyethylene terephthalate, solid phase polycondensed polyethylene terephthalate and molded preform. ''
- Example 1 the IV of the melt polycondensed polyethylene terephthalate was changed to 0.49 1 d LZ g and the terminal carboxyl number was 26 mm o 1 / A polycondensation reaction was carried out in the same manner as in Example 1 except that kg was used. Obtained melt polycondensed polyethylene tele The quality of phthalate, solid phase polycondensed polyethylene terephthalate and molded preform are shown in Tables 1 and 2.
- Example 1 the IV of the melt polycondensed polyethylene terephthalate was changed to 0.5 4 by changing the esterification reaction temperature to 273.5 ° C and the melt polycondensation temperature to 278.3 ° C.
- a polycondensation reaction was carried out in the same manner as in Example 1 except that 4 dL / g and the number of terminal carboxyls were 17 mm 0 1 / kg.
- the quality of the obtained melt polycondensed polyethylene terephthalate, solid phase polycondensed polyethylene terephthalate and molded preform is shown in Tables 1 and 2.
- the reaction product in the polycondensation reaction tank is continuously extruded in a strand shape from the discharge part, cooled with ice, and then By cutting, a granular polyethylene terephthalate having a size of about 3 mm was obtained.
- the melt polycondensed polyethylene terephthalate had an IV of 0.492 2 dL / g and a terminal carboxyl number of 17 mm o 1 / kg. This melt polycondensed polyethylene terephthalate was crystallized and dried at 160 ° C. for 5 hours under nitrogen flow.
- the crystallized polyethylene terephthalate was put into a tumbler type solid-phase polycondensation apparatus, and a solid-phase polycondensation reaction was carried out at 2 25 ° C for 27 hours under a reduced pressure of 0.1 3 kPa. .
- the obtained polyethylene terephthalate was added by spraying an aqueous solution of acetic acid lithium so that the content of the force lithium atom in the polyethylene terephthalate was 8 ppm.
- the solid phase polycondensed polyethylene terephthalate was obtained by drying.
- the preform molded body was molded in the same manner as in Example 1.
- Example 5 the esterification reaction temperature was changed to 2 7 3.5 ° C, and the IV of the melt polycondensed polyethylene terephthalate was 0.4 8 9 d L / g, and the terminal carboxyl number was 19 mmol / A polycondensation reaction was performed in the same manner as in Example 5 except that kg was used. Tables 1 and 2 show the quality of the obtained melt polycondensed polyethylene terephthalate, solid phase polycondensed polyethylene terephthalate, and molded preform.
- Example 5 the esterification reaction temperature was changed to 2 7 3.0 ° C, and IV of the melt polycondensed polyethylene terephthalate was 0.48 3 d LZg, and the number of terminal carboxyls was 2, 2 mm o 1 Zkg.
- a polycondensation reaction was performed in the same manner as in Example 5 except that.
- the ohm quality is shown in Tables 1 and 2.
- Example 5 the esterification reaction temperature was changed to 2 7 4. 9 ° C and the IV of the melt polycondensed polyethylene terephthalate was 0. ASA d L / g The number of terminal carboxyls was 15 mm o 1 / kg.
- a polycondensation reaction was carried out in the same manner as in Example 5 except that. Tables 1 and 2 show the quality of the obtained melt polycondensed polyethylene terephthalate, solid phase polycondensed polyethylene terephthalate, and molded preform.
- Example 5 the esterification reaction temperature was changed to 273.5 ° C and the melt polycondensation temperature was changed to 277.5 ° C, so that the IV of the melt polycondensed polyethylene terephthalate was 0.5 2 0
- a polycondensation reaction was carried out in the same manner as in Example 5 except that d LZ g and the number of terminal force lpoxyl were 18 mm o 1 / kg.
- Tables 1 and 2 show the quality of the obtained melt polycondensed polyethylene terephthalate, solid phase polycondensed polyethylene terephthalate, and molded preform.
- Example 9 the spray amount of the aqueous solution of acetic acid lithium was changed so that the potassium atom content in the polyethylene terephthalate was the value shown in Table 2, and then dried to solid phase polycondensation polyethylene terephthalate.
- Tables 1 and 2 show the quality of the obtained melt polycondensed polyethylene terephthalate, solid phase polycondensed polyethylene terephthalate, and molded preform.
- Example 9 instead of using an aqueous solution of potassium acetate, an aqueous solution of sodium acetate or an aqueous solution of cesium acetate was used, and spraying was performed so that the content of the alkali metal atom in the polyethylene terephthalate was the value shown in Table 2. The amount was changed and then dried to obtain solid phase polycondensation polyethylene terephthalate. Obtained melt polycondensed polyethylene terephthalate Tables 1 and 2 show the quality of the rate, solid-phase polycondensed polyethylene terephthalate and molded preform.
- a polycondensation reaction was carried out in the same manner as in Example 1 except that the conditions shown below were changed in Example 1. Instead of adding 4 parts by mass of TBMB P catalyst solution as a polycondensation catalyst per unit time from 274.5 ° C to 2 7 7. 2 ° C, the esterification reaction temperature was changed to 1% by weight germanium dioxide Z Changed to 6.8 parts by mass of ethylene glycol solution per unit time and 1 part by mass of ethylene glycol solution of phosphoric acid (5.5% by mass of phosphorus) per unit time. .
- melt polycondensation temperature was changed from 27.65 ° C to 27.70 ° C
- IV of the melt polycondensed polyethylene terephthalate was 0.5 10 dL and the terminal carboxyl number was 26. mmo 1 / kg.
- solid phase polycondensation at 2 2 5 for 27 hours to 2 20 ° C for 2 to 3 hours.
- Tables 1 and 2 show the qualities of the obtained melt polycondensed polyethylene terephthalate, solid phase polycondensed polyethylene terephthalate and molded preform.
- Example 1 TBMBP 0 o.492 1 7 0.752 ⁇
- Example 3 TBMBP 0.483 2 2 0.762 ⁇
- Example 4 TBMBP 0.520 1 8 0.769 ⁇
- Example 5 TBMBP 0.492 1 7 0.752 9 7
- Example 6 TBMBP 0.489 1 9 0.754 1 0.4
- Example 7 TBMBP 0.483 2 2 0.762 9.7
- Example 8 TBMBP 0.494 1 5 0.751 9.5
- Example 9 TBMBP 0.520 1 8 0.769 8.2
- Example 10 TBMBP 0.520 1 8 0.774 8.1
- Example 11 TBMBP 1 8 0.770 8.4
- Example 12 TBMBP 0.520 1 9 0.774 8.2
- Example 13 TBMBP 0.520 1 8 0.772 8.4 Comparative Example 1 TBMBP 0.491 2 6 0.762 ⁇ Comparative Example 2 TBMBP 0.544 1 7 0.740
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Abstract
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Priority Applications (17)
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EA200802112A EA015941B1 (ru) | 2006-04-06 | 2007-04-05 | Способ получения полиэтилентерефталата |
AU2007236595A AU2007236595B2 (en) | 2006-04-06 | 2007-04-05 | Process for production of polyethylene terephthalate |
PL07741452T PL2003159T3 (pl) | 2006-04-06 | 2007-04-05 | Sposób wytwarzania poli(tereftalanu etylenu) |
KR1020087024295A KR101293011B1 (ko) | 2006-04-06 | 2007-04-05 | 폴리에틸렌테레프탈레이트의 제조 방법 |
SI200730821T SI2003159T1 (sl) | 2006-04-06 | 2007-04-05 | Postopek izdelave polietilen tereftalata |
CN200780012036XA CN101415749B (zh) | 2006-04-06 | 2007-04-05 | 聚对苯二甲酸乙二醇酯的制备方法 |
US12/295,211 US8653232B2 (en) | 2006-04-06 | 2007-04-05 | Manufacturing method of polyethylene terephthalate |
MX2008011881A MX2008011881A (es) | 2006-04-06 | 2007-04-05 | Proceso para produccion de terftalato de polietileno. |
ES07741452T ES2378403T3 (es) | 2006-04-06 | 2007-04-05 | Método para producir tereftalato de polietileno |
BRPI0709881-2A BRPI0709881B1 (pt) | 2006-04-06 | 2007-04-05 | Método de fabricação de poli(tereftalato de etileno) |
DK07741452.2T DK2003159T3 (da) | 2006-04-06 | 2007-04-05 | Fremgangsmåde til fremstilling af polyethylen-terephthalat |
EP07741452A EP2003159B1 (en) | 2006-04-06 | 2007-04-05 | Process for production of polyethylene terephthalate |
CA2646576A CA2646576C (en) | 2006-04-06 | 2007-04-05 | Manufacturing method of polyethylene terephthalate |
AT07741452T ATE540994T1 (de) | 2006-04-06 | 2007-04-05 | Verfahren zur herstellung von polyethylenterephthalat |
JP2008509915A JP5139974B2 (ja) | 2006-04-06 | 2007-04-05 | ポリエチレンテレフタレートの製造方法 |
HK09101458.4A HK1121481A1 (en) | 2006-04-06 | 2009-02-17 | Process for production of polyethylene terephthalate |
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JP2011207984A (ja) * | 2010-03-29 | 2011-10-20 | Fujifilm Corp | ポリエステル樹脂の製造方法、ポリエステルフィルム、太陽電池用バックシート、並びに太陽電池モジュール |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102575090B (zh) * | 2009-10-27 | 2013-12-11 | 东丽株式会社 | 聚对苯二甲酸乙二醇酯组合物、其制造方法及聚对苯二甲酸乙二醇酯膜 |
CA2801397C (en) | 2010-06-03 | 2018-04-24 | Stora Enso Oyj | Hydrogen treatment of impure tall oil for the production of aromatic monomers |
US8877862B2 (en) | 2011-07-15 | 2014-11-04 | Saudi Basic Industries Corporation | Method for color stabilization of poly(butylene-co-adipate terephthalate |
US9334360B2 (en) | 2011-07-15 | 2016-05-10 | Sabic Global Technologies B.V. | Color-stabilized biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof |
US8933162B2 (en) * | 2011-07-15 | 2015-01-13 | Saudi Basic Industries Corporation | Color-stabilized biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof |
US8946345B2 (en) | 2011-08-30 | 2015-02-03 | Saudi Basic Industries Corporation | Method for the preparation of (polybutylene-co-adipate terephthalate) through the in situ phosphorus containing titanium based catalyst |
US8889820B2 (en) | 2012-02-15 | 2014-11-18 | Saudi Basic Industries Corporation | Amorphous, high glass transition temperature copolyester compositions, methods of manufacture, and articles thereof |
US8969506B2 (en) | 2012-02-15 | 2015-03-03 | Saudi Basic Industries Corporation | Amorphous, high glass transition temperature copolyester compositions, methods of manufacture, and articles thereof |
US8901273B2 (en) | 2012-02-15 | 2014-12-02 | Saudi Basic Industries Corporation | Amorphous, high glass transition temperature copolyester compositions, methods of manufacture, and articles thereof |
US8895660B2 (en) | 2012-03-01 | 2014-11-25 | Saudi Basic Industries Corporation | Poly(butylene-co-adipate terephthalate), method of manufacture, and uses thereof |
US9034983B2 (en) | 2012-03-01 | 2015-05-19 | Saudi Basic Industries Corporation | Poly(butylene-co-adipate terephthalate), method of manufacture and uses thereof |
US8901243B2 (en) | 2012-03-30 | 2014-12-02 | Saudi Basic Industries Corporation | Biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof |
FI125507B2 (en) | 2012-04-13 | 2021-12-15 | Stora Enso Oyj | Methods for deoxygenating tall oil and producing polymerizable monomers therefrom |
KR102415147B1 (ko) * | 2016-09-30 | 2022-07-01 | 도레이첨단소재 주식회사 | 압축성형체용 숏컷 섬유, 이를 이용한 압축성형체 및 이의 제조방법 |
CN109134837B (zh) * | 2018-06-29 | 2024-01-23 | 浙江尤夫高新纤维股份有限公司 | 均质高粘聚酯及其制备方法 |
CN113276527A (zh) * | 2021-05-28 | 2021-08-20 | 杭州大东南高科新材料有限公司 | 一种低萃取聚酯薄膜及其制备方法 |
Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS48101462A (ja) | 1972-04-03 | 1973-12-20 | ||
JPS5148505A (en) | 1974-10-24 | 1976-04-26 | Komatsu Mfg Co Ltd | Dokokino sosasochi |
JPS5838722A (ja) * | 1981-08-31 | 1983-03-07 | Nippon Ester Co Ltd | ポリエステルの製造方法 |
JPH0347830A (ja) | 1989-03-31 | 1991-02-28 | Mitsui Petrochem Ind Ltd | ポリエチレンテレフタレートの製造方法 |
US5017680A (en) | 1990-07-03 | 1991-05-21 | Eastman Kodak Company | Process and catalyst-inhibitor systems for preparing poly(ethylene terephthalate) |
JPH07138354A (ja) * | 1993-07-12 | 1995-05-30 | General Electric Co <Ge> | 改良されたポリエステル化触媒 |
JP2001524536A (ja) * | 1997-12-02 | 2001-12-04 | エーシーエムエー リミティド | エステル化触媒 |
JP2002167495A (ja) * | 2000-11-30 | 2002-06-11 | Teijin Ltd | ポリエチレンテレフタレート樹脂組成物及びその識別方法 |
WO2003008479A1 (fr) | 2001-07-16 | 2003-01-30 | Teijin Limited | Catalyseur destine a la production de polyester et procede de production de polyester faisant intervenir ce catalyseur |
JP2003160656A (ja) * | 2001-11-28 | 2003-06-03 | Teijin Ltd | ポリエステルの製造方法及び繊維 |
JP2003160655A (ja) * | 2001-11-28 | 2003-06-03 | Teijin Ltd | ポリエステルの製造方法及びポリエステル繊維 |
JP2003183485A (ja) * | 2001-12-21 | 2003-07-03 | Mitsubishi Chemicals Corp | 改質ポリエステル樹脂及びそれからなる射出ブローボトル |
JP2004010657A (ja) | 2002-06-04 | 2004-01-15 | Teijin Ltd | ポリエチレンテレフタレートの処理方法 |
JP2004060063A (ja) * | 2002-07-25 | 2004-02-26 | Teijin Ltd | ポリエステル未延伸糸の製造方法 |
WO2005023900A1 (en) | 2003-08-28 | 2005-03-17 | The Coca-Cola Company | Polyester composition and articles with reduced acetaldehyde content and method using vinyl esterification catalyst |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5589331A (en) | 1978-12-27 | 1980-07-05 | Diafoil Co Ltd | Production of polyester |
US4205157A (en) * | 1979-04-02 | 1980-05-27 | The Goodyear Tire & Rubber Company | Method for production of high molecular weight polyester with low catalyst level and low carboxyl content |
TWI227246B (en) * | 2001-07-16 | 2005-02-01 | Teijin Ltd | Catalyst for polyester production and process for producing polyester with the same |
ATE501287T1 (de) | 2003-01-09 | 2011-03-15 | Teijin Fibers Ltd | Strick-/webstoff aus polyethylenterephthalatfaser |
KR20050092414A (ko) | 2003-01-16 | 2005-09-21 | 데이진 화이바 가부시키가이샤 | 폴리에스테르 이수축 혼섬사 |
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Patent Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS48101462A (ja) | 1972-04-03 | 1973-12-20 | ||
JPS5148505A (en) | 1974-10-24 | 1976-04-26 | Komatsu Mfg Co Ltd | Dokokino sosasochi |
JPS5838722A (ja) * | 1981-08-31 | 1983-03-07 | Nippon Ester Co Ltd | ポリエステルの製造方法 |
JPH0347830A (ja) | 1989-03-31 | 1991-02-28 | Mitsui Petrochem Ind Ltd | ポリエチレンテレフタレートの製造方法 |
US5017680A (en) | 1990-07-03 | 1991-05-21 | Eastman Kodak Company | Process and catalyst-inhibitor systems for preparing poly(ethylene terephthalate) |
JPH07138354A (ja) * | 1993-07-12 | 1995-05-30 | General Electric Co <Ge> | 改良されたポリエステル化触媒 |
JP2001524536A (ja) * | 1997-12-02 | 2001-12-04 | エーシーエムエー リミティド | エステル化触媒 |
JP2002167495A (ja) * | 2000-11-30 | 2002-06-11 | Teijin Ltd | ポリエチレンテレフタレート樹脂組成物及びその識別方法 |
WO2003008479A1 (fr) | 2001-07-16 | 2003-01-30 | Teijin Limited | Catalyseur destine a la production de polyester et procede de production de polyester faisant intervenir ce catalyseur |
JP2003160656A (ja) * | 2001-11-28 | 2003-06-03 | Teijin Ltd | ポリエステルの製造方法及び繊維 |
JP2003160655A (ja) * | 2001-11-28 | 2003-06-03 | Teijin Ltd | ポリエステルの製造方法及びポリエステル繊維 |
JP2003183485A (ja) * | 2001-12-21 | 2003-07-03 | Mitsubishi Chemicals Corp | 改質ポリエステル樹脂及びそれからなる射出ブローボトル |
JP2004010657A (ja) | 2002-06-04 | 2004-01-15 | Teijin Ltd | ポリエチレンテレフタレートの処理方法 |
JP2004060063A (ja) * | 2002-07-25 | 2004-02-26 | Teijin Ltd | ポリエステル未延伸糸の製造方法 |
WO2005023900A1 (en) | 2003-08-28 | 2005-03-17 | The Coca-Cola Company | Polyester composition and articles with reduced acetaldehyde content and method using vinyl esterification catalyst |
Non-Patent Citations (1)
Title |
---|
MAURICE ET AL., ANAL. CHIM. ACTA, vol. 22, 1960, pages 363 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011207984A (ja) * | 2010-03-29 | 2011-10-20 | Fujifilm Corp | ポリエステル樹脂の製造方法、ポリエステルフィルム、太陽電池用バックシート、並びに太陽電池モジュール |
Also Published As
Publication number | Publication date |
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TW200745206A (en) | 2007-12-16 |
ES2378403T3 (es) | 2012-04-12 |
EP2003159B1 (en) | 2012-01-11 |
CY1112240T1 (el) | 2015-12-09 |
EP2003159A1 (en) | 2008-12-17 |
PT2003159E (pt) | 2012-01-24 |
CA2646576C (en) | 2014-02-11 |
EA200802112A1 (ru) | 2009-02-27 |
DK2003159T3 (da) | 2012-02-06 |
KR20080110605A (ko) | 2008-12-18 |
AU2007236595A1 (en) | 2007-10-18 |
CN101415749B (zh) | 2012-07-18 |
TWI402293B (zh) | 2013-07-21 |
SI2003159T1 (sl) | 2012-04-30 |
JPWO2007117028A1 (ja) | 2009-08-27 |
US8653232B2 (en) | 2014-02-18 |
ATE540994T1 (de) | 2012-01-15 |
EP2003159A4 (en) | 2010-05-19 |
HK1129122A1 (en) | 2009-11-20 |
MX2008011881A (es) | 2008-09-30 |
BRPI0709881B1 (pt) | 2018-06-12 |
CA2646576A1 (en) | 2007-10-18 |
US20090137769A1 (en) | 2009-05-28 |
BRPI0709881A2 (pt) | 2011-07-26 |
EA015941B1 (ru) | 2011-12-30 |
PL2003159T3 (pl) | 2012-06-29 |
KR101293011B1 (ko) | 2013-08-12 |
CN101415749A (zh) | 2009-04-22 |
HK1121481A1 (en) | 2009-04-24 |
AU2007236595B2 (en) | 2011-10-20 |
MY153180A (en) | 2015-01-29 |
JP5139974B2 (ja) | 2013-02-06 |
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