WO2013035559A1 - 耐熱性に優れたポリエステルおよびその製造方法 - Google Patents
耐熱性に優れたポリエステルおよびその製造方法 Download PDFInfo
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- WO2013035559A1 WO2013035559A1 PCT/JP2012/071495 JP2012071495W WO2013035559A1 WO 2013035559 A1 WO2013035559 A1 WO 2013035559A1 JP 2012071495 W JP2012071495 W JP 2012071495W WO 2013035559 A1 WO2013035559 A1 WO 2013035559A1
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- diol
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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
-
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/18—Polyhydroxylic acyclic alcohols
- C07C31/20—Dihydroxylic alcohols
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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
-
- 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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- 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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—Dicarboxylic acids and dihydroxy compounds
-
- 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
Definitions
- the present invention relates to a polyester excellent in heat resistance. More specifically, the present invention relates to a polyester having a small decrease in intrinsic viscosity during melt molding and a method for producing the same.
- Polyester is one of the most commonly used synthetic resins around the world as various fibers, films, sheets, containers, etc., because it is excellent in mechanical strength, chemical stability, transparency, and inexpensive. Among them, polyethylene terephthalate is excellent in terms of versatility and practicality and is preferably used.
- polyethylene terephthalate is produced from terephthalic acid or an ester-forming derivative thereof and ethylene glycol, but all of these raw materials are usually obtained from fossil resources.
- Petroleum which is a fossil resource, is an important raw material for the chemical industry, but in the future there are concerns about depletion and a large amount of carbon dioxide is emitted during the manufacturing process and incineration and disposal. Is inviting problems. Under such circumstances, much attention has been paid to the use of recycled raw materials and materials with low environmental impact.
- Biomass resources are plants converted from water and carbon dioxide as raw materials by photosynthesis, and include starch, carbohydrates, cellulose, and lignin. Biomass resources use carbon dioxide as a raw material in the production process. Therefore, even if materials using biomass resources are incinerated after use and decomposed into carbon dioxide and water, new carbon dioxide is emitted. It is not a matter of fact, and it can be said that it is a renewable resource because it is taken up again by the plant. If these biomass resources can be used as an alternative to petroleum resources, the reduction of fossil resources will be suppressed, and the amount of carbon dioxide emissions will also be suppressed.
- PET polyethylene terephthalate
- Patent Document 1 ethylene glycol derived from biomass resources has low purity, the resulting polymer has a low melting point, and there is a problem in heat resistance.
- Patent Document 2 a method is disclosed in which impurities derived from biomass resources used as a raw material are adsorbed with activated carbon (Patent Document 2).
- Patent Document 2 a polymer having a melting point comparable to that when using a fossil resource-derived glycol can be obtained.
- polyester is usually re-melted after chipping and then molded and processed.
- heat history near 300 ° C is applied, the polymer using biomass-derived glycol is still heat-resistant compared to the fossil-resource-derived polymer.
- the thermal decomposition reaction is accelerated, the polymer is yellowed and the viscosity is lowered, that is, the molecular weight is lowered.
- some undesired phenomena occur, such as increase in the mold base contamination of the molding machine and the generation of foreign matter.
- the present inventors have found that there is a problem to do.
- an object of the present invention is to provide a polyester excellent in heat resistance during melt molding. That is, it is to provide a polyester having a small decrease in intrinsic viscosity during melt molding and a method for producing the same.
- the polyester of the present invention that solves the above problems is a polyester obtained from a dicarboxylic acid and / or an ester-forming derivative thereof and a diol, and the component derived from 1,2-propanediol contained in the polyester is 15 to 500 ppm. It is contained.
- the polyester of the present invention contains 15 to 500 ppm of a component derived from 1,2-propanediol in the polyester, the polyester has excellent heat resistance during melt molding, that is, a decrease in intrinsic viscosity during melt molding is small. Become polyester.
- the polyester of the present invention suppresses the formation of a mold base and foreign matter in a molding machine, enables continuous operation and increases production efficiency.
- the present inventors have studied earnestly on the belief that it is necessary to further increase the purity of the biomass resource-derived glycol in order to solve the above problems. As a result, it has been found that as the purity is increased, the heat resistance during melt molding is improved. Furthermore, in the study, incidentally, 1,2-propanediol, which is an impurity in biomass-resource-derived glycol, is not purely reduced as an impurity, but has high purity when contained in a certain range of polyester. It has been found that the heat resistance at the time of melt molding is improved rather than the polyester obtained from the fossil resource-derived glycol, that is, the decrease in intrinsic viscosity at the time of melt molding is suppressed.
- a polyester containing 15 to 500 ppm of a component derived from 1,2-propanediol contained in the polyester is excellent in heat resistance during melt molding, that is, has a small decrease in intrinsic viscosity during melt molding. Reached.
- diols may be cyclized to a metal such as a polycondensation catalyst to coordinate as a bidentate ligand.
- 1,2-propanediol can be regarded as a compound in which a methyl group is bonded as a side chain to one of two carbon atoms in ethylene glycol.
- the side chain has more substituents, and the more bulky the substituents, the easier it is to cyclize due to its steric overhang effect.
- 1,2-propanediol which can be regarded as having a methyl group as a side chain, is more divalent to the metal than ethylene glycol. It can be said that it is easy to coordinate. Therefore, it is considered that a trace amount of 1,2-propanediol contained in the polyester is preferentially coordinated with the metal as the polymerization catalyst. Thus, it is considered that the heat resistance at the time of melt molding is improved by a mechanism in which only the activity of the thermal decomposition reaction is suppressed without suppressing the polymerization activity of the catalyst metal.
- the polyester of the present invention preferably contains, as a copolymerization component, at least one selected from 5-sulfoisophthalate and / or an ester-forming derivative thereof and a polyoxyalkylene glycol having a molecular weight of 500 to 20000.
- ethylene glycol is preferable.
- a molded product made of polyester having excellent heat resistance in this way is a molded product with excellent molding processability, high quality stability, and excellent mechanical properties.
- the method for producing a polyester according to the present invention comprises a method for producing a polyester by subjecting a dicarboxylic acid and / or its ester-forming derivative and a diol to esterification or transesterification, followed by polycondensation reaction under reduced pressure.
- a diol having a 2-propanediol content of 45 to 1000 ppm is used.
- the diol is preferably ethylene glycol.
- the content of 1,2-propanediol is preferably 45 to 1000 ppm, and a polyester excellent in heat resistance can be prepared.
- the diol is preferably ethylene glycol.
- the raw diol is distilled at a theoretical plate number of 40 or more and a reflux ratio of 10 or more, and adsorbed and separated in an activated carbon filtration layer having a space velocity of 0.1 to 1.1 hr ⁇ 1. It is preferable to purify in combination.
- the raw material diol is preferably biomass resource-derived ethylene glycol.
- the polyester of the present invention is obtained from a dicarboxylic acid and / or an ester-forming derivative thereof and a diol, and the component derived from 1,2-propanediol contained in the polyester is 15 to 500 ppm. If the content of the component derived from 1,2-propanediol in the polyester is more than the above range, the heat resistance of the polyester deteriorates. If the content is less, the effect of improving the heat resistance of the polyester cannot be obtained.
- the component derived from 1,2-propanediol is the total amount of 1,2-propanediol detected when the polyester is decomposed and analyzed, and is copolymerized in the polymer chain.
- Examples of the dicarboxylic acid and / or ester-forming derivative thereof which are monomers of the polyester of the present invention include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl-4,4′-dicarboxylic acid and ester-forming derivatives thereof.
- the ester-forming derivatives referred to in the present invention are lower alkyl esters, acid anhydrides, acyl chlorides and the like of these dicarboxylic acids, and methyl esters, ethyl esters, hydroxyethyl esters and the like are preferably used.
- a more preferred embodiment of the dicarboxylic acid and / or ester-forming derivative thereof of the present invention is terephthalic acid and / or dimethyl ester thereof.
- terephthalic acid and / or its dimethyl ester may be derived from biomass resources.
- the method for obtaining the biomass resource-derived terephthalic acid is not particularly limited, and any method may be used. For example, after obtaining isobutanol from corn, saccharides, or wood, it is converted to isobutylene and then dimerized. After isooctene is obtained, p-xylene is synthesized through a method known in the literature (Chemistechtechnik, vol. 38, No. 3, P116-119; 1986), that is, radical cleavage, recombination, and cyclization. Thus, there is a method for obtaining terephthalic acid (WO2009-079213).
- p-cymene was synthesized from cineole obtained from a plant of the genus Eucalyptus (Journal of Chemical Society of Japan, (2), P217-219; 1986), and then passed through p-methylbenzoic acid (Organic Synthesis, 27; 1947), and a method for obtaining terephthalic acid.
- Still another method is a method of obtaining terephthalic acid from furandicarboxylic acid and ethylene by Diels-Alder reaction (WO 2009-0664515). The biomass resource-derived terephthalic acid thus obtained may be further converted into an ester-forming derivative.
- the diol of the present invention is preferably a diol having a 1,2-propanediol content of preferably 45 to 1000 ppm.
- diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, cyclohexanedimethanol and the like.
- ethylene glycol is preferable.
- ethylene glycol ethylene glycol derived from biomass resources often contains 1,2-propanediol, so it is more preferable to use ethylene glycol derived from biomass resources whose content has been adjusted by purification. .
- a method for obtaining ethylene glycol derived from biomass resources is not particularly limited, and any method may be used. Examples thereof include the following methods. For example, there are methods of obtaining from biomass resources such as corn, sugar cane, wheat or crop stalks. These biomass resources are first converted to starch, starch is converted to glucose with water and enzymes, and then converted to sorbitol through a hydrogenation reaction. The sorbitol continues to be hydrogenated in the presence of a catalyst at a constant temperature and pressure. There is a method of obtaining ethylene glycol by purifying a mixture of various glycols.
- bioethanol is obtained from a carbohydrate crop such as sugar cane by a biological treatment method, then converted to ethylene, and further ethylene oxide is obtained via ethylene oxide.
- a method of obtaining glycerin from biomass resources and then obtaining ethylene glycol via ethylene oxide is another method.
- the ethylene glycol thus obtained contains various impurities, but is preferably purified so that the content of 1,2-propanediol, which is an impurity, is 45 to 1000 ppm.
- examples of the purification method of ethylene glycol derived from biomass resources include distillation purification, extraction separation, adsorption separation, and membrane separation, but it is preferable to combine distillation purification and adsorption separation.
- the number of theoretical plates is preferably 40 or more, and preferably 60 or less from the economical viewpoint.
- the reflux ratio of distillation is preferably 10 or more, and preferably 20 or less from the economical viewpoint.
- the kind of distillation tower is not specifically limited, For example, a packed tower, a plate tower, etc. are mentioned. Further, it may be carried out in a single distillation column or in a plurality of distillation columns.
- the distillation may be either a batch type or a continuous type, but a continuous type is preferred industrially.
- the biomass resource-derived ethylene glycol is first heated to convert impurities to a compound that is easily adsorbed on activated carbon, and then adsorbed on activated carbon.
- the heating time at this time is preferably 15 to 30 hours, and the temperature is preferably 190 to 200 ° C. If the heating time is short or the treatment temperature is low, impurities that cannot be converted into compounds that are easily adsorbed by activated carbon may remain.
- the biomass resource-derived ethylene glycol after heating is cooled and then contacted with activated carbon. At this time, the temperature after cooling is preferably 0 to 100 ° C.
- the activated carbon include coal-based activated carbon and wood-based activated carbon.
- coal-based activated carbon examples include Diahope 008 (Calgon Carbon Japan Co., Ltd.), and examples of the wood-based activated carbon include Dazai SGA (Nimura Chemical Industry Co., Ltd.). Of these, woody activated carbon, Dazai SGA, is particularly preferable.
- the activated carbon shape include powdered activated carbon, granular activated carbon, and fibrous activated carbon, and granular activated carbon is particularly preferable.
- the maximum size of the granular activated carbon particles is preferably 1 to 3 mm.
- the contact method with the biomass resource-derived ethylene glycol is preferably an osmotic filtration method.
- the thickness of the activated carbon filtration layer is preferably 200 to 500 cm, more preferably 200 to 300 cm.
- the contact between the biomass resource-derived ethylene glycol and the activated carbon is preferably at a space velocity of 0.1 to 1.1 hr ⁇ 1 .
- the space velocity is expressed as a velocity that indicates how many times (volume) the processed material has passed through the packed substance (volume) per hour. Either distillation purification or adsorption separation may be performed first.
- the bioification rate of the obtained polyester can be obtained by measuring the radioactive carbon 14 C concentration (pMC).
- concentration of radioactive carbon 14 C can be measured by the following radiocarbon concentration measurement method.
- the radiocarbon concentration measurement method uses an accelerator mass spectrometer (AMS: Accelerator Mass Spectrometry) to calculate the carbon isotopes ( 12 C, 13 C, 14 C) contained in the sample to be analyzed using the weight difference of the atoms. It is a method of physically separating and measuring the abundance of each isotope atom.
- the carbon atom is usually 12 C, and the isotope 13 C is present in about 1.1%. 14 C is called a radioisotope and its half-life regularly decreases at about 5370 years.
- the bioreduction rate of the polyester obtained is preferably 10% or more, and more preferably 15% or more.
- the polyester of the present invention is obtained by using terephthalic acid and / or its dimethyl ester as a dicarboxylic acid and / or an ester-forming derivative component thereof (hereinafter sometimes abbreviated as a dicarboxylic acid component) and ethylene glycol as a diol component.
- terephthalic acid and / or its dimethyl ester as a dicarboxylic acid and / or an ester-forming derivative component thereof (hereinafter sometimes abbreviated as a dicarboxylic acid component) and ethylene glycol as a diol component.
- Polyethylene terephthalate to be used is preferable, and when it is a polyester copolymer mainly containing ethylene terephthalate units, the degree of improvement in heat resistance becomes more remarkable.
- copolymer component of the polyester of the present invention examples include isophthalic acid, 5-sulfoisophthalic acid salt (5-sulfoisophthalic acid lithium salt, 5-sulfoisophthalic acid potassium salt, 5-sulfoisophthalic acid sodium salt, etc.), phthalic acid, and the like.
- Aromatic dicarboxylic acids such as naphthalene-2,6-dicarboxylic acid and ester-forming derivatives thereof, oxalic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1 And dicarboxylic acid components such as aliphatic dicarboxylic acids such as 1,12-dodecanedicarboxylic acid and ester-forming derivatives thereof.
- a copolymerization component of polyester using ethylene glycol as a main diol component 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, molecular weight of 500 to 20000
- diol components such as polyoxyalkylene glycol (polyethylene glycol, etc.), diethylene glycol, 2-methyl-1,3-propanediol, and bisphenol A-ethylene oxide adduct.
- 5-sulfoisophthalate such as lithium 5-sulfoisophthalate, potassium 5-sulfoisophthalate, and sodium 5-sulfoisophthalate, and ester-forming derivatives thereof, and polymers having a molecular weight of 500 to 20000.
- Oxyalkylene glycol is more preferred.
- polyoxyalkylene glycol polyethylene glycol is preferable, and polyethylene glycol having a molecular weight of 500 to 10,000 is particularly preferable.
- the 5-sulfoisophthalate is preferably copolymerized in an amount of 0.1 to 10 mol% based on all dicarboxylic acid components constituting the polyester.
- the polyoxyalkylene glycol having a molecular weight of 500 to 20000 is preferably copolymerized in an amount of 0.1 to 10.0% by weight based on the weight of the resulting polyester.
- copolymer components may be used alone, but when two or more types are copolymerized, the effect of improving the heat resistance of the polyester becomes more remarkable.
- the polyester of the present invention is usually produced by any one of the following processes.
- a low polymer is obtained by a transesterification reaction, and a high molecular weight polymer is obtained by a subsequent polycondensation reaction.
- the reaction temperature is 250 ° C. or lower and the pressure is 1.2 ⁇ 100,000 Pa or higher.
- the polymerization temperature is preferably shortened as the reaction temperature is 280 ° C. or lower and the pressure is reduced, but it is preferable to maintain 110 Pa or higher.
- 1,2-propanediol having a boiling point lower than that of ethylene glycol is preferentially volatilized and may not be contained in the polyester in a necessary amount.
- the reaction temperature is 230 ° C. or lower and the pressure is atmospheric pressure or higher.
- the polymerization temperature is preferably shortened as the reaction temperature is 280 ° C. or lower and the pressure is reduced, but it is preferable to maintain 110 Pa or higher.
- 1,2-propanediol having a boiling point lower than that of ethylene glycol is preferentially volatilized at a higher temperature and lower pressure in each reaction stage, and the necessary amount may not be contained in the polyester.
- a compound such as magnesium, manganese, calcium, cobalt, lithium, and titanium may be used as a catalyst as in the case of the transesterification catalyst.
- a titanium compound, an aluminum compound, a tin compound, an antimony compound, a germanium compound, or the like is used as a catalyst used in the polycondensation.
- magnesium compound used in this case examples include magnesium oxide, magnesium hydroxide, magnesium alkoxide, magnesium acetate, and magnesium carbonate.
- manganese compounds include manganese chloride, manganese bromide, manganese nitrate, manganese carbonate, manganese acetylacetonate, and manganese acetate.
- the calcium compound examples include calcium oxide, calcium hydroxide, calcium alkoxide, calcium acetate, and calcium carbonate.
- cobalt compound examples include cobalt chloride, cobalt nitrate, cobalt carbonate, cobalt acetylacetonate, cobalt naphthenate, and cobalt acetate tetrahydrate.
- lithium compound examples include lithium oxide, lithium hydroxide, lithium alkoxide, lithium acetate, and lithium carbonate.
- titanium compounds include titanium alkoxides such as titanium complexes, tetra-i-propyl titanate, tetra-n-butyl titanate, tetra-n-butyl titanate tetramer, titanium oxides obtained by hydrolysis of titanium alkoxide, and titanium acetylacetonate. Etc.
- a titanium complex having a polycarboxylic acid and / or a hydroxycarboxylic acid and / or a polyhydric alcohol as a chelating agent is preferable from the viewpoint of the thermal stability of the polymer, the color tone, and the small amount of deposit around the mouthpiece.
- the chelating agent for the titanium compound include lactic acid, citric acid, mannitol, tripentaerythritol and the like.
- Examples of the aluminum compound include aluminum carboxylate, aluminum alkoxide, aluminum chelate compound, basic aluminum compound, and the like, specifically, aluminum acetate, aluminum hydroxide, aluminum carbonate, aluminum ethoxide, aluminum isopropoxide, aluminum acetyl. Examples include acetonate and basic aluminum acetate.
- tin compounds include monobutyltin oxide, tin acetate, tin octylate and tin alkoxide.
- Antimony compounds include antimony alkoxide, antimony glycolate and antimony trioxide.
- germanium compounds include germanium alkoxide and germanium oxide.
- These metal compounds may be hydrates.
- the polyester is preferably added with a phosphorus compound as a stabilizer.
- a phosphorus compound as a stabilizer.
- phosphoric acid, trimethyl phosphate, ethyl diethylphosphonoacetate and the like are preferable, and 3,9-bis (2,6-di-t-butyl-4-methylphenoxy) represented by the following chemical formula (1) ) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane (PEP-36: manufactured by Asahi Denka Co., Ltd.) and tetrakis (2,4- Trivalent phosphorus compounds such as di-t-butyl-5-methylphenyl) [1,1-biphenyl] -4,4'-diylbisphosphonite (GSY-P101: manufactured by Osaki Kogyo Co., Ltd.) improve color tone and heat resistance From the viewpoint of
- a dye used for a resin or the like as a color tone adjusting agent may be added.
- COLOR INDEX GENERIC NAME, blue color tone modifiers such as SOLVENT BLUE 104 and SOLVENT BLUE 45, and purple color tone modifiers such as SOLVENT VIOLET 36 do not contain halogens that are likely to cause equipment corrosion. The heat resistance at high temperatures is relatively good and the color developability is excellent, which is preferable. These may be used alone or in combination of two or more.
- an antioxidant an ultraviolet absorber, a flame retardant, a fluorescent brightening agent, a matting agent, a plasticizer or an antifoaming agent, or other additives may be blended as necessary.
- the polyalkylene terephthalate obtained by the above method may be further subjected to solid phase polymerization.
- the solid-state polymerization is not particularly limited in apparatus and method, but is carried out by heat treatment under an inert gas atmosphere or under reduced pressure. Any inert gas may be used as long as it is inert to the polyester, and examples thereof include nitrogen, helium, carbon dioxide, etc. Nitrogen is preferably used from the viewpoint of economy. Further, under reduced pressure, it is advantageous to use more reduced pressure conditions because the time required for the solid-phase polycondensation reaction can be shortened. However, maintaining 110 Pa or more can reduce the component derived from 1,2-propanediol in the polyester. It is preferable for remaining.
- the polyester product obtained in the present invention can be recycled.
- the polyester waste of the present invention is used as a raw material, and a depolymerization reaction is performed with a glycol component to obtain bis (hydroxyalkyl) terephthalate.
- This may be polymerized again, but is preferably further transesterified with methanol or ethanol to give dimethyl terephthalate or diethyl terephthalate.
- terephthalic acid dialkyl esters are preferred because they can be purified to high purity by distillation. The terephthalic acid dialkyl ester thus obtained can be used for polymerization again.
- the polyester obtained in the present invention can be produced by batch polymerization, semi-continuous polymerization, or continuous polymerization.
- the polyester chip obtained in the present invention can be formed into various molded products such as fibers, films, sheets, bottles and the like by a normal polyester molding method.
- the product can be used in areas such as fibers, films and resins, and various end products can be manufactured.
- a method for obtaining a polyester fiber can employ a normal melt spinning-stretching process. Specifically, after the polyalkylene terephthalate is heated to the melting point or higher and melted, it is discharged from the pores, cooled and solidified with cooling air, applied with an oil agent, taken up by the take-up roller, and disposed after the take-up roller. The undrawn yarn can be collected by winding with a winding device.
- the undrawn yarn wound in this way becomes a polyester fiber to which physical properties such as mechanical properties are applied by drawing with a pair of heated rollers and finally applying tension or relaxation heat treatment. .
- it can carry out continuously, without winding once after taking up in the above-mentioned melt spinning process, and it is preferable to set it as continuous extending
- the draw ratio, the stretching temperature, and the heat treatment conditions can be appropriately selected depending on the fineness, strength, elongation, shrinkage, etc. of the target fiber.
- Terephthalic acid High-purity terephthalic acid manufactured by Mitsui Chemicals (1,2-propanediol ⁇ 15 ppm (not detected)) ⁇ Dimethyl terephthalate: SK Chemical Co., Ltd. (1,2-propanediol ⁇ 15 ppm (not detected))
- Polyethylene glycol Sanyo Kasei Co., Ltd.
- Color tone of polymer was measured as a Hunter value (L, a, b value) using a color difference meter (SM color computer model SM-T45, manufactured by Suga Test Instruments Co., Ltd.).
- the thermal stability index ( ⁇ IV) which is an index of decrease in intrinsic viscosity at the time of melting, is obtained by chipping the polymer collected from the start of measurement to the end of measurement after the start of extrusion after holding at 295 ° C. ⁇ 60 minutes. It mixed, the intrinsic viscosity (IVb) was measured, and it calculated
- ⁇ IV (IVa) ⁇ (IVb) IVa: Intrinsic viscosity before melt extrusion IVb: Intrinsic viscosity after melt extrusion
- a 1490 ⁇ g / ml aqueous solution of 1,2-butanediol was prepared and used as an internal standard solution A.
- 0.1 g of a sample was weighed into a vial, 0.015 ml of internal standard solution A and 1 ml of aqueous ammonia were added and sealed, heated at 150 ° C. for 3 hours, and then allowed to cool to room temperature.
- the mixture was shaken for 15 minutes and centrifuged at 4000 G for 3 minutes.
- the supernatant liquid was taken out and measured with a gas chromatograph (Hewlett Packard 5890 series II, inlet: split / splitless inlet, detector: hydrogen flame ionization detector) under the following setting conditions, and a calibration curve described later was obtained. Used to determine the content.
- a gas chromatograph Hewlett Packard 5890 series II, inlet: split / splitless inlet, detector: hydrogen flame ionization detector
- Injector temperature 220 ° C
- Column head pressure 20 psi
- Carrier gas Helium Sample introduction method: Division (Linear flow rate 25 ml / min)
- Bulkhead purge Helium 3.0 ml / min
- Sample introduction amount 1.0 ⁇ l Detector temperature: 220 ° C
- Gas flow rate hydrogen 40 ml / min, air 400 ml / min, nitrogen 40 ml / min
- Oven temperature rise start temperature 60 ° C. (holding time 2 minutes)
- Oven temperature rise stop temperature 220 ° C (holding time 30 seconds)
- Oven heating rate 20 ° C / min (linear slope)
- a calibration curve for 1,2-propanediol was prepared according to the following procedure.
- a 2500 ⁇ g / ml aqueous solution of 1,2-propanediol was prepared and used as standard mother liquor B.
- Add 0.003 to 0.08 ml of standard mother liquor B and 0.025 ml of internal standard solution A in a 5 ml volumetric flask, and maintain a constant volume with a mixed solvent (containing methanol: purified water 2: 1 and ethylene glycol 1.1%).
- Seven types of standard solutions C were prepared by changing the amount of standard mother solution B.
- the supernatant liquid was taken out, measured under the above-mentioned setting conditions by gas chromatography (manufactured by Hewlett Packard, 5890 series II), and the content was determined using a calibration curve described later. As a result, standard addition of 1,2-propanediol The recovery rate was 105%.
- ethylene glycol was weighed, dissolved and fixed in acetone in 5 ml volumetric flask.
- the prepared solution was measured using a gas chromatograph (Hewlett Packard 5890 series II, inlet: split / splitless inlet, detector: hydrogen flame ionization detector) under the following setting conditions. -The content was determined using a calibration curve measured and prepared in the same manner using propanediol.
- Injector temperature 250 ° C
- Column head pressure 15 psi
- Carrier gas Helium Sample introduction method: Division (Linear flow rate 50ml / min)
- Bulkhead purge Helium 3.0 ml / min
- Sample introduction amount 1.0 ⁇ l
- Detector temperature 250 ° C
- Gas flow rate hydrogen 40ml / min, air 400ml / min, nitrogen 40ml / min
- Oven temperature rise start temperature 50 ° C (holding time 3 minutes)
- Oven temperature rise stop temperature 250 ° C (holding time 1 minute)
- Oven heating rate 15 ° C / min (linear slope)
- the sample was pulverized with sandpaper and a pulverizer, then heated with copper oxide, completely oxidized to carbon dioxide, and reduced to graphite with iron powder to convert it into a carbon single compound.
- the obtained graphite sample was introduced into an AMS apparatus, and the 14 C concentration was measured. Note that the 14 C concentration of oxalic acid (supplied by the American Standards and Science and Technology Association NIST), which is a standard substance, was also measured.
- the ratio of 14 C and 12 C in the sample (14 C / 12 C) to 14 As, the ratio of 14 C and 12 C in standard (14 C / 12 C) and 14 Ar, the following equation delta 14 C was determined.
- ⁇ 14 C ⁇ ( 14 As ⁇ 14 Ar) / 14 Ar ⁇ ⁇ 1000
- pMC percent Modern Carbon
- Reference example 1 The obtained 20 kg biomass resource-derived ethylene glycol (manufactured by Changchun Taisei Group) was subjected to a distillation operation under the conditions of a theoretical plate number of 40, a pressure of 50 mmHg, and a reflux ratio of 10 to obtain crude ethylene glycol as a tower bottom residue.
- This crude ethylene glycol contained 3510 ppm of 1,2-propanediol.
- the obtained crude ethylene glycol was heated in a heating kettle with a preset temperature of 190 ° C. for 15 hours, and then cooled to room temperature.
- activated carbon (Nimura Chemical Co., Ltd .: Dazai SGA) was washed with soft water and dried, and the activated carbon after drying was filled in the activated carbon treatment facility.
- the activated carbon layer had a thickness of 300 cm and a space velocity of 0.57 hr ⁇ 1 , and was collected after flowing the phobic ethylene glycol which had been heated and cooled as described above into the activated carbon layer.
- a biomass resource-derived ethylene glycol (purified product) having a content of 1,2-propanediol of 220 ppm was obtained.
- Reference example 4 Biomass resource-derived ethylene glycol (manufactured by Changchun Taisei Group) was heated in a heating kettle with a set temperature of 190 ° C. for 10 hours, and then cooled to room temperature.
- the activated carbon was washed with soft water and dried, and the activated carbon after drying was filled in an activated carbon treatment facility.
- the activated carbon layer had a thickness of 150 cm and a space velocity of 1.14 hr ⁇ 1 .
- the biomass resource-derived ethylene glycol that had been heated and cooled as described above was flowed into the activated carbon layer and then collected. Finally, a biomass resource-derived ethylene glycol (crude product) having a content of 1,2-propanediol of 2780 ppm was obtained.
- Reference Example 6 Ethylene glycol derived from fossil resources (produced by Mitsubishi Chemical Corporation) in which 1,2-propanediol is not detected (less than 15 ppm) is referred to as ethylene glycol of Reference Example 6.
- Example 1 Hereinafter, all the ethylene glycol used in Example 1 was the biomass resource-derived ethylene glycol (refined product) obtained in Reference Example 1.
- Table 1 summarizes the types of biomass resource-derived ethylene glycol and dicarboxylic acid components, the types of copolymerization components, esterification catalysts or transesterification catalysts, and the amounts added.
- Table 2 summarizes the types and amounts of the polymerization catalyst, phosphorus compound and other additives added to the polycondensation tank, and the amount of titanium oxide particles added.
- Example 2 Hereinafter, all the ethylene glycol used in Example 2 was the biomass resource-derived ethylene glycol (refined product) obtained in Reference Example 1.
- antimony trioxide equivalent to 250 ppm in terms of antimony atoms and trimethyl phosphate equivalent to 20 ppm in terms of phosphorus atoms were added to the esterification reaction product as an ethylene glycol solution. Further, after 5 minutes, an ethylene glycol slurry of titanium oxide particles was added in an amount corresponding to 0.1% by weight in terms of titanium oxide particles to the obtained polymer. Thereafter, the reaction system was decompressed while stirring at 30 rpm to start the reaction. The reactor was gradually heated from 250 ° C. to 280 ° C., and the pressure was reduced to 110 Pa. The time to reach the final temperature and final pressure was both 60 minutes.
- Example 5 Polymer pellets were obtained in the same manner as in Example 1 except that 100 kg of dimethyl terephthalate and 58 kg of ethylene glycol were charged and 1.0 kg of polyethylene glycol having an average molecular weight of 1000 was charged at the same time. The results are summarized in Table 3.
- Example 6 Polymer pellets were obtained in the same manner as in Example 2 except that polyethylene glycol having an average molecular weight of 1000 corresponding to 1% by weight with respect to the weight of the obtained polymer was added to the esterification reaction product. The results are summarized in Table 3.
- Example 7 Polymer pellets were obtained in the same manner as in Example 2 except that polyethylene glycol having an average molecular weight of 1000 corresponding to 8% by weight of the obtained polymer was added to the esterification reaction product. The results are summarized in Table 3.
- Example 10 Polymer pellets were obtained in the same manner as in Example 1 except that 100 kg of dimethyl terephthalate and 58 kg of ethylene glycol were charged and 1.5 kg of sodium 5-sulfoisophthalate dimethyl ester was charged at the same time. The results are summarized in Table 3.
- Example 11 Polymer pellets were obtained in the same manner as in Example 2, except that 1 mol% of 5-dimethylsulfoisophthalic acid sodium dimethyl ester was added to the esterification reaction product based on the total dicarboxylic acid component constituting the resulting polymer. The results are summarized in Table 3.
- Example 12 Polymer pellets were obtained in the same manner as in Example 2 except that 8 mol% of 5-sulfoisophthalic acid sodium dimethyl ester was added to the esterification reaction product based on the total dicarboxylic acid component constituting the resulting polymer. The results are summarized in Table 3.
- Example 15 Polymer pellets were prepared in the same manner as in Example 1 except that 100 kg of dimethyl terephthalate and 58 kg of ethylene glycol were charged and 1.0 kg of polyethylene glycol having an average molecular weight of 1000 and 3.0 kg of sodium 5-sulfoisophthalate dimethyl ester were charged. Obtained. The results are summarized in Table 3.
- Example 16 Esterification reaction of polyethylene glycol having an average molecular weight of 1000 equivalent to 1% by weight with respect to the weight of the obtained polymer and 2-mol% sodium 5-sulfoisophthalic acid sodium dimethyl ester based on all dicarboxylic acid components constituting the obtained polymer Polymer pellets were obtained in the same manner as in Example 2 except for adding to the product. The results are summarized in Table 3.
- Examples 17 and 18 Polymer pellets were obtained in the same manner as in Example 16 except that the ethylene glycol used was changed as shown in Table 1. The results are summarized in Table 3.
- Examples 19-26 The same manner as in Example 16 except that the type and addition amount of the phosphorus compound to be added, the polymerization catalyst to be used and its addition amount, other additives and their addition amount, and the addition amount of titanium oxide were changed as shown in Table 2. Thus, polymer pellets were obtained. The results are summarized in Table 3.
- Example 27 The polyethylene terephthalate pellets obtained in Example 1 were vacuum dried at 150 ° C. for 12 hours, melted at a spinning temperature of 285 ° C., and then discharged from a spinneret having a hole diameter of 0.18 mm ⁇ and a hole number of 36, and a peripheral speed of 1000 m.
- An undrawn yarn was obtained by taking up with a take-up roller per minute. At this time, although some deposits were observed around the nozzle holes during spinning, thread breakage hardly occurred and almost no increase in filtration pressure was observed.
- the obtained undrawn yarn was subjected to drawing-heat treatment at a drawing temperature of 90 ° C. and a heat treatment temperature of 140 ° C. with a hot roll drawing machine at a draw ratio of 3.0 times to obtain a drawn yarn.
- Table 4 summarizes the results of measurement of the deposit around the base during spinning, the yarn breakage frequency, and the strength of the drawn yarn.
- Example 28-52 In the same manner as in Example 27, the polyethylene terephthalate pellets obtained in Examples 2 to 26 were spun and stretched, respectively. At this time, almost no deposit was observed around the die hole during spinning, and no yarn breakage occurred. The results are summarized in Table 4.
- Table 5 summarizes the types of ethylene glycol and dicarboxylic acid components, types of copolymerization components, esterification catalysts, and transesterification catalysts, and amounts added.
- Table 6 summarizes the types and amounts of the polymerization catalyst, phosphorus compound and other additives added to the polycondensation tank, and the amount of titanium oxide particles added.
- Comparative Examples 1 and 2 Polymer pellets were obtained in the same manner as in Example 1 except that the ethylene glycol used was changed as shown in Table 5. The evaluation results of the obtained polymer pellets are summarized in Table 7.
- Comparative Examples 3-5 Polymer pellets were obtained in the same manner as in Example 2 except that the ethylene glycol used was changed as shown in Table 5. The results are summarized in Table 7.
- Comparative Examples 6 and 7 Polymer pellets were obtained in the same manner as in Example 5 except that the ethylene glycol used was changed as shown in Table 5. The results are summarized in Table 7.
- Comparative Example 9 Polymer pellets were obtained in the same manner as in Comparative Example 8, except that polyethylene glycol having an average molecular weight of 1000 corresponding to 8% by weight of the obtained polymer was added to the esterification reaction product. The results are summarized in Table 7.
- Comparative Examples 12 and 13 Polymer pellets were obtained in the same manner as in Example 10 except that the ethylene glycol used was changed as shown in Table 5. The results are summarized in Table 7.
- Comparative Examples 14, 16, and 17 Polymer pellets were obtained in the same manner as in Example 11 except that the ethylene glycol used was changed as shown in Table 5. The results are summarized in Table 7.
- Comparative Example 15 Polymer pellets were obtained in the same manner as in Comparative Example 14 except that 8 mol% of 5-sulfoisophthalic acid sodium dimethyl ester was added to the esterification reaction product based on the total dicarboxylic acid component constituting the resulting polymer. The results are summarized in Table 7.
- Comparative Examples 18 and 19 Polymer pellets were obtained in the same manner as in Example 15 except that the ethylene glycol used was changed as shown in Table 5. The results are summarized in Table 7.
- Comparative Examples 20-22 Polymer pellets were obtained in the same manner as in Example 16 except that the ethylene glycol used was changed as shown in Table 5. The results are summarized in Table 7.
- Comparative Examples 23-30 The same manner as in Comparative Example 22 except that the type and amount of phosphorus compound to be added, the polymerization catalyst to be used and its addition amount, other additives and their addition amount, and the addition amount of titanium oxide were changed as shown in Table 6. Thus, polymer pellets were obtained. The results are summarized in Table 7.
- Comparative Examples 31-60 In the same manner as in Example 27, the polyethylene terephthalate pellets obtained in Comparative Examples 1 to 30 were spun and stretched, respectively. At this time, deposits were observed around the mouthpiece hole during spinning, and yarn breakage occurred. Table 8 summarizes the results of measurement of the deposit around the base during spinning, the yarn breakage frequency, and the strength of the drawn yarn.
Abstract
Description
pMC=(14Csa/14C50)×100
14C50:標準物質の14C濃度(1950年代の自然界における循環炭素中の14C濃度)
14Csa:測定サンプルの14C濃度
105:100=X:Y
・バイオマス資源由来エチレングリコール:長春大成集団製、(エチレングリコール=98.138重量%、1,2-プロパンジオール=5410ppm、1,2-ブタンジオール=2390ppm、2,3-ブタンジオール=6310ppm、1,4-ブタンジオール=4510ppm)。
・化石資源由来エチレングリコール:三菱化学社製、(エチレングリコール=99.989重量%、1,2-プロパンジオール<15ppm(検出せず)、ジエチレングリコール=110ppm)
・テレフタル酸:三井化学社製高純度テレフタル酸(1,2-プロパンジオール<15ppm(検出せず))
・テレフタル酸ジメチル:SKケミカル社製(1,2-プロパンジオール<15ppm(検出せず))
・ポリエチレングリコール:三洋化成社製(1,2-プロパンジオール<15ppm(検出せず))、平均分子量1000
・5-スルホイソフタル酸ナトリウムジメチルエステル:三洋化成社製(1,2-プロパンジオール<15ppm(検出せず))
オルソクロロフェノールを溶媒として25℃で測定した。
色差計(スガ試験機社製、SMカラーコンピュータ型式SM-T45)を用いて、ハンター値(L、a、b値)として測定した。
予め150℃×20hr×真空下(133Pa以下)で乾燥した試料の固有粘度(IVa)を測定した。この乾燥した試料6.0gを、宝工業社製メルトインデクサー(MX-101B)を使用し、以下の設定条件で溶融押出した。
荷重 1000g
オリフィス内径 2.092mmφ
測定距離 25.4mm
シリンダー部温度×保持時間 295℃×60分
ΔIV=(IVa)-(IVb)
IVa:溶融押出前の固有粘度
IVb:溶融押出後の固有粘度
2-アミノエタノールを溶媒とし、内部標準物質である1,6-ヘキサンジオールを加えて260℃で分解した。冷却後、メタノールを加えたのち酸で中和し、析出物をろ過した。ろ液をガスクロマトグラフィ(島津製作所社製、GC-14B)にて測定した。
本分析に用いた試薬は以下の通りである。
・1,2-プロパンジオール(和光純薬工業株式会社製、特級)
・1,2-ブタンジオール(東京化成工業株式会社製、>99%、1,2-プロパンジオール<15ppm(検出せず))
・アンモニア水(和光純薬工業株式会社製、特級28-30%)
・メタノール(和光純薬工業株式会社製、残留農薬-PCB試験用、1,2-プロパンジオール<15ppm(検出せず))
・テレフタル酸(和光純薬工業株式会社製、一級、1,2-プロパンジオール<15ppm(検出せず))
・精製水(ミリポア社製、Milli-Q Integral3で調製)
インジェクタ温度:220℃
カラムヘッド圧:20psi
キャリアガス:ヘリウム
試料導入方法:分割(線流速 25ml/分)
隔壁パージ:ヘリウム 3.0ml/分
試料導入量:1.0μl
ディテクタ温度:220℃
ガス流量:水素40ml/分,空気400ml/分,窒素40ml/分
オーブン昇温開始温度:60℃(保持時間2分)
オーブン昇温停止温度:220℃(保持時間30秒)
オーブン昇温速度:20℃/分(直線傾斜)
本分析に用いた試薬は以下の通りである。
・1,2-プロパンジオール(和光純薬工業株式会社製、特級)
・アセトン(和光純薬工業株式会社製、残農・PCB試験用、1,2-プロパンジオール<15ppm(検出せず))
インジェクタ温度:250℃
カラムヘッド圧:15psi
キャリアガス:ヘリウム
試料導入方法:分割(線流速 50ml/分)
隔壁パージ:ヘリウム 3.0ml/分
試料導入量:1.0μl
ディテクタ温度:250℃
ガス流量:水素40ml/分,空気400ml/分,窒素40ml/分
オーブン昇温開始温度:50℃(保持時間3分)
オーブン昇温停止温度:250℃(保持時間1分)
オーブン昇温速度:15℃/分(直線傾斜)
ポリエステル繊維の紡出開始から120時間(繊維1tを紡糸)後の口金孔周辺の堆積物量を、長焦点顕微鏡を用いて観察した。繊維1tを紡糸した際に、堆積物がほとんど認められず、糸切れも発生しない状態を◎(合格・良好)、堆積物が認められ、1回以上糸切れが発生する状態を×(不合格)として判定した。
東洋ボードウイン社製テンシロン引張試験機を用いて、試料長25cm、引張速度30cm/分でS-S曲線を求め、ポリエステルの延伸糸の強度および伸度を算出した。
ASTM D6866に従いポリエステルのバイオ化率を求めた。
Δ14C={(14As-14Ar)/14Ar}×1000
このΔ14Cから次式により、pMC(percent Modern Carbon)を求めた。
pMC=Δ14C/10+100
バイオ化率(%)=0.95×pMC
入手した20kgバイオマス資源由来エチレングリコール(長春大成集団製)を蒸留操作として、理論段数40段、圧力50mmHg、還流比10の条件で実施し、塔底残留物として粗エチレングリコールを得た。この粗エチレングリコールは、1,2-プロパンジオールを3510ppm含有していた。得られた粗エチレングリコールを設定温度190℃の加熱釜中で15時間加熱した後、室温まで冷却した。
活性炭層の厚さを200cmとし、空間速度を0.86hr-1とした以外は参考例1と同様にして、最終的に1,2-プロパンジオールの含有量が900ppmのバイオマス資源由来エチレングリコール(精製品)を得た。
蒸留操作後の粗エチレングリコールの加熱処理時間を30時間とし、活性炭層の厚さを500cmとし、空間速度を0.34hr-1とした以外は参考例1と同様にして、最終的に1,2-プロパンジオールの含有量が50ppmのバイオマス資源由来エチレングリコール(精製品)を得た。
バイオマス資源由来エチレングリコール(長春大成集団製)を設定温度190℃の加熱釜中で10時間加熱した後、室温まで冷却した。
入手した20kgバイオマス資源由来エチレングリコール(長春大成集団製)を1回目の蒸留操作として、理論段数30段、圧力50mmHg、還流比5の条件にて実施したところ、塔底残留物として粗エチレングリコールを得た。この粗エチレングリコールは、1,2-プロパンジオールを4190ppm含有していた。続いて2回目の蒸留として、理論段数30段、圧力50mmHg、還流比5の条件で実施した。最終的に塔底残留物として、1,2-プロパンジオールの含有量が3030ppmのバイオマス資源由来エチレングリコール(粗精製品)を得た。
1,2-プロパンジオールが検出されない(15ppm未満)化石資源由来エチレングリコール(三菱化学社製)を、参考例6のエチレングリコールとする。
得られるポリマーに対してマグネシウム原子換算で60ppm相当の酢酸マグネシウムと、テレフタル酸ジメチル100kgとエチレングリコール58kgを、150℃、窒素雰囲気下で溶融後、攪拌しながら230℃まで3時間かけて昇温し、メタノールを留出させ、エステル交換反応をおこない、ビス(ヒドロキシエチル)テレフタレートを得た。
以下、実施例1で用いたエチレングリコールは全て参考例1で得られたバイオマス資源由来エチレングリコール(精製品)を用いた。
以下、実施例2で用いたエチレングリコールは全て参考例1で得られたバイオマス資源由来エチレングリコール(精製品)を用いた。
用いるエチレングリコールを表1に示した通り変更した以外は、製造例1および実施例2と同様にしてポリマーペレットを得た。得られたポリマーペレットの評価結果を表3にまとめた。
テレフタル酸ジメチル100kgとエチレングリコール58kgを仕込むと同時に平均分子量1000のポリエチレングリコールを1.0kg仕込んだ以外は、実施例1と同様にしてポリマーペレットを得た。結果を表3にまとめた。
得られるポリマーの重量に対して1重量%相当の平均分子量1000のポリエチレングリコールをエステル化反応物に添加した以外は、実施例2と同様にしてポリマーペレットを得た。結果を表3にまとめた。
得られるポリマーの重量に対して8重量%相当の平均分子量1000のポリエチレングリコールをエステル化反応物に添加した以外は、実施例2と同様にしてポリマーペレットを得た。結果を表3にまとめた。
用いるエチレングリコールを表1に示した通り変更した以外は、実施例6と同様にしてポリマーペレットを得た。結果を表3にまとめた。
テレフタル酸ジメチル100kgとエチレングリコール58kgを仕込むと同時に5-スルホイソフタル酸ナトリウムジメチルエステルを1.5kg仕込んだ以外は、実施例1と同様にしてポリマーペレットを得た。結果を表3にまとめた。
得られるポリマーを構成する全ジカルボン酸成分を基準として1mol%相当の5-スルホイソフタル酸ナトリウムジメチルエステルをエステル化反応物に添加した以外は、実施例2と同様にしてポリマーペレットを得た。結果を表3にまとめた。
得られるポリマーを構成する全ジカルボン酸成分を基準として8mol%相当の5-スルホイソフタル酸ナトリウムジメチルエステルをエステル化反応物に添加した以外は、実施例2と同様にしてポリマーペレットを得た。結果を表3にまとめた。
用いるエチレングリコールを表1に示した通り変更した以外は、実施例11と同様にしてポリマーペレットを得た。結果を表3にまとめた。
テレフタル酸ジメチル100kgとエチレングリコール58kgを仕込むと同時に平均分子量1000のポリエチレングリコールを1.0kg、5-スルホイソフタル酸ナトリウムジメチルエステルを3.0kg仕込んだ以外は、実施例1と同様にしてポリマーペレットを得た。結果を表3にまとめた。
得られるポリマーの重量に対して1重量%相当の平均分子量1000のポリエチレングリコールと、得られるポリマーを構成する全ジカルボン酸成分を基準として2mol%相当の5-スルホイソフタル酸ナトリウムジメチルエステルをエステル化反応物に添加した以外は、実施例2と同様にしてポリマーペレットを得た。結果を表3にまとめた。
用いるエチレングリコールを表1に示した通り変更した以外は、実施例16と同様にしてポリマーペレットを得た。結果を表3にまとめた。
添加するリン化合物の種類と添加量、用いる重合触媒とその添加量、その他添加剤とその添加量、および酸化チタンの添加量を表2に示した通り変更した以外は、実施例16と同様にしてポリマーペレットを得た。結果を表3にまとめた。
実施例1で得られたポリエチレンテレフタレートのペレットを150℃で12時間真空乾燥した後、紡糸温度285℃で溶融した後、孔径0.18mmφ、孔数36個の紡糸口金から吐出し、周速1000m/分の引き取りローラで引取って、未延伸糸を得た。この際、紡糸時の口金孔周辺の堆積物は多少見られたが、糸切れはほとんど発生せず、濾圧上昇もほとんど認められなかった。得られた未延伸糸をホットロール延伸機にて延伸温度90℃、熱処理温度140℃とし、延伸倍率3.0倍として、延伸-熱処理を施し、延伸糸を得た。紡糸時の口金周りの堆積物と糸切れ頻度および延伸糸の強伸度を測定した結果を表4にまとめた。
実施例27と同様にして、実施例2~26で得られたポリエチレンテレフタレートのペレットをそれぞれ紡糸・延伸した。この際、紡糸時の口金孔周辺の堆積物はほとんど認められず、糸切れも発生しなかった。結果を表4にまとめた。
用いるエチレングリコールを表5の通り変更した以外は、実施例1と同様にしてポリマーペレットを得た。得られたポリマーペレットの評価結果を表7にまとめた。
用いるエチレングリコールを表5の通り変更した以外は、実施例2と同様にしてポリマーペレットを得た。結果を表7にまとめた。
用いるエチレングリコールを表5の通り変更した以外は、実施例5と同様にしてポリマーペレットを得た。結果を表7にまとめた。
用いるエチレングリコールを表5の通り変更した以外は、実施例6と同様にしてポリマーペレットを得た。結果を表7にまとめた。
得られるポリマーの重量に対して8重量%相当の平均分子量1000のポリエチレングリコールをエステル化反応物に添加した以外は、比較例8と同様にしてポリマーペレットを得た。結果を表7にまとめた。
用いるエチレングリコールを表5の通り変更した以外は、実施例10と同様にしてポリマーペレットを得た。結果を表7にまとめた。
用いるエチレングリコールを表5の通り変更した以外は、実施例11と同様にしてポリマーペレットを得た。結果を表7にまとめた。
得られるポリマーを構成する全ジカルボン酸成分を基準として8mol%相当の5-スルホイソフタル酸ナトリウムジメチルエステルをエステル化反応物に添加した以外は、比較例14と同様にしてポリマーペレットを得た。結果を表7にまとめた。
用いるエチレングリコールを表5の通り変更した以外は、実施例15と同様にしてポリマーペレットを得た。結果を表7にまとめた。
用いるエチレングリコールを表5の通り変更した以外は、実施例16と同様にしてポリマーペレットを得た。結果を表7にまとめた。
添加するリン化合物の種類と添加量、用いる重合触媒とその添加量、その他添加剤とその添加量、および酸化チタンの添加量を表6に示した通り変更した以外は、比較例22と同様にしてポリマーペレットを得た。結果を表7にまとめた。
実施例27と同様にして、比較例1~30で得られたポリエチレンテレフタレートのペレットをそれぞれ紡糸・延伸した。この際、紡糸時の口金孔周辺には堆積物が認められ、糸切れが発生した。紡糸時の口金周りの堆積物と糸切れ頻度および延伸糸の強伸度を測定した結果を表8にまとめた。
Claims (10)
- ジカルボン酸および/またはそのエステル形成性誘導体とジオールから得られるポリエステルであって、前記ポリエステル中に含まれる1,2-プロパンジオール由来の成分が15~500ppm含有されていることを特徴とするポリエステル。
- 5-スルホイソフタル酸塩および/またはそのエステル形成性誘導体を共重合成分として含むことを特徴とする請求項1に記載のポリエステル。
- 分子量が500~20000のポリオキシアルキレングリコールを共重合成分として含むことを特徴とする請求項1または2に記載のポリエステル。
- 前記ジオールがエチレングリコールである請求項1から3のいずれか記載のポリエステル。
- 請求項1~4のいずれか1項に記載のポリエステルからなる成形品。
- 1,2-プロパンジオールの含有量が45~1000ppmであるジオール。
- 前記ジオールがエチレングリコールである請求項6記載のジオール。
- ジオールを、理論段数が40段以上、還流比10以上での蒸留および、空間速度0.1~1.1hr-1の活性炭濾過層での吸着分離を組み合わせて精製することを特徴とする請求項6または7に記載のジオールの製造方法。
- ジカルボン酸および/またはそのエステル形成性誘導体とジオールとをエステル化またはエステル交換反応させた後、減圧下で重縮合反応してポリエステルを製造する方法において、1,2-プロパンジオールの含有量が45~1000ppmであるジオールを用いることを特徴とするポリエステルの製造方法。
- 前記ジオールがエチレングリコールである請求項9記載のポリエステルの製造方法。
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EP12829902.1A EP2684906B1 (en) | 2011-09-06 | 2012-08-24 | Polyester with excellent heat resistance and method for producing same |
BR112013024714-2A BR112013024714B1 (pt) | 2011-09-06 | 2012-08-24 | Poliester obtido a partir de um acido dicarboxilico e/ou um derivado formador de ester do mesmo e um diol, moldados, diol, metodo de fabricaqao de um diol e metodo de fabricaqao de poliester |
CA2834247A CA2834247A1 (en) | 2011-09-06 | 2012-08-24 | Polyester with excellent thermostability and manufacturing method therefor |
CN201280021260.6A CN103502303B (zh) | 2011-09-06 | 2012-08-24 | 耐热性优异的聚酯和其制造方法 |
US14/114,937 US9175133B2 (en) | 2011-09-06 | 2012-08-24 | Polyester with excellent thermostability and manufacturing method therefor |
JP2012539534A JP5316725B1 (ja) | 2011-09-06 | 2012-08-24 | 耐熱性に優れたポリエステルおよびその製造方法 |
KR1020137024436A KR101391223B1 (ko) | 2011-09-06 | 2012-08-24 | 내열성이 뛰어난 폴리에스테르 및 그 제조방법 |
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EP (1) | EP2684906B1 (ja) |
JP (1) | JP5316725B1 (ja) |
KR (1) | KR101391223B1 (ja) |
CN (1) | CN103502303B (ja) |
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CN103502303B (zh) | 2015-04-29 |
KR101391223B1 (ko) | 2014-05-07 |
TWI429678B (zh) | 2014-03-11 |
EP2684906A4 (en) | 2014-04-16 |
MY163183A (en) | 2017-08-15 |
BR112013024714A2 (pt) | 2016-12-20 |
US20140058059A1 (en) | 2014-02-27 |
BR112013024714B1 (pt) | 2020-11-24 |
US9175133B2 (en) | 2015-11-03 |
EP2684906A1 (en) | 2014-01-15 |
CA2834247A1 (en) | 2013-03-14 |
JP5316725B1 (ja) | 2013-10-16 |
CN103502303A (zh) | 2014-01-08 |
KR20130116369A (ko) | 2013-10-23 |
TW201319116A (zh) | 2013-05-16 |
EP2684906B1 (en) | 2016-04-06 |
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