WO2005075539A1 - ポリエステル重合触媒およびこれを用いて製造されたポリエステル並びにポリエステルの製造方法 - Google Patents
ポリエステル重合触媒およびこれを用いて製造されたポリエステル並びにポリエステルの製造方法 Download PDFInfo
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- WO2005075539A1 WO2005075539A1 PCT/JP2005/001795 JP2005001795W WO2005075539A1 WO 2005075539 A1 WO2005075539 A1 WO 2005075539A1 JP 2005001795 W JP2005001795 W JP 2005001795W WO 2005075539 A1 WO2005075539 A1 WO 2005075539A1
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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
- C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds thereof
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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
- C08G63/87—Non-metals or inter-compounds thereof
Definitions
- Polyester polymerization catalyst polyester produced using the same, and method for producing polyester
- the present invention relates to a polyester polymerization catalyst, a polyester produced by using the same, and a method for producing a polyester. More specifically, the present invention relates to a catalyst having excellent catalytic activity, excellent color tone, heat stability and transparency, and particularly excellent The present invention relates to a polyester polymerization catalyst which provides a polyester improved in point, a polyester produced using the same, and a method for producing the polyester.
- Polyesters typified by polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN) have excellent mechanical and chemical properties. Accordingly, a wide range of products, such as textiles for clothing and industrial materials, films and sheets for packaging and magnetic tape, bottles as hollow molded products, casings for electric and electronic parts, and other engineering plastic molded products. Used in various fields. In particular, saturated polyester bottles such as polyethylene terephthalate have excellent mechanical strength, heat resistance, transparency, and gas-nobility, so they can be used for filling beverages such as juice, carbonated beverages, and soft drinks, as well as eye drops and cosmetics. It is widely used as a container for such applications.
- PET polyethylene terephthalate
- PBT polybutylene terephthalate
- PEN polyethylene naphthalate
- PET polyethylene terephthalate
- a typical polyester which is mainly composed of an aromatic dicarboxylic acid and an alkylene glycol, has an esterification reaction between terephthalic acid or dimethyl terephthalate and ethylene glycol.
- Produces a mixture of oligomers such as bis (2-hydroxyethyl) terephthalate by transesterification, liquid-phase polycondensation using a catalyst at high temperature and under vacuum, followed by solid-phase polycondensation after granulation.
- Molding pellets are produced.
- the polyester pellets thus manufactured are manufactured by injection molding to produce a preform, then biaxially stretching such as blow molding of the preform, and then forming into a bottle shape.
- antimony or germanium compounds have been widely used as a polyester polycondensation catalyst used for such polycondensation of polyester.
- Antimony trioxide is a catalyst that is inexpensive and has excellent catalytic activity.However, if this is used as a main component, that is, in an amount added so that a practical polymerization rate can be exhibited, metal trioxide can be used during polycondensation. Precipitation of antimony causes darkening and foreign matter in the polyester, which also causes surface defects on the film. In addition, when it is used as a raw material for a hollow molded article, it is difficult to obtain a hollow molded article having excellent transparency. Under these circumstances, polyesters are desired, which do not contain antimony at all or do not contain antimony as the main component of the catalyst.
- this polymerization catalyst is a polymerization catalyst containing a metal component other than antimony, germanium, and titanium as a main metal component of the catalyst, and has excellent catalytic activity, excellent color tone and thermal stability, and transparency of molded articles.
- a polymerization catalyst which is excellent in properties and gives a polyester with less foreign matter.
- Patent Document 1 It has been known that aluminum compounds are generally inferior in catalytic activity (see, for example, Patent Document 1). However, by combining a phosphorus compound with an aluminum compound as a novel polycondensation catalyst that meets the above requirements, the polymerization activity is increased. It is disclosed and noted that it is improved (see, for example, Patent Documents 14 to 14).
- Patent Document 1 Japanese Patent Publication No. 46-40711
- Patent Document 1 JP 2001-131276 A
- Patent Document 2 JP 2001-163963 A
- Patent Document 3 JP 2001-163964 A
- Patent Document 4 Japanese Patent Application Laid-Open No. 2002-220446 Further, it is disclosed that the above-mentioned polycondensation catalyst system can provide a polyester having excellent heat stability, little generation of foreign matters and good transparency (see Patent Document 5). ).
- Patent Document 5 Japanese Patent Application Laid-Open No. 2001-354759
- the polyester obtained by the above-mentioned polycondensation catalyst system has good color tone, transparency and thermal stability, and meets the above requirements.
- the polyester obtained by this method may have a high content of foreign substances insoluble in the polyester due to differences in manufacturers and production lots of the aluminum compound, which is a component of the polycondensation catalyst, and the production conditions of the polyester.
- it has a problem that it cannot always be obtained stably at a low level, and reaches a level that is sufficiently satisfactory for ultra-fine fibers, highly transparent films for optics, or ultra-highly transparent molded products. It was not expected to be improved.
- FIG. 1 27 A1—MNR catalyst of an ethylene glycol solution of the aluminum compound of Example C3
- FIG. 3 shows a 31 P—MN R spectrum of a mixture of the aluminum compound solution of Example C3 and the phosphorus conjugate solution.
- FIG. 4 31 P—MN R spectrum of a mixture of the aluminum compound solution of Reference Example C1 and the phosphorus conjugate solution
- An object of the present invention is to provide an antimony conjugate having the above-mentioned disadvantages, a germanium compound and a titanium compound, which do not contain a catalyst as a main component, and which use an aluminum compound as a catalyst metal component to provide excellent catalytic activity. Excellent in color tone and thermal stability and excellent in the transparency of molded products, especially in the fields of ultra-fine fibers with few foreign substances, highly transparent films for optical use, and ultra-highly transparent molded products. Polyester and polyester An object of the present invention is to provide a polyester polymerization catalyst for providing a ester, a polyester produced using the same, and a method for producing a polyester.
- Polyester produced in the presence of at least one kind selected from the group consisting of aluminum compounds and at least one kind of polycondensation catalyst selected from the phosphorus conjugates! A polyester characterized in that the content of aluminum-based foreign matters insoluble in the polyester is 3500 ppm or less.
- Polyester produced in the presence of at least one kind selected from the group consisting of aluminum compounds and at least one kind of polycondensation catalyst selected from the phosphorus conjugates! A polyester characterized in that the haze value of the uniaxially stretched film is 2% or less.
- a polyester comprising at least an aluminum element, an alkaline earth metal element, an alkali metal element and a phosphorus element and having the following characteristics.
- the polyester according to any one of (1) to (5) which comprises at least an aluminum element, an alkaline earth metal element, an alkali metal element and a phosphorus element and has the following characteristics. .
- a polyester polymerization catalyst comprising an aluminum compound and a phosphorous conjugate, wherein the aluminum compound and the phosphorous sulfide are mixed in a solvent.
- the integrated value of the NMR spectrum peak of the phosphorus atom having a hydroxyl group bonded thereto is 10% of the integrated value of the NMR spectrum peak of the hydroxyl atom bonded phosphorus atom of the phosphorus compound alone solution before being mixed with the solution of the aluminum compound.
- the polymerization catalyst for polyester according to any one of (8) to (10), which is characterized by the above.
- the aluminum compound is characterized in that it is at least one selected from aluminum acetate, basic aluminum acetate, aluminum lactate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetyl acetonate ( 8)
- the polyester polymerization catalyst according to any one of the above (17).
- the catalyst activity is excellent, the molded article is excellent in transparency, and the foreign matter is particularly small!
- the present invention provides a polyester polymerization catalyst for providing a polyester, a polyester produced using the same, and a method for producing a polyester.
- aluminum compound constituting the polymerization catalyst of the present invention known aluminum compounds can be used without limitation.
- the aluminum compound include aluminum formate, aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, and aluminum triacetate.
- carboxylate inorganic acid salt and chelate compound are preferred.
- aluminum acetate, aluminum lactate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetylacetonate are further preferred. Especially preferred.
- the aluminum content is high, and aluminum acetate, aluminum chloride, aluminum hydroxide, and aluminum hydroxide chloride are more preferable. Further viewpoint of solubility aluminum acetate, basic aluminum acetate, aluminum chloride, Hydroxide and salt aluminum are preferred. Further, from the viewpoint of not corroding the apparatus, it is particularly preferable to use aluminum acetate and basic aluminum acetate.
- hydroxyl chloride aluminum is a general term for those commonly called polychloride aluminum, basic chloride aluminum, and the like, and those used for water supply can be used. These are represented, for example, by the general structural formula [Al (OH) C1] (where l ⁇ n ⁇ 5). this
- the above-mentioned aluminum acetate is a generic term for those having the structure of aluminum salt of acetic acid represented by basic aluminum acetate, aluminum triacetate, aluminum acetate solution, etc., among which, solubility and solution stability From the viewpoint of properties, use of basic aluminum acetate is preferred.
- the basic aluminum acetates aluminum monoacetate, aluminum diacetate, or those stabilized with boric acid are preferable.
- a material stabilized with boric acid it is preferable to use a material stabilized with boric acid in an amount equal to or less than an equimolar amount to basic aluminum acetate, and in particular, 1Z2 to 1Z3 mol ⁇
- the use of basic aluminum acetate stabilized with acid is preferred! / ⁇ .
- the stabilizer for basic aluminum acetate include urea and thiourea in addition to boric acid.
- any of the above-mentioned basic aluminum acetates which are soluble in a solvent such as water-glycol, particularly those which are soluble in water and Z or ethylene glycol, can be used for the catalytic activity and the quality of the obtained polyester. Preferred from the point of view.
- Solvents that can be used in the present invention are water and alkylene glycols.
- Alkylene glycols include ethylene glycol, diethylene glycol, triethylene glycol Propylene glycol, dipropylene glycol, tripropylene glycol, trimethylene glycol, ditrimethylene glycol, tetramethylene glycol, ditetramethylene glycol, neopentyldaricol and the like.
- it is ethylene glycol, trimethylene glycol, tetramethylene glycol, more preferably ethylene glycol. It is preferable to use one soluble in water and Z or ethylene glycol because the effects of the present invention can be remarkably exhibited.
- the above aluminum compound Te Contact ⁇ to 27 A1- NMR ⁇ vectors to be quantified by the method described in V Ru is preferred instrument embodiment use was dissolved in ethylene glycol - 15 — It is more preferable to use an ethylene glycol solution of an aluminum compound in which the integrated value of the peak appearing at 30 ppm is 0.3 or more with respect to the integrated value of the reference peak.
- the integrated value ratio of the peak is more preferably 0.35 or more. 0.50 or more is more preferable 0.50 or more is particularly preferable. If the integral value ratio of the peak is less than 0.30, the amount of aluminum-based foreign matter insoluble in polyester described later increases, and it may not be possible to secure 3500 ppm or less, which is not preferable.
- the method for setting the integrated value ratio of the peaks to 0.3 or more is not limited, but it is preferable that the temperature of the aluminum compound is not increased to 110 ° C. or more when the aluminum compound is formed into a solution. It is. 105 ° C or lower is more preferable 100 ° C or lower is more preferable.
- the aluminum compound is preferably added to the reaction system as an ethylene glycol solution as described above.
- the method of preparing the ethylene glycol solution is not limited, either.
- the aluminum glycol compound is dissolved in water, and then ethylene glycol is added to the aqueous solution.
- the embodiment is preferably carried out by a liquid displacement method in which water is distilled off by heating.
- solution includes all steps related to solution, such as dissolution or liquid replacement.
- the method of low-temperature filtration in the liquid replacement is performed under reduced pressure to achieve both low temperature and short time.
- I spoon of liquid replacement 55- 105 ° C is good Mashiku, 60- 100 o C in performing the force particularly preferably ⁇ .
- an aluminum alloy used for melting is used as a method of reducing the integrated value ratio of the peak to 0.3 or less.
- the quality of the pumium compound is also important. Selecting an item with a low degree of association is also an effective method.
- the method for suppressing the association of the aluminum compound before dissolution is not limited. For example, an additive that suppresses association during the preparation of the aluminum compound is added, the temperature of concentration and drying of the liquid when the aluminum compound is taken out as a solid in the preparation step is lowered, or the temperature during the drying is reduced. It is effective to reduce the degree of drying and produce the product with moisture. It is also a preferred embodiment to use the aluminum compound in the form of a solution such as an aqueous solution without isolation.
- Selection criteria for the aluminum compound having a low association degree include, for example, specifying the amount of insoluble matter when the aluminum compound is dissolved in water, specifying the crystallinity of the aluminum compound, and specifying the amount of water of crystallization of the aluminum compound. Is specified. It is also a preferred embodiment to use an additive for improving the solubility of the aluminum compound in a solvent such as water, or a compound for improving the stability of the aluminum compound against hydrolysis or the like.
- Water is added to basic aluminum acetate at a temperature of 50 ° C. or lower, preferably at room temperature for several hours or more.
- the stirring time is preferably at least 3 hours, more preferably at least 6 hours, particularly preferably at least 12 hours. Then, heat and stir at 60 ° C or more for several hours or more.
- the temperature in this case is preferably in the range of 60-100 ° C, more preferably 60-95 ° C. Shorter heating times are preferred.
- the concentration of the aqueous solution is preferably lOgZl-30gZl, particularly preferably 15gZl-20gZl.
- Ethylene glycol is added to the above aqueous solution.
- the added amount of ethylene glycol is preferably 0.5 to 5.0 times, more preferably 0.8 to 2.0 times the volume of the aqueous solution.
- a uniform water-Z ethylene glycol mixed solution is obtained.
- the solution is heated and water is distilled off to obtain an ethylene glycol solution.
- the temperature is preferably 70 ° C or higher and 200 ° C or lower. It is more preferred to stir at 150 ° C. or lower, further 120 ° C. or lower, particularly 110 ° C. or lower to distill off water. Also, when distilling The pressure may be reduced.
- heating is performed under reduced pressure and in an atmosphere of an inert gas such as Z or nitrogen or argon to distill off water to prepare a catalyst solution or slurry.
- an inert gas such as Z or nitrogen or argon
- ethylene glycol can be quickly distilled off at a lower temperature.
- distillation can be performed even at 80 ° C or lower, and the heat history given to the system can be further reduced.
- the above-mentioned basic aluminum acetate is soluble in a solvent such as water-glycol, and in particular, the one soluble in water and Z or ethylene glycol is preferably used in view of the catalytic activity and the quality of the obtained polyester. Is preferred.
- An aqueous solution of aluminum lactate is prepared.
- the preparation may be performed at room temperature or under heating !, but preferably at room temperature.
- the concentration of the aqueous solution is preferably from 20 gZl to 100 gZl, and more preferably from 50 to 80 gZl.
- Ethylene glycol is added to the aqueous solution.
- the amount of ethylene glycol added to the aqueous solution is 115 times the volume of the aqueous solution, and more preferably 2-3 times the volume.
- the temperature is preferably 70 ° C or higher, and more preferably 120 ° C or lower. More preferably, water is distilled off by stirring at 90 to 110 ° C for several hours.
- the amount of aluminum compound of the invention 0.1 relative to the number of moles of the entire constituent units of the carboxylic acid components such as dicarboxylic acids and polycarboxylic acids obtained polyester 0 01-0. 05 Monore 0/0 force preferably, still more preferably ⁇ or 0. 005- 0.02 Monore 0/0. If the amount used is less than 0.001 mol%, the catalytic activity may not be sufficiently exhibited. If the amount used is more than 0.05 mol%, thermal stability and thermal oxidation stability may be reduced, and aluminum may be caused. In some cases, the generation of foreign matter and the increase in coloring may become a problem.
- the polymerization catalyst of the present invention has a great feature in that it exhibits sufficient catalytic activity even when the addition amount of the aluminum component is small. As a result, thermal stability and thermal stability are excellent, and foreign substances and coloring caused by aluminum are reduced.
- Phosphorus compound The phosphorus compound constituting the polymerization catalyst of the present invention is not particularly limited, but is not limited to phosphoric acid and phosphoric acid esters such as trimethylphosphoric acid, triethylphosphoric acid, phenylphosphoric acid, triphenylphosphoric acid, phosphorous acid, and trimethylphosphite. , Triethyl phosphite, triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenyl-diene phosphite, etc. Phosphorous ester and the like can be mentioned.
- the phosphorylated compound of the present invention is at least one selected from the group consisting of phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinous acid compounds, and phosphine compound compounds. It is a lindani product.
- the use of these phosphorus conjugates has the effect of improving the catalytic activity and the effect of improving the physical properties such as the thermal stability of the polyester.
- the use of a phosphonic acid-based compound is preferable because the effect of improving the physical properties and the effect of improving the catalytic activity are large.
- the use of a compound having an aromatic ring structure is preferable because the effect of improving physical properties and the effect of improving catalytic activity are large.
- the phosphonic acid compound, phosphinic acid compound, phosphine oxide compound, phosphonous acid compound, phosphinous acid compound and phosphine compound referred to in the present invention are represented by the following formulas (Chemical Formula 1) and (Chemical Formula 6), respectively. Refers to a compound having the structure represented.
- Examples of the phosphonic acid compound of the present invention include dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, getyl phenylphosphonate, diphenyl phenylphosphonate, and dimethyl benzylphosphonate. And benzylphosphonate.
- Examples of the phosphinic acid-based compound of the present invention include, for example, diphenylphosphinic acid, methyldiphenylphosphinate, diphenylphosphinic acid, phenylphosphinic acid, methylphenylphosphinic acid, and methylphenol. Phosphinic acid and the like.
- Examples of the phosphine oxide-based compound of the present invention include diphenyl phosphine oxide, methyl diphenyl phosphine oxide, and triphenyl phosphine oxide.
- phosphinic acid compounds phosphine oxide compounds, phosphonous acid compounds
- the compounds represented by the following formulas (Formula 7) to (Formula 12) are preferable as the phosphorus conjugate of the present invention.
- R 4 , R 5 and R 6 each independently represent hydrogen, a hydrocarbon group having 115 carbon atoms, a hydroxyl group or a halogen group, or a hydrocarbon group having 115 carbon atoms including an alkoxyl group or an amino group.
- R 2 and R 3 each independently represent hydrogen, a hydrocarbon group having 150 carbon atoms, or a hydrocarbon group having 150 carbon atoms including a hydroxyl group or an alkoxyl group.
- the hydrocarbon group may contain an alicyclic structure such as cyclohexyl or an aromatic ring structure such as phenyl-naphthyl.
- Linyi conjugate of the present invention in the above formula (Chemical Formula 13) — (Chemical Formula 15) Compounds in which R 4 , R 5 and R 6 are groups having an aromatic ring structure are particularly preferred.
- the phosphorus compound of the present invention include dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, getyl phenolphosphonate, diphenyl phenylphosphonate, dimethyl benzylphosphonate, benzyl Getyl phosphonate, diphenyl phosphinic acid, methyl diphenyl phosphinate, phenyl diphenyl phosphinate, phenyl phosphinic acid, methyl phenyl phosphinate, phenyl phenyl phosphinate, diphenyl phosphine oxide, Methyl diphenyl phosphine oxide, triphenyl phosphine oxide and the like can
- a metal-based phosphorus-based conjugate is particularly preferred as the phosphorus-based conjugate.
- the metal salt conjugate of phosphorus is not particularly limited as long as it is a metal salt of the phosphorus conjugate, but the use of a metal salt of a phosphonic acid compound V, polyester The effect of improving the physical properties and the effect of improving the catalytic activity are greatly preferred.
- the metal salt of the phosphorus compound include a monometal salt, a dimetal salt, and a trimetal salt.
- the metal part of the metal salt is selected from Li, Na, K, Be, Mg, Sr, Ba, Mn, Ni, Cu, and Zn.
- the improvement effect is large and is preferable.
- Li, Na, and Mg are particularly preferred.
- R 1 represents hydrogen, a hydrocarbon group having 115 carbon atoms, a hydroxyl group or a halogen group, or a hydrocarbon group having 115 carbon atoms including an alkoxyl group or an amino group.
- R 2 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group, and
- R 3 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group. Also Represents an alkoxyl group or a hydrocarbon group having 150 carbon atoms including a carbonyl.
- the hydrocarbon group includes an alicyclic structure such as cyclohexyl and a branched structure and an aromatic ring structure such as phenyl dinaphthyl. )
- R 1 examples include phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl and the like.
- R 2 examples include hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, long-chain aliphatic, and phenyl.
- R 30 for example, hydroxyl
- Chloride ion Chloride ion, alcohol ion, acetate ion acetylacetone ion and the like.
- R 1 represents hydrogen, a hydrocarbon group having 115 carbon atoms, a hydroxyl group or a halogen group, or a hydrocarbon group having 115 carbon atoms including an alkoxyl group or an amino group.
- R 3 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group or a hydrocarbon group having 1 to 50 carbon atoms including carbonyl, 1 is an integer of 1 or more, and m is 0 or 1 or more. And 1 + m is 4 or less.
- M represents a (1 + m) -valent metal cation.
- the hydrocarbon group is an alicyclic structure such as cyclohexyl or a branched structure or a phenyl dinaphthyl or the like. It may contain an aromatic ring structure.
- R 1 examples include phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl and the like.
- R 30 for example, hydroxide Among these phosphorus conjugates, the use of a compound having an aromatic ring structure is preferable because the effect of improving the physical properties and the effect of improving the catalytic activity are large.
- M is Li, Na, K, Be, Mg, Sr, Ba, Mn, Ni, Cu or Zn. .
- Li, Na, and Mg are particularly preferred.
- Examples of the metal salt compound of phosphorus according to the present invention include lithium [ethyl (1naphthyl) methylphosphonate], sodium [ethyl (1naphthyl) methylphosphonate], and magnesium bis [ethyl (1naphthyl) methylphosphonate].
- lithium [(1 naphthyl) methyl phosphonate], sodium [(1 naphthyl) methyl phosphonate], magnesium bis [(1 naphthyl) methyl phosphonate], lithium [benzyl phenyl phosphonate], sodium [Ethyl benzylphosphonate], magnesium bis [benzyl phosphonate], sodium benzylphosphonate, and magnesium bis [benzylphosphonic acid] are particularly preferred.
- Rinii conjugates in the present invention, at least a P-OH bond is used as the Rinni conjugate.
- Phosphorus compounds that also have one are particularly preferred.
- the inclusion of these phosphorus conjugates particularly enhances the effect of improving the physical properties of the polyester.
- the use of these phosphorus compounds together with the aluminum compound of the present invention can improve the catalytic activity. The improvement effect is large.
- the phosphorus conjugate having at least one P—OH bond is not particularly limited as long as it is a phosphorus conjugate having at least one P—OH in the molecule.
- the use of a phosphonic acid-based compound having at least one P-OH bond is preferred because the effect of improving the properties of the polyester and the effect of improving the catalytic activity are large.
- the compound represented by the following general formula (Chem. 18) is used. Is greatly preferred.
- R 1 represents hydrogen, a hydrocarbon group having 150 carbon atoms, a hydroxyl group or a halogen group, or a hydrocarbon group having 115 carbon atoms including an alkoxyl group or an amino group.
- R 2 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or a hydrocarbon group having 1 to 50 carbon atoms, including a hydroxyl group or an alkoxyl group, and n represents an integer of 1 or more. May contain an alicyclic structure, a branched structure, or an aromatic ring structure such as phenyl-naphthyl.
- R 1 examples include phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl and the like.
- R 2 examples include hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, long-chain aliphatic, phenyl, Examples include a naphthyl group, a substituted phenyl group, a naphthyl group, and a group represented by CH CH OH.
- Use of a compound having an aromatic ring structure among the above-mentioned phosphorus conjugates is preferred because the effect of improving the physical properties and the effect of improving the catalytic activity are large.
- Examples of the phosphorylated compound having at least one P-OH bond of the present invention include: (1 naphthyl) methylphosphonic acid ethyl, (1 naphthyl) methylphosphonic acid, (2-naphthyl) methylphosphonic acid ethyl, benzylphosphonic acid ethyl, Benzylphosphonic acid, (9 Anthryl) methylethylphosphonate, 4-Hydroxybenzylphosphonylethyl, 2-Methylbenzylphosphonylethyl, 4-cyclobenzylbenzylphosphonate, 4-aminomethylbenzylphosphonate, 4-methoxybenzyl Ethyl phosphonate and the like.
- Rinii conjugate represented by the chemical formula (Formula 19).
- R 1 represents a hydrocarbon group or a hydroxyl group or a halogen Motoma others a hydrocarbon group having a carbon number of 1 one 49 containing an alkoxyl group or an amino group, a 1 one 49 carbon atoms, R 2 , R 3
- the hydrocarbon group may have an alicyclic structure, a branched structure, or an aromatic ring structure.
- the phosphorus conjugate of the present invention is a phosphorus conjugate having a phenol moiety in the same molecule.
- a phosphorus conjugate having a phenol moiety in the same molecule By containing a phosphorus conjugate having a phenol moiety in the same molecule, the effect of improving the physical properties of the polyester is enhanced.
- a phosphorus conjugate having a phenol moiety in the same molecule during the polymerization of polyester. Greater effect of increasing catalyst activity and therefore higher polyester productivity.
- the phosphorus compound having a phenol moiety in the same molecule is not particularly limited as long as it is a phosphorus compound having a phenol structure, but a phosphonic acid compound, a phosphinic acid compound, a phosphine compound having a phenol moiety in the same molecule.
- the use of one or more compounds selected from the group consisting of an oxide compound, a phosphonous acid compound, a phosphinic acid compound, and a phosphine compound is preferable because the effect of improving the physical properties of the polyester and the effect of improving the catalytic activity are large. .
- the use of a phosphonic acid compound having one or more phenol moieties in the same molecule is particularly preferred because of the effect of improving the physical properties of the polyester and the effect of improving the catalytic activity.
- R 1 is a substituent such as a hydrocarbon group, a hydroxyl group, a halogen group, an alkoxyl group or an amino group, etc.
- Represents a hydrocarbon group having 1 to 50 carbon atoms including: R 4 , R 5 , and R 6 are each independently Represents a hydrocarbon group having 1 to 50 carbon atoms including a substituent such as hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group or an amino group.
- R 2 and R 3 each independently represent hydrogen, a hydrocarbon group having 150 carbon atoms, or a hydrocarbon group having 115 carbon atoms including a substituent such as a hydroxyl group or an alkoxyl group.
- the hydrocarbon group may include an alicyclic structure such as a branched-chain cyclohexyl or an aromatic ring structure such as phenyl-naphthyl.
- the terminals of R 2 and R 4 may be bonded to each other.
- Examples of the phosphorus conjugate having a phenol moiety in the same molecule of the present invention include, for example, p-hydroxyphenylphosphonic acid, dimethyl p-hydroxyphenylphosphonate, getyl p-hydroxyphenylphosphonate, p-hydroxy Diphenyl phosphonate, bis (p-hydroxyphenyl) phosphinic acid, methyl bis (p-hydroxyphenyl) phosphinate, bis (p-hydroxyphenyl) phosphinic acid phenol, p- Hydroxyphenyl phosphinic acid, methyl p-hydroxyphenyl phosphinate, p-hydroxyphenyl phosphinate, p-hydroxyphenyl phosphinic acid, p-hydroxyphenyl phosphinate Methyl finate, p-hydroxyphenylphosphinic acid phosphate, bis (p-hydroxyphenyl) phosphine oxide, Scan (p- hydroxy Hue - Le) pho
- SANKO-220 manufactured by Sanko Co., Ltd.
- At least one selected from the metal salt-binding properties of the specific phosphorus represented by 33) is particularly preferred.
- R ⁇ R 2 each independently represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms.
- R 3 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group.
- R 4 is hydrogen, a hydrocarbon group having 150 carbon atoms, a hydroxyl group or an alkoxyl group or a hydrocarbon having 1 to 50 carbon atoms including carbonyl Table to a group.
- R 4 0- for example, Mizusani ⁇ ions, Arcola one Toion, acetate ion, and ⁇ cetyl acetone ions.
- 1 is an integer of 1 or more
- m is 0 or 1 or more
- M represents a (1 + m) -valent metal cation
- n represents an integer of 1 or more
- the hydrocarbon group is an alicyclic structure such as cycloalkylhexyl. It may contain a branched structure or an aromatic ring structure such as phenyl-naphthyl.
- At least one compound selected from compounds having the following general formula (Formula 34) is preferable.
- M n + represents an n-valent metal cation.
- N represents 1, 2, 3 or 4.
- M is It is preferable to use one selected from the group consisting of Li, Na, K, Be, Mg, Sr, Ba, Mn, Ni, Cu and Zn, because the effect of improving the catalytic activity is large. Of these, Li, Na, and Mg are particularly preferred.
- the specific phosphorus metal salt compound of the present invention includes lithium [3,5-di-tert-butyl-4-hydroxybenzylphosphonate], sodium [3,5-di-tert-butyl-4-hydroxybenzyl] Ethyl phosphonate], sodium [3,5-di-tert-butyl-4-hydroxybenzylinophosphonate], potassium [3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethinole], magnesium bis [3,5-di-tert] -Butyl-4-hydroxybenzylphosphonate], magnesium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate], beryllium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate Tyl], strontium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid Ethyl, norium bis [3,5-di-tert-butyl-4-
- lithium [3,5-di-tert-butyl-4-hydroxybenzylphosphonate] sodium [3,5-di-tert-butyl-4-hydroxybenzylphosphonate]
- magnesium bis [3,5- D-tert-butyl-4-hydroxybenzylphosphonate] is particularly preferred.
- phosphorus conjugates having a phenol moiety in the same molecule a specific phosphorus conjugate having at least one P-OH bond represented by the following general formula (Formula 35) is selected. At least one is particularly preferred.
- R 2 each independently represents hydrogen or a hydrocarbon group having 130 carbon atoms.
- R 3 represents hydrogen, a hydrocarbon group having 1 to 150 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group.
- n represents an integer of 1 or more.
- the hydrocarbon group may include an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl-naphthyl.
- At least one selected from the group consisting of compounds represented by the following general formula (Formula 36) is preferable.
- R 3 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or a hydrocarbon group having 1 to 50 carbon atoms including an alkoxy group.
- the hydrocarbon group is a cycloalkyl group. Including an alicyclic structure, a branched structure, and an aromatic ring structure such as phenyl dinaphthyl!
- R 3 for example, hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, long-chain aliphatic group, phenyl group, naphthyl group Groups such as butyl, substituted phenyl, naphthyl, and CH CH OH.
- Specific phosphorylated compounds having at least one P-OH bond include ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and 3,5-di-tert-butyl-4-hydroxybenzylphosphonate.
- methyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and methyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate are particularly preferred.
- R ⁇ R 2 each independently represents hydrogen or a hydrocarbon group having 110 to 30 carbon atoms.
- R 3 and R 4 each independently represent hydrogen or a hydrocarbon group having 1 to 50 carbon atoms.
- R 3 and R 4 each independently represent hydrogen, a hydrocarbon group having 115 carbon atoms, or a hydrocarbon group having 115 carbon atoms including a hydroxyl group or an alkoxyl group.
- the group may include an alicyclic structure or a branched structure such as cyclohexyl, or an aromatic ring structure such as phenyl-naphthyl.
- R 3 and R 4 for example, short-chain aliphatic groups such as hydrogen, methyl group and butyl group, long-chain aliphatic groups such as octadecyl, phenyl group, naphthyl group and substituted phenyl group And an aromatic group such as a naphthyl group and a group represented by CH 2 CH OH.
- the specific phosphorus compound of the present invention includes diisopropyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate di-n-butyl, 3,5-diethyl dioctadecyl tert-butyl-4-hydroxybenzylphosphonate; diphenyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate; Among these, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and diphenyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate are particularly preferred.
- a particularly desirable one of the phosphorus conjugates of the present invention is at least one of the compounds represented by the chemical formulas (Chem. 39) and (Chem. 40). It is a kind of lindani compound.
- Irganoxl222 manufactured by Ciba Specialty Chemicals
- Ciba Specialty Chemicals is commercially available
- Irganoxl425 Chinoku's Specialty Chemicals Co., Ltd.
- Linyi conjugates are known as heat stabilizers for polyesters. However, even when these compounds are used in combination with a conventional metal-containing polyester polymerization catalyst, they can greatly promote melt polymerization. The power that was unknown until now.
- an antimony conjugate, a titanium conjugate, a Suzui conjugate, or a germanium compound as a polymerization catalyst the phosphorus conjugate of the present invention is used. The addition of is not observed to promote polymerization to a substantially useful level.
- the amount of Rini ⁇ of making the polyesters according to the method of the present invention 0.1 with respect to the number of moles of all the structural units of the polycarboxylic acid component of the polyester obtained 0 001 0.1 Monore 0 / 0 power child preferred, it forces more preferably 0. 005- 0.05 Monore 0/0.
- a catalyst exhibiting a sufficient catalytic effect can be obtained even when the addition amount of aluminum in the polyester polymerization catalyst is small.
- the amount of the phosphorus compound is less than 0.0001 mol%, the effect of the addition may not be exhibited, and if it exceeds 0.1 mol%, on the contrary, the catalytic activity as a polyester polymerization catalyst is low. In some cases, the tendency of the decrease depends on the amount of aluminum used and the like.
- the above phosphorus compound which has been heat-treated in advance in water and at least one solvent selected from the group which also has alkylene glycol power.
- the treatment improves the activity of the polycondensation catalyst by using the above-mentioned phosphorus compound in combination with the above-mentioned aluminum or aluminum compound, and reduces the foreign matter-forming ability caused by the polycondensation catalyst.
- the solvent used when the phosphorus compound is subjected to heat treatment in advance is not limited as long as it is at least one selected from the group consisting of water and an alkylene glycol, and it is preferable to use a solvent that dissolves an arbitrary phosphorus compound.
- the alkylene glycol it is preferable to use glycol which is a constituent component of the target polyester such as ethylene glycol.
- the heat treatment in a solvent is preferably performed by dissolving the phosphorous conjugate, and it is also preferable that the heat treatment be performed. Further, it is not necessary that the compound retains the original structure after the heat treatment, and the compound may be modified by the heat treatment to improve the solubility in a solvent.
- the temperature of the heat treatment is not particularly limited, but is preferably in the range of 20 to 250 ° C. More preferably, it is in the range of 100-200 ° C.
- the upper limit of the temperature is preferably around the boiling point of the solvent used.
- the heating time varies depending on conditions such as temperature.When the temperature is near the boiling point of the solvent, it is preferably in the range of 1 minute to 50 hours, more preferably 30 minutes to 10 hours, and still more preferably 115 hours. Range.
- the pressure of the heat treatment system may be normal pressure, or higher or lower, and is not particularly limited.
- the concentration of the solution is preferably from 500 to 300 gZl, more preferably from 5 to 300 gZl, even more preferably from 10 to 100 gZl as the phosphorus compound.
- the heat treatment is preferably performed in an atmosphere of an inert gas such as nitrogen.
- the storage temperature of the solution or slurry after heating is not particularly limited, but is preferably in the range of 0 ° C to 100 ° C, more preferably in the range of 20 ° C to 60 ° C.
- the solution is preferably stored in an atmosphere of an inert gas such as nitrogen.
- the phosphorus compound preferably contains a hydroxyl group, and is an embodiment. Therefore, the ligated conjugate has at least one hydroxyl group in one molecule. Is preferred.
- acid conjugates and acid-ester mixed conjugates of an acid and an ester are applicable.
- the phosphorylated compound is pre-treated with a water-containing solvent such as water or alkylene glycol to hydrolyze the ester bond! In a preferred embodiment, a part of the ester bond is converted to a hydroxyl group.
- the amount of conversion to hydroxyl groups is not limited, but the amount of insoluble foreign matter to the polyester is extremely small, and the effect of reducing the amount of insoluble foreign matter to polyester by the introduction of the hydroxyl group is manifested in a very small amount.
- An amount of about mol% is effective. Therefore, even when an ester-type phosphorus-containing compound in which all the hydroxyl groups in the phosphorus compound are esterified is used, the effect is also exhibited by the hydroxyl group formed at the time of the mixing treatment with the aluminum compound solution.
- ester-type lindani products is not excluded!
- the catalyst of the present invention is obtained by mixing an aluminum compound and a phosphorous conjugate in a solvent.
- a mixing method a method in which aluminum or a compound thereof is added to a solution of the phosphorus-containing compound as a powder, a solution, or a slurry, or a method in which a phosphorus compound is added to a solution of aluminum or a compound thereof in a powder, solution, or Any method of adding as a slurry may be used.
- the heat treatment for heating the phosphorus ligature and the dissolution of aluminum may be performed in a single solution or after mixing.
- the step of removing water from the solution may be before or after the mixing with the Linyi conjugate.
- the solution or slurry obtained by these operations can be used as the polycondensation catalyst of the present invention
- the most preferred form is to separate a solution of aluminum or its compound and a heat-treated solution of phosphorus compound separately. And then mix.
- the NMR spectrum peak of the phosphorus atom bonded to the hydroxyl group in the above mixed solution is It is preferable that the peak shifts to a higher magnetic field side from the NMR spectrum peak of the phosphorus atom bonded to the hydroxyl group of the phosphorus conjugate alone solution before mixing, and the peak becomes broad.
- the integrated value of the NMR ⁇ vector peak of the phosphorus atom bonded to the hydroxyl group in the above mixed solution is 10% or more of the integrated value of the NMR ⁇ vector peak of the phosphorus atom bonded to the hydroxyl group of the phosphorus compound alone solution before mixing. Is a preferred embodiment. 15% or more is more preferable 20% or more is more preferable.
- the effect of suppressing the formation of foreign matter insoluble in polyester due to the aluminum polycondensation catalyst is reduced, and the content of foreign matter insoluble in polyester is increased.
- the solvent of the mixed solution is ethylene glycol.
- the method of mixing the ethylene glycol solution of the aluminum compound and the phosphorus compound solution is not limited, but the phosphorus solution is stirred.
- the conditions for the addition are not limited. In the case of a phosphorus compound containing a hydroxyl group, mixing at room temperature is preferred. On the other hand, in the case of an ester-type phosphorus-conjugated product in which all hydroxyl groups are esterified, it is necessary to cause generation of hydroxyl groups, so that heating is required.
- the heating temperature is not limited, but is preferably 50-200 ° C.
- the mixing conditions are appropriately set depending on the structure of the phosphorus compound or aluminum compound to be used. The setting of the conditions is an embodiment, and it is preferable that the change of the NMR spectrum when the two solutions are mixed is followed and the mixing conditions satisfying the above requirements are set.
- a phosphorus-containing compound that does not contain a hydroxyl group When using a phosphorus-containing compound that does not contain a hydroxyl group, use a phosphorus compound alone that has been heat-treated as an ethylene glycol solution to form a hydroxyl group before mixing with the aluminum glycol solution of the aluminum compound. Is preferred. A small amount of water may be added during the pretreatment to promote the formation of hydroxyl groups.
- the mixture ratio of the aluminum compound and the phosphorus conjugate is such that the molar ratio of aluminum atom and phosphorus atom is represented by the formula (1). Is preferred.
- PZA1 (molar ratio) 0.5 ⁇ PZA1 (molar ratio) ⁇ 20 (1)
- Exceeding the range of the above formula (1) is not preferable because the polycondensation catalyst activity decreases and the effect of suppressing the formation of foreign matters insoluble in polyester decreases.
- PZA1 (molar ratio) is preferably 0.8-10, more preferably 1.0-5.
- the NMR spectrum peak of the phosphorus atom to which the hydroxyl group is bonded shifts to the high magnetic field side.
- the phenomenon is that the hydroxyl group in the phosphorus compound is shifted to the aluminum atom in the aluminum compound. It is presumed that it is caused by coordination to form a complex.
- the method of storing the above mixed solution of the aluminum compound and the phosphorus compound is not particularly limited, either.
- the mixing method is not limited, and examples thereof include extruding a predetermined amount of each solution with a metering pump and mixing while stirring with a stirring mixer, or mixing in a static mixer or a pipe.
- the mixture When mixing and supplying in advance, it is preferable to store the mixture at 10-45 ° C. 15-40 ° C is more preferred. When stored at a temperature higher than the temperature range, gelling of the aluminum compound or the complex of the aluminum compound and the phosphorous conjugate occurs, and at a low temperature side, the fluidity of the mixed solution is reduced due to precipitation of the phosphorous sulfide and the like. This is not preferable because it leads to unfavorable results such as a decrease in the quantitativeness of the supply to the polycondensation reaction system.
- the preservation method is not particularly limited, but a solution obtained by stirring and mixing an ethylene glycol solution of an aluminum compound and ethylene glycol of a phosphorus compound at a predetermined mixing ratio for 30 minutes is taken out and taken out.
- the method of storing in a constant temperature bath or a constant temperature room within the range is mentioned.
- the mechanism when the content of foreign matter insoluble in the polyester is reduced by satisfying the above requirements, the mechanism can be clarified. However, the hydroxyl group in the phosphorus compound with respect to the aluminum atom of the aluminum compound is reduced. It is presumed that the formation of a complex of an aluminum compound and a phosphorus compound by coordination of the compound suppresses the formation of foreign substances insoluble in the polyester caused by the aluminum compound, which is caused.
- the effect of the present invention solves the conventional problem that the amount of foreign matters insoluble in the polyester obtained by the manufacturer and the lot of the aluminum compound varies greatly.
- the problem was eliminated without lowering the polycondensation activity or increasing the side reaction during the formation of the polyester, and the amount of foreign matters insoluble in the polyester was constantly maintained at a low level.
- the polymerization catalyst of the present invention contains an alkali metal, an alkaline earth metal, or a compound thereof! /.
- a small amount of an alkali metal, an alkaline earth metal, and a compound thereof is preferably coexisted as a second metal-containing component. It is.
- the coexistence of a powerful second metal-containing component in the catalyst system has the effect of suppressing the production of diethylene glycol and increasing the catalytic activity, and therefore, a catalyst component with a higher reaction rate can be obtained, which is effective for improving productivity. It is.
- a catalyst having sufficient catalytic activity can be obtained by adding an alkali metal compound or an alkaline earth metal compound to an aluminum compound.
- a known catalyst using an alkali metal compound or an alkaline earth metal compound in combination with an alkali metal compound or an alkaline earth metal compound has the ability to obtain a polyester having excellent thermal stability when such a known catalyst is used.
- the resulting polyester has a low hydrolysis resistance and a large amount of foreign substances due to the alkali metal compound. Physical properties When used for films, film physical properties and the like deteriorate.
- the thermal stability of the obtained polyester is reduced in order to obtain practical activity, and the amount of foreign matters that generate large coloring due to heating increases, and Hydrolysis is also reduced.
- the amount of alkali metal, alkaline earth metal and its compound used is 0.1 mol% or more, the thermal stability is reduced, the generation of foreign substances and coloration, and the hydrolysis resistance are reduced. May occur.
- the M is less than 1 X 10- 6, the effect is not clear also be added.
- Alkali metals and alkaline earth metals constituting the second metal-containing component include Li, Na, K, Rb, Cs, Be, Of at least one selected from Mg, Ca, Sr, and Ba, the use of at least one selected from Li, Na, Mg or a compound thereof is more preferable.
- compounds of alkali metals and alkaline earth metals include, for example, unsaturated aliphatic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, and oxalic acid, and unsaturated aliphatic carboxylic acids such as acrylic acid and methacrylic acid.
- Acid aromatic carboxylate such as benzoic acid, halogen-containing carboxylate such as trichloroacetic acid, hydroxycarboxylate such as lactic acid, citric acid, salicylic acid, carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, carbonic acid
- Inorganic acid salts such as hydrogen, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid, and bromic acid; and organic sulfones such as 1 propanesulfonic acid, 1 pentanesulfonic acid, and naphthalenesulfonic acid Sulphate, organic sulfates such as lauryl sulfate, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, tert-butoxy, etc.
- Examples include chelates, hydrides, oxides, hydroxides and the like with lucoxide, acetyl acetate and the like.
- strong alkalis such as hydroxides are used among these alkali metals, alkaline earth metals or compounds thereof, they are difficult to dissolve in diols such as ethylene glycol or organic solvents such as alcohols. Because of the tendency, the aqueous solution must be added to the polymerization system, which may be a problem in the polymerization process.
- the alkali metal or a compound thereof or an alkaline earth metal or a compound thereof suitable for the present invention is preferably a saturated aliphatic carboxylate, an unsaturated aliphatic carboxylate, or an aromatic salt of an alkali metal or an alkaline earth metal.
- a saturated aliphatic carboxylate of an alkali metal or an alkaline earth metal particularly an acetate.
- the polycondensation catalyst of the present invention is obtained by adding other polycondensation catalysts such as an antimony conjugate, a germanium compound, and a titanium conjugate to each other. It is effective and effective to improve the productivity by shortening the polymerization time, and it is preferable to use them together within the range of the addition amount without causing a problem in the product.
- the antimony conjugate is preferably added in an amount of 50 ppm or less as an antimony atom to the polyester obtained by polymerization.
- a more preferred amount of added kashi is 30 ppm or less. If the amount of antimony added is 50 ppm or more, precipitation of metallic antimony occurs, which is not preferable because blackening and foreign matter are generated in polyester.
- the germanium compound is preferably added in an amount of 20 ppm or less as a germanium atom to the polyester obtained by polymerization.
- a more preferable addition amount is 10 ppm or less. If the amount of germanium added is 20 ppm or more, it is not preferable because it is disadvantageous in terms of cost.
- the titanium conjugate in an amount of 5 ppm or less as a titanium atom to the polyester obtained by polymerization.
- a more preferred addition amount is 3 ppm or less, and still more preferably lppm or less. If the amount of titanium added is 5 ppm or more, it is not preferable because coloring of the obtained polyester becomes remarkable and thermal stability is remarkably reduced.
- the antimony conjugate which can be used in the present invention is not particularly limited, but preferred compounds include antimony trioxide, antimony pentoxide, antimony acetate, antimony glycoside, and the like. It is preferred to use antimony.
- the germanium compound is not particularly limited, but examples thereof include germanium dioxide and germanium tetrachloride, and germanium dioxide is particularly preferable.
- the titanium compound that can be used in the present invention is not particularly limited; however, tetra-n-propinoretitanate, tetraisopropinoretitanate, tetra-n-butynoletitanate, tetraisobutyltitanate, tetra-tert-butyltitanate, tetracyclo Hexyl titanate, tetraphenyl titanate, tetrabenzyl titanate, lithium titanate, potassium titanate, ammonium titanate, titanium oxide, titanium and silicon dioxide alkali metals and alkalis Complex oxide with an earth metal, etc., orthoester or condensed orthoester of titanium, reaction product of titanium orthoester or condensed orthoester with hydroxycarboxylic acid, orthoester or condensed orthoester of titanium and hydrocarboxylate A reaction product comprising a carboxylic acid and a phosphorus
- reaction product consisting of a complex oxidized product of titanium and silicon, a complex oxidized product of titanium and magnesium, an orthoester or condensed orthoester of titanium, a hydroxycarboxylic acid and a phosphorylated product are preferable.
- Suzuki conjugate examples include dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexethylditin oxide, triethyltin hydrate oxide, monobutylhydroxytin oxide, triisobutyltin acetate, diphenyltin dilaurate. And monobutyltin trichloride, dibutyltin sulfide, dibutylhydroxysoxide, methylstannoic acid, ethylstannoic acid, and the like. In particular, use of monobutylhydroxytin oxide is preferred.
- a cobalt compound is added as a cobalt atom to the polyester of the present invention in an amount of less than 10 ppm as a cobalt atom to the polyester. It is more preferably at most 5 ppm, and even more preferably at most 3 ppm.
- the cobalt compound is not particularly limited, but specific examples thereof include cobalt acetate, cobalt nitrate, sodium chloride conjugate, cobalt acetylacetonate, cobalt naphthenate, and hydrates thereof. Can be Among them, cobalt acetate tetrahydrate is particularly preferred.
- the production of the polyester according to the present invention uses the polyester polymerization catalyst of the present invention as a catalyst. Except for use, the method can be performed by a method including a conventionally known process.
- a direct esterification method in which terephthalic acid and ethylene glycol and, if necessary, other copolymerization components are directly reacted to distill water and esterify, followed by polycondensation under reduced pressure
- a transesterification method in which dimethyl terephthalate is reacted with ethylene glycol and, if necessary, other copolymer components to remove methyl alcohol and transesterify, followed by polycondensation under reduced pressure.
- melt-polymerized polyester may be heated and crystallized after absorbing moisture, or steam may be directly blown onto the polyester chip to heat and crystallize.
- the melt polycondensation reaction may be performed in a batch reactor or a continuous reactor.
- the esterification reaction or ester exchange reaction may be performed in one stage, or may be performed in multiple stages.
- the melt polycondensation reaction may be performed in one stage, or may be performed in multiple stages.
- the solid-phase polymerization reaction can be carried out in a batch-type apparatus or a continuous-type apparatus, similarly to the melt polycondensation reaction.
- the melt polycondensation and the solid phase polymerization may be performed continuously or may be performed separately. In the following, a description will be given of a preferred example of a continuous method and an example of a production method using PET as an example.
- a slurry containing 1.0-1.5 mol, preferably 1.03-1.1 mol of ethylene glycol per 1 mol of terephthalic acid or its ester derivative was prepared, and this slurry was subjected to the esterification reaction step. Supply continuously.
- esterification reaction water or alcohol generated by the reaction is fed out of the system using a rectification column under the condition that ethylene glycol is refluxed using a multistage apparatus in which 13 esterification reactors are connected in series. Perform while removing.
- the temperature of the first stage esterification reaction is 240-270. C, preferably 245-265. C, the pressure is 0.2-3 kgZcm 2 G, preferably 0.5-2 kgZcm 2 G.
- the temperature of the final esterification reaction is usually 250-290 ° C, preferably 255-275. C and pressure is normal.
- One 1.5 kgZcm 2 G preferably. It is 1.3 kg / cm 2 G.
- the reaction conditions of the intermediate esterification reaction are those between the above-mentioned first-stage reaction conditions and the last-stage reaction conditions. This The increase in the conversion of these esterification reactions is preferably distributed smoothly at each stage. Ultimately, the esterification reaction rate is desired to reach 90% or more, preferably 93% or more. By the esterification reaction, a low-order condensate having a molecular weight of about 500 to 5000 is obtained.
- the above esterification reaction can be carried out in the absence of a catalyst by the catalytic action of terephthalic acid as an acid, but the reaction is carried out in the presence of a polycondensation catalyst.
- tertiary amines such as triethylamine, tree n-butylamine and benzyldimethylamine, tetraethylammonium hydroxide, tetran-butylammonium hydroxide, trimethylbenzylammonium hydroxide.
- a quaternary ammonium hydroxide such as sodium chloride and a basic disulfide such as lithium carbonate, sodium carbonate, potassium carbonate, and sodium acetate
- polyethylene terephthalate is mainly used. It is preferable because the ratio of dioxyethylene terephthalate component units in the chain can be kept at a relatively low level (5 mol% or less based on the total diol component).
- the transesterification reaction uses a device in which one or two transesterification reactors are connected in series, and under the conditions in which ethylene glycol is distilled back, the methanol produced by the reaction is removed outside the system by a rectification column. While doing.
- the temperature of the first-stage transesterification reaction is from 180 to 250 ° C, preferably from 200 to 240 ° C.
- the temperature of the final transesterification is usually 230-270. C, preferably 240-265.
- C and as a transesterification catalyst, a fatty acid salt such as Zn, Cd, Mg, Mn, Co, Ca, Ba, a carbonate, or a Pb, Zn, Sb, Ge oxide or the like is used.
- a low-order condensate having a molecular weight of about 200 to 500 can be obtained by these transesterification reactions.
- the transesterification catalyst be blocked by adding a phosphorus compound at the end of the transesterification reaction.
- the phosphorous conjugate is generally prepared by using phosphoric acid, phosphorous acid and its ester derivative. Is also good.
- the addition time of the catalyst is not particularly limited as long as it is before the polycondensation step.
- the addition time of the catalyst in the early stage of the esterification reaction is increased.
- the oligomer has an acid value (AV) of 2000-5000eqZton
- the phosphorus compound may be added as a mixture with the aluminum compound or may be added separately at the same time.Also, before the polycondensation reaction, the phosphorus compound may be added separately after the addition of the aluminum compound. good.
- the solution obtained by mixing the above-mentioned aluminum compound and the phosphorus conjugate is added after the esterification reaction or the transesterification reaction is completed.
- the acid value (AV) of the oligomer at this time is not particularly limited, but is usually 100 to 800 eq.
- the catalyst can be added during the subsequent polycondensation step.
- the place and method of adding the mixed solution are not limited at all! For example, it may be added to a transfer pipe to a transesterification reactor or a transesterification reactor, or may be added in a polycondensation step! In a preferred embodiment, the addition is carried out to an in-line mixer installed in a transfer pipe from the transesterification reactor to the polycondensation reactor. According to this method, the added phosphorus-containing product and the esterification-product or ester-exchange product can be uniformly mixed, and the effects of the present invention can be more efficiently achieved. It is preferable because it can be realized.
- the structure of the in-line mixer used in this method is not limited at all! For example, it may be added to a transfer pipe to a transesterification reactor or a transesterification reactor, or may be added in a polycondensation step! In a preferred embodiment, the addition is carried out to an in-line mixer installed in a transfer pipe from the transesterification reactor to the polycondensation reactor
- JP-A-8-299771 there is no limitation as long as the uniform mixing effect can be exhibited.
- an in-line mixer for dispersing and mixing a slurry disclosed in JP-A-8-299771 is suitable.
- the polymerization catalyst In order to improve the generation of foreign matter and the transparency, it is preferable to add the polymerization catalyst to the in-line mixer from the viewpoint that sufficient stirring is preferably performed when the polymerization catalyst is added.
- the fluctuation of Tel tends to be more stable. Therefore, it is better to perform the polycondensation step at a temperature as low as possible.
- the polycondensation reaction conditions are as follows: the reaction temperature of the first stage polycondensation is 250-290 ° C, preferably 260-280 ° C, and the pressure is 500-20 Torr, preferably 200-30 Torr. The temperature of the polycondensation reaction is 265-300. C, preferably 275-295. C and the pressure is 10-0. LTorr, preferably 5-0.5 Torr.
- the reaction conditions for the intermediate polycondensation reaction are those between the above-described first-stage reaction conditions and final-stage reaction conditions. Preferably, the degree of increase in intrinsic viscosity reached in each of these polycondensation reaction steps is smoothly distributed.
- the melt-polycondensation obtained in this manner is used.
- the polyester is solid state polymerized.
- the polyester is subjected to solid-state polymerization by a conventionally known method.
- the above-mentioned polyester to be subjected to solid-state polymerization is preliminarily heated at a temperature of 100 to 210 ° C for 115 hours under an inert gas, a reduced pressure, or an atmosphere of steam or an inert gas containing steam. Crystallized.
- solid-phase polymerization is performed at 190-230 ° C in an inert gas atmosphere or under reduced pressure for 110 hours.
- the catalyst of the present invention has catalytic activity not only in polycondensation reaction but also in esterification reaction and transesterification reaction.
- the catalyst of the present invention can be used in a transesterification reaction between an alkyl ester of a dicarboxylic acid such as dimethyl terephthalate and a glycol such as ethylene glycol.
- the catalyst of the present invention has catalytic activity not only in melt polymerization but also in solid-phase polymerization and solution polymerization, and it is possible to produce a polyester by the method of V and deviation. .
- the amount of aluminum-based foreign matter insoluble in the polyester determined by the evaluation method shown in the examples is 3500 ppm or less.
- the content of aluminum-based foreign matter is more preferably 2500 ppm or less. 1500 ppm or less is even more preferred. Particularly preferred is 100 ppm or less.
- the amount of the aluminum-based foreign matter insoluble in the polyester exceeds 3500 ppm, the fine foreign matter insoluble in the polyester causes the haze of the molded body to deteriorate when molded as a molded body such as a film or a bottle. It is not preferable. In addition, it also leads to a problem that filter clogging during filtration of the polyester in the polycondensation step or the molding step increases.
- the method of reducing the amount of aluminum-based foreign matters insoluble in polyester to 3500 ppm or less can be achieved by appropriately employing the above-described catalyst preparation method, addition timing, and addition method.
- the amount of aluminum-based foreign matter that is insoluble in polyester is a converted value to the last, and the content relative to the total amount of polyester used in the above evaluation is a very small amount of ppb level.
- the reason why the transparency of the molded article is degraded by the extremely small amount of foreign matter is that aluminum-based foreign matter insoluble in the polyester measured by the above-mentioned evaluation method has a low affinity for polyester, so that the It is presumed that voids are formed at the interface between the polyester and the aluminum-based foreign matter due to molding stress, and light is scattered by the voids, resulting in a decrease in the transparency of the molded body.
- the haze value of the uniaxially stretched film evaluated by the evaluation method shown in the examples is preferably 2% or less.
- the haze value is more preferably 1.8% or less, and still more preferably 1.6% or less. If the haze value exceeds 2%, it is not preferable because a molded article formed by molding such as a film or a bottle with stretching may have a high transparency and a molded article may not be obtained. ,.
- the method for reducing the haze value of the uniaxially stretched film to 2% or less is not limited, but the haze value is greatly affected by the amount of aluminum-based foreign matter insoluble in polyester and Tel.
- the characteristic values are optimized.
- the polyester of the present invention In order to mold the polyester of the present invention into a film, it may be necessary to impart electrostatic adhesion.
- the polyester preferably satisfies the following constitutions and properties.
- the polyester preferably contains at least an aluminum element, an alkaline earth metal element, an alkali metal element and a phosphorus element, and further preferably has the following characteristics (1)-(4).
- the haze value of the uniaxially stretched film from which the polyester strength is also obtained is 2.0% or less.
- the aluminum element content in the polyester is more preferably from 5 to 100 ppm, still more preferably from 7 to 80 ppm, and even more preferably from 10 to 60 ppm.
- Aluminum element content is 3 If it is less than ppm, the activity of the polycondensation catalyst is undesirably reduced. On the other hand, if it exceeds 200 ppm, the activity of the polycondensation catalyst will level off, and the amount of foreign matter insoluble in the polyester due to the aluminum element will increase.
- the alkali metal element content in the polyester is more preferably 1 to 40 ppm, more preferably 2 to 30 ppm, and still more preferably 3 to 20 ppm.
- the content of the alkali metal element is less than 0.5 ppm, the decrease in the melting specific resistance of the polyester is small, and the electrostatic adhesion is poor.
- the condensation reaction between the daricol components which is a side reaction, increases.
- ethylene glycol is used as the glycol component
- An increase in the side reaction is not preferred because a decrease in the melting point of the polyester and a decrease in the quality such as thermal oxidation stability are reduced.
- it exceeds 50 ppm the melt resistivity of the polyester decreases, the effect of suppressing the condensation reaction between the glycol components reaches a plateau, and the coloring of the polyester increases, resulting in a decrease in the color tone.
- the content of alkaline earth metal element in the polyester is more preferably from 5 to 160 ppm, still more preferably from 10 to 120 ppm, more preferably from 15 to 100 ppm.
- the content of the alkaline earth metal element is less than 3 ppm, a decrease in the melting specific resistance of the polyester is reduced and the electrostatic adhesion is deteriorated.
- the stability of the polyester such as thermal stability, is reduced, and the coloring of the polyester is increased, which is not preferable.
- Phosphorous element Z aluminum element + alkaline earth metal element (atomic ratio) 15-1.9 is more preferred, 0.20-1.8 is more preferred, and 0.25-1.7 is even more preferred.
- the phosphorus element Z aluminum element + alkaline earth metal element (atomic ratio) is less than 0.10, the polycondensation catalyst activity of polyester is undesirably reduced.
- the phosphorus element Z aluminum element + alkaline earth metal element (atomic ratio) exceeds 2.0, the decrease in the melting specific resistance of the polyester is reduced and the electrostatic adhesion is deteriorated.
- melt specific resistance of the polyester 0. 8 ⁇ 10 8 ⁇ 'cm or less and more preferably tool 0. 5 X 10 8 ⁇ ⁇ cm and more preferably tool 0. 3 X 10 8 ⁇ ' cm or less and more preferably more. If the melting specific resistance of the polyester is higher than 1.0 ⁇ 10 8 ⁇ 'cm, the electrostatic adhesion is deteriorated, the casting speed is reduced, and the productivity is deteriorated.
- the melting specific resistance is defined as This is correlated with the highest casting speed that can be cast while suppressing the occurrence of pinnables, that is, electrostatic adhesion. The lower the melt resistivity of a polymer, the faster it can be cast, and the facet of film productivity is also very important.
- the haze value of the uniaxially stretched film is more preferably 1.8% or less, more preferably 1.6% or less, and still more preferably 4% or less.
- the haze value exceeds 2%, it is not preferable because a molded article formed by stretching such as a film or a bottle cannot be obtained with high transparency.
- packaging films industrial films, optical films, magnetic tape films, photographic films, can laminating films, contensor films, heat shrink films, gas noria films, white films, easy cuts It can be suitably used as a raw material for films and the like.
- it can be processed by vacuum forming, pressure forming, embossing, etc., and can be applied to tray containers for food and miscellaneous goods, cups, blister packs, carrier tapes for electronic components, and sheets used as trays for electronic component delivery. is there.
- Polyester referred to in the present invention is a polyhydric carboxylic acid containing dicarboxylic acid and one or more selected from ester-forming derivatives thereof and a polyhydric alcohol containing glycol.
- the term refers to a substance which forms the above, or a substance which forms hydroxycarboxylic acid and an ester-forming derivative thereof, or a substance which forms a cyclic ester.
- the dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecandicarboxylic acid, 1 1,3-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5- Saturated aliphatic dicarboxylic acids exemplified by norbornane dicarboxylic acid, dimer acid and the like, and ester-forming derivatives thereof, and unsaturated aliphatic dicarboxylic acids exemplified by fumaric
- Saturated aliphatic dicarboxylic acids or their ester-forming derivatives orthophthalic acid, isophthalic acid, terephthalic acid, 5- (alkali metal) sulfoisophthalic acid, diphthalic acid, 1,3 naphthalenedicarboxylic acid, 1,4 naphthalenedic acid 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4-biphenylsulfonic acid, Aromatic dicarboxylic acids exemplified by 4,4-biphenyl ether dicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p, dicarboxylic acid, pamoic acid, anthracene dicarboxylic acid and the like, and ester-forming derivatives thereof Is mentioned.
- terephthalic acid and naphthalenedicarboxylic acid are preferably used in terms of the physical properties of the resulting polyester, and other dicarboxylic acids are included as necessary.
- Terephthalic acid and naphthalenedicarboxylic acid are preferably at least 70 mol%, more preferably at least 80 mol%, particularly preferably at least 90 mol%, based on the total acid components.
- Polycarboxylic acids other than these dicarboxylic acids include ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3, 4, 3 ', 4'-biphenyltetracarboxylic acid Acids and their ester-forming derivatives.
- Glycols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1, 2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, 1,10-decamethylene glycol, 1,12-dodecanediol, Polyethylene glycol, polytrimethylene glycol, polytetramethyle Aliphatic glycols exemplified by glycols, hydroquinon
- glycols ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, and 1,4-cyclohexanedimethanol are preferred.
- Each of these preferred glycols is preferably at least 70 mol%, more preferably at least 80 mol%, particularly preferably at least 90 mol%, based on the total glycol component.
- Polyhydric alcohols other than these glycols include trimethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol, hexanetriol and the like.
- Hydroxycarboxylic acids include lactic acid, citric acid, malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, 4-hydroxycyclohexanecarboxylic acid, or These ester-forming derivatives and the like can be mentioned.
- cyclic ester examples include ⁇ - proprotatatone, propiolatatone, ⁇ -methyl-piperataton, ⁇ valerolatatone, glycolide, lactide and the like.
- ester-forming derivatives of polycarboxylic acids or hydroxycarboxylic acids include these alkyl esters, acid chlorides, and acid anhydrides.
- polyester of the present invention examples include polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, poly (1,4-cyclohexane dimethylene terephthalate), polyethylene naphthalate, polybutylene naphthalate, polypropylene naphthalate and a copolymer thereof.
- polyethylene terephthalate and its copolymer are particularly preferred.
- the copolymer preferably contains the above repeating unit in an amount of 60 mol% or more, more preferably 70 mol% or more.
- this polyester force also The thermal stability of the polyester can be further increased by removing or deactivating the catalyst by adding a phosphorus compound or the like.
- the polyester of the present invention may contain organic, inorganic, and organometallic toners, as well as a fluorescent whitening agent, and the like. Coloring such as yellowing can be suppressed to a more excellent level. It also contains other optional polymer antistatic agents, antifoaming agents, dyeing improvers, dyes, pigments, matting agents, fluorescent brighteners, stabilizers, antioxidants, and other additives. May be.
- the anti-oxidation inhibitor aromatic amine-based, phenol-based, etc. anti-oxidation inhibitors can be used, and as the stabilizer, phosphorus-based such as phosphoric acid or phosphate ester-based, sulfur-based, etc. Stabilizers such as amines can be used.
- additives can be added during or after the polymerization of the polyester, or at any stage during the molding of the polyester.
- the suitable stage depends on the characteristics of the compound and the required performance of the polyester molded article. Each is different according to.
- the polyester polymerized using the polyester polymerization catalyst of the present invention can produce fibers by a conventional melt spinning method.
- pigments such as titanium oxide are added to form full-dull or semi-dull fibers
- sulfoisophthalate is copolymerized to make it easy to dye
- phosphorus-based monomers are copolymerized to impart flame retardancy.
- Various techniques such as can be applied.
- the polyester of the present invention is suitably used as a hollow container for beverage containers such as mineral water, juice, wine and whiskey, baby bottles, bottled food containers, containers for hairdressing products and cosmetics, and detergent containers for homes and dishes.
- beverage containers such as mineral water, juice, wine and whiskey, baby bottles, bottled food containers, containers for hairdressing products and cosmetics, and detergent containers for homes and dishes.
- the polyester of the present invention can be extruded into a sheet-like material with an extruding force and can be formed into a sheet.
- a sheet is processed by vacuum forming, pressure forming, embossing, or the like, and is used as a tray container, a cup, a blister pack, a carrier tape for electronic components, and a tray for electronic component delivery for food and miscellaneous goods.
- the sheet can also be used as various cards
- the polyester polymerized using the polyester polymerization catalyst of the present invention can be used for an unstretched film or an oriented film such as biaxially stretched. In the film, particles such as silica may be added to impart slipperiness.
- the polyester film is preferably an antistatic film, an easily adhesive film, a card, a dummy can, agriculture, a building material, a cosmetic material, a wallpaper, an OHP film, a printing, an ink jet recording.
- For sublimation transfer recording for laser beam printer recording, for electrophotographic recording, for thermal transfer recording, for thermal transfer recording, for printed circuit board wiring, for membrane switches, for plasma displays, for touch panels, for masking films, for photoengraving, For Lentogen film, Photo negative film, Retardation film, Polarizing film, Polarizing film protection (TAC), Protecting film, Photosensitive resin film, Field of view expanding film, Diffusion sheet, Reflective film , Antireflection film, conductive film, separator, UV protection, knock grind It used to such use.
- the polyester resin of the present invention can provide a high quality molded product with little deterioration.
- a gas-noline resin layer such as polybutyl alcohol or polymeta-xylylenediamine adipate, a light-blocking resin layer, or a recycled polyester layer is provided in the intermediate layer.
- metal such as aluminum, silicon oxide, silicon oxide, aluminum oxide, aluminum oxide, zinc oxide, zinc oxide, diamond-like carbon, and the like can be obtained by using a method such as vapor deposition or CVD (chemical vapor deposition). It is also possible to coat with such a layer.
- other inorganic nucleating agents such as polyethylene and other talc such as polyethylene can be added.
- the insoluble content of the aluminum compound in water was calculated by the following equation.
- the aluminum compound is an aqueous solution
- a part of the aqueous solution is sampled, and the solid content in the aqueous solution is measured by evaporating the aqueous solution to dryness.
- the solid content is used as the weight of the aluminum compound to determine the concentration of the aluminum compound in the aqueous solution. It was determined by filtering an amount of the aqueous solution in which the amount of the aluminum compound in the aqueous solution was 30 g.
- aqueous solution when the concentration of the aluminum compound in the aqueous solution was higher than 2% by mass, pure water was diluted with aluminum to a concentration of 2% by mass, followed by filtration. The dilution was performed under the same conditions as those for dissolving the solid aluminum compound. The above operation was performed in a clean bench.
- Measurement solution Add 20 parts by volume of deuterated dimethyl sulfoxide to 80 parts by volume of sample
- the peak integrated value measured under the above conditions was set to 1.0 as a reference, and the ratio was expressed as a ratio of the peak integrated value appearing in one of 15 to 30 ppm of the ethylene glycol solution of the aluminum compound measured by the above method.
- Measurement solution 20 parts by volume of deuterated dimethyl sulfoxide is added to 80 parts by volume of the sample.
- the oligomer was pulverized with a handy mill (pulverizer) without being exposed to drying. 1.00 g of the sample was precisely weighed, and 20 ml of pyridine was added. Several zeolite were added, and the mixture was boiled under reflux for 15 minutes to dissolve. Immediately after boiling and refluxing, 10 ml of pure water was added, and the mixture was allowed to cool to room temperature. Titration was performed with N / 10-NaOH using phenolphthalein as an indicator. Do the same for the blank without any sample. When the oligomer did not dissolve in pyridine, the reaction was performed in benzyl alcohol. AVo (eqZton) is calculated according to the following equation.
- the factor (F) of the solution is determined according to the following formula.
- polyester pellets (length: about 3 mm, diameter: about 2 mm, cylinder) obtained by melt polycondensation and solid-phase polycondensation was mixed with phenol Zl, 1,2,2-tetrachloroethane by 6/4 (weight Ratio) Dissolved in a mixed solvent at 80-100 ° C for several hours, and measured at a temperature of 30 ° C using an Ubbelohde viscometer. The concentration was measured at several points around 4 gZl, and the IV was determined according to a standard method.
- the L value and b value of the hunter were measured using a color difference meter (manufactured by Tokyo Denshoku Co., Ltd .: Model ND-1001 DP).
- Polyester 0.1 lg was decomposed by heating at 250 ° C. in 2 ml of methanol and then separated and quantified by gas chromatography.
- the measurement was carried out under the conditions of PHA (wave height analyzer) 100-300 using X-ray output 50kV-70mA, using pentaerythritol as a spectral crystal, and a PC (proportional counter) as a detector.
- PHA microwave height analyzer
- PC proportional counter
- the amount of aluminum element in the resin was determined by high frequency inductively coupled plasma emission spectrometry.
- the amount of aluminum-based foreign matter insoluble in the polyester measured by the above-mentioned evaluation method is preferably 3500 ppm or less, more preferably 2000 ppm, and still more preferably 100 ppm or less as apparent aluminum element amount.
- the content of fine foreign matter insoluble in polyester increases.
- the haze of the molded body is increased. If the filter clogging during filtration of the polyester in the polymerization step or the molding step increases, this leads to the following problem, which is not preferable.
- the polyester was heated to a melting point of + 20 ° C. and melted in a stainless steel circular ring having a thickness of 5 mm and an inner diameter of 50 mm to prepare a sample screw.
- the amount of the element was determined by fluorescent X-ray analysis, and the result was expressed in ppm. In determining the amount, a calibration curve was obtained from a sample of which the amount of each element was known in advance.
- Two electrode plates are placed in polyester melted at 275 ° C, and a current value G) when a voltage of 120 V is applied is measured, and a specific resistance value i is obtained by the following equation.
- the polyester resin was dried under vacuum at 130 ° C for 12 hours, and heat-pressed to create 1000 ⁇ 10 sheets.
- the heat press temperature, pressure and time were 320 ° C, 100 kgZcm 2 G and 3 seconds, respectively.
- the sheet was put into water and rapidly cooled.
- the obtained sheet was uniaxially stretched 3.5 times with a batch stretching machine (manufactured by TM LONG CO., INC, FILM STRETCHER) to obtain a uniaxially stretched film of 300 ⁇ 20 / zm.
- the stretching temperature was 95 ° C for the blowing temperature and 100 ° C for the Z plate temperature.
- the stretching speed was set at 150,000% Z.
- the haze of the obtained uniaxially stretched film was measured using a haze meter (300A, manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS-K7136. The measurement was performed five times, and the average value was obtained. The haze value was represented by a value converted to a film thickness of 300 ⁇ m.
- the polyester was dried with a dryer using dehumidified nitrogen, and a preform was molded at a resin temperature of 295 ° C. using an M-150C (DM) injection molding machine manufactured by Koki Seisakusho.
- the plug part of this preform was heated and crystallized with a home-made plug part crystallizer, and then biaxially stretch-blow-molded using a Corplast LB-01E stretch-blow molding machine. Set to Then, it was heat-set in a mold for about 7 seconds to obtain a 1500 cc hollow molded body (the body was circular).
- the transparency of the hollow molded body obtained by molding according to the above method (2) was evaluated using the following three-step visual evaluation method.
- Irganoxl 222 (manufactured by Chinoku Specialty Chemicals Co., Ltd.) represented by (I-Dani 39) as a phosphorus compound was charged into a flask together with ethylene glycol, and heated with stirring at a liquid temperature of 160 ° C for 12 hours while stirring under nitrogen displacement. An ethylene glycol solution of the phosphorus compound was prepared.
- Ethylene glycol solution of the above aluminum compound A mixture of the ethylene glycol solution of the phosphorus compound and the ethylene glycol solution obtained in Preparation Example 1 was charged into a flask, and the temperature was raised to 160 ° C with stirring without replacing with nitrogen, and maintained for 30 minutes. Then, the mixture was cooled to about 40 ° C to obtain a polymerization catalyst for polyester.
- Example 1 of preparing a mixture of an ethylene glycol solution of an aluminum compound and an ethylene glycol solution of a phosphorus compound V.
- Aluminum is used for the acid component in the polyester.
- atoms and each 0.014 mole 0/0, and 0.028 molar% to become so Ka ⁇ E as phosphorus atom then under a nitrogen atmosphere, the mixture was stirred for 10 minutes at 250 ° C under normal pressure.
- the pressure of the reaction system was gradually decreased to 13.3 Pa (0.1 ITorr) while the temperature was raised to 280 ° C over 60 minutes, and the polycondensation reaction was further performed at 280 ° C and 13.3 Pa.
- the resin under slight pressure is discharged into cold water in the form of a strand and quenched.Then, the resin is held in cold water for 20 seconds, and then pressed to form a cylindrical pellet having a length of about 3 mm and a diameter of about 2 mm. Obtained.
- Table 1 shows the time required for the polycondensation reaction (polymerization time) and the IV of the obtained polyester.
- the polyester pellets obtained by melt polymerization are dried under reduced pressure (13.3 Pa or less, 80 ° C, 12 hours), and then crystallized (13.3 Pa or less, 130 ° C, 3 hours, 13.3P a, 160 ° C, 3 hours). After cooling, the polyester pellet was subjected to solid-state polymerization in a solid-state polymerization reactor while maintaining the inside of the system at 13.5 Pa or less and 215 ° C to obtain polyester pellets with an IV of 0.78 dLZg. .
- Table 1 shows the evaluation results of the transparency and foreign substances of the hollow molded article according to the methods described in (2), (3) and (4) above.
- Example 6 an ethylene glycol solution of 50 gZl of magnesium acetate tetrahydrate was added as a polycondensation catalyst in an amount of 0.1 Olmol% as a magnesium atom to an acid component.
- Comparative Example 2 did not use an A1-based catalyst. was added Echirendari call solution Sansani ⁇ antimony polycondensation catalyst so that 0.04 mole 0/0 as antimony atom relative to the acid component in the polyester.
- table 1
- Example No. of preparation of mixture of aluminum compound solution and phosphorus compound solution is shown. (Example B—1, 2, 3, 6, 7, 8 and Reference Example B—1, 2)
- An aqueous solution of 67 gZl was prepared at room temperature using aluminum lactate. Ethylene glycol was added to the obtained aqueous solution of aluminum lactate and heated at about 100 ° C. to distill off water to obtain about 29 g Zl of an ethylene glycol solution.
- High purity BHET obtained by chemical recovery of PET bottles and high purity terephthalic acid were charged into a 2-litre stainless steel autoclave equipped with a stirrer, and an esterification reaction was carried out. The esteri-dani reaction was performed at 255 ° C. The charge ratio of high-purity BHET to high-purity terephthalic acid was adjusted to obtain a polyester oligomer.
- the acid value of the final product oligomers AVo
- BHET or terephthalic acid with high purity is added to the mixture, and the esterification reaction is performed at 255 ° C so that the OHV% with respect to all the terminal groups of the oligomer is 300 ⁇ 950eqZton and the OHV% is 65 ⁇ 5%. did.
- An in-line mixer consisting of two continuous esterification reactors and three polycondensation reactors, and having a high-speed stirrer on the transfer line to the second esterification reactor
- the continuous polyester manufacturing equipment installed was prepared by mixing 1 part by mass of high-purity terephthalic acid with 0.45 parts by mass of ethylene glycol and continuously supplying the slurry.
- the first esterified tank is supplied at a reaction temperature of 250 ° C., 0.1 MPa
- the second esterified tank is 250 ° C.
- the reaction time in the first and second esterified tanks is adjusted at 250 ° C., IMPa
- ethylene Darcol was charged into the second Esteroi Dari reaction tank to obtain a polyester oligomer.
- the AVo and OHVo of the oligomer at the outlet of the first esterification reactor were 1600 eq / ton and 1400 eq / ton, respectively.
- the AVo and Vo of the oligomer at the outlet of the second esterification reaction tank were 650 eqZton and 1520 eqZton, respectively, and the OH V% was 70 mol%.
- the oligomer is continuously transferred to a continuous polycondensation apparatus comprising three reaction tanks, and an ethylene glycol solution of the aluminum compound prepared by the above method and a phosphorus compound are supplied to an in-line mixer installed in the transfer line.
- the initial polycondensation reactor is 265 ° C, 0.009MPa
- the middle polycondensation reactor is 265-275 ° C, 0.0007MPa
- the final polycondensation reactor is 270-280 ° C, 0. 62 PETs were obtained.
- Table 3 shows the characteristic values of the obtained PET.
- the NMR spectrum of the mixture of the aluminum compound solution and the phosphorus conjugate solution at the outlet of the stirring mixer does not exist in the spectrum of the phosphorus compound ethylene glycol solution before mixing with the aluminum compound ethylene glycol solution.
- a broad peak (referred to as coordination peak) was observed in the range of 5-24 ppm.
- the integral value of the coordination peak is determined by the NMR of the phosphorus atom bonded to the hydroxyl group, which is observed in the vicinity of 25-27 ppm in the NMR ⁇ vector of the ethylene glycol solution of the phosphorus conjugate before mixing with the ethylene glycol solution of the aluminum compound. ⁇ It was 45% of the integrated value of the vector peak.
- Example C 3 The procedure was performed in the same manner as in Example C1 except for the conditions described in Table 3.
- the NMR spectrum of an ethylene glycol mixed solution of the aluminum compound of Reference Example C1 was as shown in FIG. 2 and had an integration ratio of 0.19.
- the NMR spectrum of the mixed solution of the compound solution and the phosphorus conjugate solution showed almost no coordination peak.
- the ethylene glycol solution of the aluminum compound prepared by the method of Example 1 and the ethylene glycol solution of the phosphorus conjugate were mixed at room temperature in a quantitative ratio such that the molar ratio of aluminum atoms to phosphorus atoms was 1: 2.40. After stirring and mixing for a minute, a polycondensation catalyst solution was obtained. NMR spectra of the above-mentioned phosphorus compound in an ethylene glycol solution and a polycondensation catalyst solution were measured. The NMR spectrum of the polycondensation catalyst solution does not exist in the spectrum of the ethylene glycol solution of the phosphorus conjugate before mixing with the ethylene glycol solution of the aluminum compound.
- a broad peak in the range of 5 to 24 ppm (referred to as a coordination peak) ) was observed.
- Figure 3 shows the studio.
- the integrated value of the coordination peak is the NMR ⁇ vector peak of the hydroxyl-bonded phosphorus atom, which is observed at around 25-27 ppm in the NMR spectrum of the ethylene glycol solution of the phosphorus compound before mixing with the ethylene glycol solution of the aluminum compound. It was 50% of the integrated value of the peak.
- the resulting mixed solution was stored at 20-35 ° C.
- Example C-1 In the same manner as in Example C-1, except that the polycondensation catalyst solution prepared by the above method and stored for about one month was changed so as to be continuously supplied to the in-line mixer, the same method as in Example 1 was used.
- the PET of Example 3 was obtained by the method. Table 3 shows the properties of the obtained PET.
- the PET obtained in Example C13 and Comparative Example C13 was subjected to solid-state polycondensation by a conventional method to obtain I VO.75dlZg, which was dried with a drier using dehumidified air.
- a preform was molded at a resin temperature of 295 ° C using a -150C (DM) injection molding machine.
- DM -150C
- the density is the density deviation Measurement was performed at 30 ° C on a density gradient line of a mixed solution of calcium nitrate and Z water.
- the haze of the hollow molded body was measured by cutting a sample from the body (thickness: about 0.45 mm) of the hollow molded body and using a haze meter model NDH2000 manufactured by Nippon Denshoku Co., Ltd. Table 3 shows the evaluation results. Table 3
- Magnesium acetate tetrahydrate and sodium acetate were dissolved in ethylene glycol at a concentration of 50 gZl and lOgZl, respectively, to form solutions.
- a slurry prepared by mixing 1 part by mass of high-purity terephthalic acid with 0.4 part by mass of ethylene glycol in a continuous polyester production apparatus comprising two continuous esterification reactors and three polycondensation reactors was continuously supplied, and the first esterified tank was reacted at a reaction temperature of 250 ° C. and 0.1 MPa, and the second esterified reactor was reacted at 255 ° C. and IMPa to obtain a lower condensate.
- the low-order condensate product was continuously transferred to a continuous polycondensation apparatus consisting of three reactors, and the initial polymerization reactor power was 265 ° C and 0.009 MPa, and the middle polymerization reactor power was 270 ° C and 0.09 MPa.
- PET of UV 0.61 was obtained.
- the mixed solution, magnesium compound solution and sodium compound solution composed of the aluminum compound and the phosphorus compound prepared by the above-described method in the second esteri-dani reactor were respectively added to the amounts shown in Table 4 as the amounts remaining in the PET. It was soaked.
- Table 4 shows the evaluation results of the obtained PET.
- the PET obtained in this example has a low polymer melting specific resistance and excellent electrostatic adhesion, has a small amount of foreign matter insoluble in polyester, and has a low haze of the axially stretched film. Further, the DEG content is low and the color tone is good. Therefore, for example, it was of high quality as a raw material for producing films and sheets. Table 4 shows the results.
- Example D-1 was carried out in the same manner as in Example D-1, except that the preparation of the ethylene glycol solution of the aluminum compound was changed to distill water at a liquid temperature of 150 to 170 ° C under normal pressure.
- the polycondensation time of the obtained PET was inferior to that of each property, but was about 1.5 times that of Example 1. Table 5 shows the results.
- Example D-1 and Example D-1 except that the ethylene glycol solution of the aluminum compound and the ethylene glycol solution of the phosphorus compound were not mixed, but were changed so as to be continuously supplied to the second esterification reactor from separate supply ports. The same was done. Table 5 shows the results
- the amounts of aluminum, magnesium, sodium and phosphorus in the PET were determined in the same manner as in Example 1 except that the supply amounts of the respective compounds were changed so that the amounts shown in Table 5 were obtained. Table 5 shows the results.
- AI-NR stress ratio
- AI element direct (ppm) 30 30 30 30 30 21 21 21 30
- an antimony conjugate having a defect, a germanium compound and a titanium compound are not contained as a main component of a catalyst, and an aluminum compound is used as a catalyst metal component.
- Polyesters which are excellent, and which can exert their characteristics in the fields of ultra-fine fibers with few foreign substances, highly transparent films for optics, and ultra-highly transparent molded articles, are obtained.
- a polyester polymerization catalyst having a high activity capable of providing such a polyester and a method for producing a polyester using the same are obtained.
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Abstract
Description
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EP05709847A EP1719790A4 (en) | 2004-02-10 | 2005-02-08 | POLYMER CATALYST OF A POLYESTER, POLYEST ER PRODUCED WITH THIS CATALYST AND POLYESTER PRODUCT PROCESS |
US10/588,652 US20070106055A1 (en) | 2004-02-10 | 2005-02-08 | Polyester polymerization catalyst, polyester produced therewith and process for producing the polyester |
JP2005517775A JPWO2005075539A1 (ja) | 2004-02-10 | 2005-02-08 | ポリエステル重合触媒およびこれを用いて製造されたポリエステル並びにポリエステルの製造方法 |
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Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2008094933A (ja) * | 2006-10-11 | 2008-04-24 | Toyobo Co Ltd | ポリエステルの製造方法 |
JP2008094935A (ja) * | 2006-10-11 | 2008-04-24 | Toyobo Co Ltd | ポリエステルの製造方法 |
US7838596B2 (en) | 2005-09-16 | 2010-11-23 | Eastman Chemical Company | Late addition to effect compositional modifications in condensation polymers |
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JP2002327052A (ja) * | 2001-04-27 | 2002-11-15 | Toyobo Co Ltd | ポリエステルならびにポリエステルの製造方法 |
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- 2005-02-08 WO PCT/JP2005/001795 patent/WO2005075539A1/ja active Application Filing
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US9267007B2 (en) | 2005-09-16 | 2016-02-23 | Grupo Petrotemex, S.A. De C.V. | Method for addition of additives into a polymer melt |
JP2008094935A (ja) * | 2006-10-11 | 2008-04-24 | Toyobo Co Ltd | ポリエステルの製造方法 |
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JP7356357B2 (ja) | 2017-06-02 | 2023-10-04 | エスケー ケミカルズ カンパニー リミテッド | ポリエステル繊維の製造方法 |
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WO2024062999A1 (ja) * | 2022-09-22 | 2024-03-28 | 東洋紡株式会社 | バイオマス資源由来のポリエステル樹脂を用いたポリエステルフィルムの製造方法およびポリエステルフィルム |
Also Published As
Publication number | Publication date |
---|---|
JPWO2005075539A1 (ja) | 2007-10-11 |
EP1719790A1 (en) | 2006-11-08 |
TW200602381A (en) | 2006-01-16 |
US20070106055A1 (en) | 2007-05-10 |
EP1719790A4 (en) | 2007-01-24 |
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