JP4457759B2 - Catalyst for producing polyester, method for producing polyester using the same, and titanium-containing polyethylene terephthalate - Google Patents

Description

  The present invention relates to a catalyst for producing a polyester, a method for producing a polyester using the catalyst, and a titanium-containing polyethylene terephthalate having excellent characteristics.

  Conventionally, polyesters typified by polyethylene terephthalate have excellent mechanical strength, chemical stability, gas barrier properties, hygiene, etc., and are relatively inexpensive and lightweight, so various packaging materials such as bottles and films Or it has been widely used as a fiber.

  And these polyesters are conventionally produced mainly using an antimony compound as a polycondensation catalyst, but when using an antimony compound, there is a problem of foreign matter and haze due to antimony metal precipitation in the obtained polyester, Alternatively, since an antimony compound requires a large amount of catalyst of 300 to 400 ppm, development of a highly active polyester production catalyst that can replace the antimony compound has been strongly desired.

  Many methods of using a 4A group compound, especially a titanium compound as a polycondensation catalyst have been proposed as a method for producing a polyester resin without using an antimony compound. As a titanium compound-based polycondensation catalyst, for example, simultaneous hydrolysis of a titanium compound and a metal compound of a metal selected from the group of IA, IIA, VIIIA, IB, IIB, IIIB and IVB of the periodic table It is known to use the coprecipitates produced by precipitation by means of alone or as a mixture. Specifically, it is shown that a coprecipitate obtained by simultaneously hydrolyzing tetraisopropoxytitanium and an alkoxy compound such as magnesium with water in absolute ethanol is used as a catalyst (patent document). 1).

  The preparation of the catalyst exemplified here requires a number of steps, such as hydrolysis of the alkoxy compound, centrifugation, washing and drying. Moreover, since the prepared catalyst is dried once and then subjected to a polycondensation reaction as a slurry of a solvent such as ethylene glycol, the catalyst particles are coarse and may remain as foreign matter in the resulting polyester.

  In addition, it is also known that a composite oxide mainly composed of titanium and silicon is mixed with a diol or an ester-forming derivative thereof in advance, and a mixture heated to 160 to 220 ° C. is used as a catalyst. Shows that a coprecipitate obtained by hydrolyzing a mixture of tetraisopropoxy titanium and ethyl orthosilicate with water in ethanol is used as a catalyst after heat treatment in ethylene glycol at 198 ° C. (See Patent Document 2).

  By using the catalyst exemplified here, the amount of foreign matter in the polyester obtained than when antimony is used as the catalyst tends to be reduced, but according to the study by the present inventors, it is put to practical use. Turned out to be insufficient. Furthermore, the catalyst exemplified here needs to be mixed in the catalyst component at the time of preparation, heated to form a gel, and then dried under reduced pressure, and the preparation requires many steps.

  In addition, it is known to use polysiloxane as a co-catalyst at the time of polymerization for the purpose of improving the color tone, and specifically, the use of organic polyborosiloxane has been shown (see Patent Document 3). The polysiloxane disclosed here is obtained by mixing diphenyldichlorosilane and boric acid and then reacting them for 12 hours, and it takes a long time to prepare the catalyst.

  Furthermore, it is known that a titanium compound and at least one compound selected from a magnesium compound, an aluminum compound, a barium compound, and the like are added at the time of polymerization. Specifically, tetrabutoxy titanium and magnesium acetate are used. Has been shown to be added during polymerization (see Patent Document 4).

  However, in the method shown here, there are problems that the color tone of the obtained polyester is poor and that the amount of acetaldehyde contained after solid phase polymerization is large. In addition, among these catalysts, when a plurality of metal compounds are combined to form a catalyst, it is necessary to specify the addition timing of each metal compound.

  Polyesters produced by using these titanium compounds as polycondensation catalysts may have insufficient thermal stability, represented by acid value, etc., compared to polyesters produced using antimony compounds. It was.

As described above, a titanium compound-based catalyst has been proposed as a catalyst for polyester production in place of the antimony compound. However, according to the study by the present inventors, the conventional titanium compound-based catalyst has a complicated manufacturing process. In many methods using a conventional titanium compound catalyst, the decomposition reaction proceeds because the time required for the polycondensation reaction is long, and the color tone of the resulting polyester tends to deteriorate. The thermal stability is insufficient, the volume resistivity is high and insufficient, and the acetaldehyde residual amount in the resin and the amount of contained foreign matter are still unsatisfactory as an industrial production method. It turned out to be. Therefore, development of a catalyst for producing a polyester having a further excellent activity and capable of producing a high-quality polyester and being easy to produce and handle is strongly desired.
Special table 2002-503274 gazette JP 2001-288262 A JP 59-142221 A JP 2000-143789 A

  The present invention has been made in view of the above circumstances, and is easy to manufacture and handle, and improves the disadvantage that the color tone deteriorates because a long time is required for the polycondensation reaction caused by the conventional catalyst. The present invention provides a catalyst for producing a polyester capable of producing a polyester having improved properties, volume resistivity, acetaldehyde content and content of foreign matter, and has excellent characteristics by using such a catalyst. The present invention provides a method for producing a polyester having a good productivity.

  And the titanium atom derived from the titanium compound used as a catalyst for the polycondensation reaction has a specific structure in the obtained polyethylene terephthalate, thereby providing titanium-containing polyethylene terephthalate having excellent characteristics. .

  As a result of intensive studies in view of the above problems, the present inventors, as a polycondensation catalyst, at least (1) a group 4A compound (hereinafter sometimes referred to as “compound (1)”), (2) magnesium, calcium, And a compound of at least one element selected from the group consisting of zinc (hereinafter sometimes referred to as “compound (2)”), (3) a silicate compound (hereinafter referred to as “compound (3)”), and It has been found that a polyester production catalyst containing an oxygen-containing organic solvent is highly active as a polyester production catalyst, and that polyethylene terephthalate produced using this catalyst is extremely excellent in quality. It came to complete.

  That is, the first gist of the present invention is at least (1) a compound of at least one element selected from the group consisting of a group 4A compound, (2) magnesium, calcium, and zinc, and (3) a silicate compound. And a catalyst for producing a polyester comprising an oxygen-containing organic solvent, wherein the compound (1) is alkoxytitanium and the oxygen-containing organic solvent is ethylene glycol. .

  The polyester production catalyst is preferably prepared at 150 ° C. or lower.

  In this polyester production catalyst, the compound (2) is preferably a magnesium compound. In this case, it is particularly preferable to contain a hexagonal crystal in which one atom of the group 4A element derived from the compound (1) and / or one atom of the magnesium element derived from the compound (2) is solvated with six ethylene glycol molecules.

  Moreover, as a compound (3), an orthosilicate ester compound is preferable.

  The mixing ratio of the compound (1) and the compound (2) is the total (molar ratio) of Group 4A elements: magnesium, calcium, and zinc elements, and may be in the range of 95: 5 to 5:95. preferable.

  The second gist of the present invention is that a dicarboxylic acid component mainly composed of an aromatic dicarboxylic acid and / or an ester-forming derivative thereof and a dihydric alcohol component are subjected to polymerization through an esterification reaction and / or a transesterification reaction. The present invention resides in a method for producing a polyester, which comprises using the catalyst for producing a polyester of the present invention when producing a polyester by a condensation reaction.

  The polyester production catalyst of the present invention is easy to produce and excellent in handleability, and according to the polyester production catalyst of the present invention, the color tone is good, the thermal stability, the volume specific resistance value or the amount of acetaldehyde and the contained foreign matter. Polyesters with further improved amounts can be produced.

  According to the polyester production method of the present invention using this polyester production catalyst, a polyester having excellent properties can be produced with good productivity.

  The titanium-containing polyethylene terephthalate of the present invention, which is produced in this manner and contains a titanium atom derived from a titanium compound used as a polycondensation reaction catalyst in a specific structure, has excellent characteristics and is useful for various applications. is there.

  Hereinafter, the present invention will be described in detail. However, the description of the constituent elements described below is a representative example of embodiments of the present invention, and the present invention is not limited to these contents.

  The polyester production catalyst of the present invention comprises at least one element selected from the group consisting of (1) a group 4A compound (compound (1)), (2) magnesium, calcium and zinc (hereinafter referred to as “compound (2)”. ) Element ”(compound (2)), and an oxygen-containing organic solvent.

  Examples of the compound (1) include a titanium compound, a zirconium compound, and a hafnium compound. Of these, a titanium compound is preferably used.

  Specifically, as the titanium compound, for example, alkoxy titanium such as tetramethoxy titanium, tetraethoxy titanium, tetraisopropoxy titanium, tetrabutoxy titanium, and organic titanium compounds such as acetylacetonate salt of titanium are usually used. Of these, alkoxy titanium is preferred. The alkoxy group of alkoxytitanium may be linear or branched, and the carbon number thereof is preferably 1-30, more preferably 1-10.

  These compounds (1) may be used individually by 1 type, and may use 2 or more types together.

  The compound (2) is preferably a magnesium and / or calcium compound, and particularly preferably a magnesium compound. The compound (2) may be any compound (2) as long as the counter ion of the element does not adversely affect the polycondensation reaction. Specifically, the compound (2) element hydroxide, acetate, etc. Carboxylates, nitrates, halides, carbonates, alkoxides, acetylacetonates, and the like can be used. Of these, carboxylates such as acetate of the compound (2) element and alkoxides are preferably used. As for carbon number of carboxylate and an alkoxide, 1-30 are preferable, More preferably, it is 1-10.

  These compounds (2) may be used individually by 1 type, and may use 2 or more types together. By using these compounds (2), the volume specific resistance value of the resulting polyester tends to decrease, which is particularly suitable for obtaining a polyester for film use.

  Examples of oxygen-containing organic solvents include monohydric alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, decamethylene glycol , Neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, diethylene glycol, polyethylene glycol, polytetramethylene ether glycol and other aliphatic dihydric alcohols, 1,2-cyclohexanediol, 1,4-cyclohexane Diol, 1,1-cyclohexane dimethylol, 1,4-cyclohexane dimethylol, alicyclic dihydric alcohols such as 2,5-norbornane dimethylol, and xyl Glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4′-hydroxyphenyl) propane, 2,2-bis (4′-β-hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) sulfone , Aromatic divalent alcohols such as bis (4-β-hydroxyethoxyphenyl) sulfonic acid, and divalents such as ethylene oxide adducts or propylene oxide adducts of 2,2-bis (4′-hydroxyphenyl) propane Alcohols etc. can be mentioned. Of these oxygen-containing organic compounds, dihydric alcohols are preferably used, of which aliphatic dihydric alcohols are preferred, ethylene glycol and tetramethylene glycol are more preferred, and ethylene glycol is particularly preferred. The

  These oxygen-containing organic compounds may be used alone or in combination of two or more.

  The amount of the group 4A metal atom derived from the compound (1) contained in the catalyst for producing a polyester of the present invention is usually preferably 10 to 100,000 ppm, more preferably 50 to 50,000 ppm, particularly preferably based on the oxygen-containing organic solvent. Is 100-10000 ppm.

  The ratio of the compound (2) to the compound (1) is selected from the group consisting of the 4A group atom derived from the compound (1) and the compound (2) element derived from the compound (2) (magnesium, calcium, and zinc). At least one atom) in the range of 4A group atom: compound (2) element = 95: 5 to 5:95, especially 95: 5 to 10:90, especially 90:10 The range is preferably 10:90. Even if the ratio of the compound (2) to the compound (1) is too large or too small, the catalyst activity control action by the combined use of the compound (1) and the compound (2) described below cannot be sufficiently obtained.

  By using the catalyst for producing a polyester of the present invention containing the compound (1), the compound (2) and an oxygen-containing organic compound, a polyester having a good color tone can be obtained. Although the details of the reason are unclear, the activity of the compound (1) as a polycondensation reaction catalyst of the 4A group compound by taking a specific structure during the polycondensation reaction. This is considered to be due to controlling the decomposition reaction that causes coloring.

  The polyester production catalyst of the present invention is a collective liquid catalyst containing all of the compound (1), the compound (2), and the oxygen-containing organic solvent. It may be. However, the catalyst for producing a polyester of the present invention has less solids than the case where a conventionally known hydrolysis coprecipitate is used as a catalyst, that is, the precipitation of solids is small, so that the foreign matter in the obtained polyester is reduced. Another characteristic is that there are few. Further, when the compound (2) is a magnesium compound, solids tend to be precipitated more often than calcium compounds and zinc compounds, but unlike the case where a conventionally known hydrolysis coprecipitate is used as a catalyst for polyester production. Since solids are generated in an oxygen-containing organic solvent, the precipitated solids become fine and are unlikely to cause sedimentation or solidification. The fact that the precipitated solid matter is fine is considered to be one of the reasons why there are few foreign matters in the obtained polyester. Moreover, since it is a collective liquid catalyst, compared with a conventionally well-known catalyst, handling, storage, addition operation in a manufacturing process, etc. are easy. On the other hand, in general, the liquid catalyst may easily deteriorate in quality, but the catalyst for producing a polyester of the present invention is unlikely to deteriorate in quality and has another characteristic that it can be stored for a long time.

In preparing the polyester production catalyst of the present invention, a method of mixing the compound (1), the compound (2) and the oxygen-containing organic solvent is generally used. The mixing method of the compound (1), the compound (2), and the oxygen-containing organic solvent is not particularly limited, and mixing is performed using a batch method in which mixing is performed in advance in a mixing tank or a mixer or the like in a pipe during liquid feeding. Although the continuous method to perform is mentioned, Usually, it carries out by the batch method. The order of mixing the compound (1), the compound (2), and the oxygen-containing organic solvent is not particularly limited, and examples thereof include the following methods (1) to (5). Among these, (1), The methods (2), (3) and (4) are preferably used.
(1) A method in which compound (1) is added to an oxygen-containing organic solvent, followed by addition of compound (2)
(2) A method in which compound (2) is added to an oxygen-containing organic solvent, followed by addition of compound (1)
(3) Method of mixing the compound (1) and the compound (2) and subsequently mixing the oxygen-containing organic solvent
(4) A method in which the compound (1) is added to the oxygen-containing organic solvent, and then a mixture of the compound (2) and the oxygen-containing organic solvent is added.
(5) Method of adding the compound (2) to the oxygen-containing organic solvent and subsequently adding the mixture of the compound (1) and the oxygen-containing organic solvent. The catalyst for producing the polyester of the present invention further comprises (3) a silicate ester It is preferable to contain a compound (compound (3)).

As the compound (3), a general formula R ² _n Si (OR ¹ ) _4-n (wherein R ¹ and R ² each independently represents a substituent. The substituent is a linear or branched alkyl. And an aryl group such as a phenyl group, and n is an integer of 0 to 3.). Specific examples thereof include compounds such as tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabenzyloxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane. Among these, an orthosilicate ester compound in which n is 0 is particularly preferably used, and the carbon number of R ¹ and R ² is preferably 1 to 30, more preferably 1 to 10.

  When the catalyst for polyester production of the present invention contains the compound (3), the ratio of the compound (3) to the compound (1) is such that the silicon atom derived from the compound (3) and the group 4A atom derived from the compound (1) The molar ratio is usually in the range of silicon atom: 4A group atom = 95: 5 to 5:95, particularly in the range of 90:10 to 5:95, especially in the range of 90:10 to 30:70. preferable. If the amount of the compound (3) used is too large, the catalytic activity may be lowered, and if it is too small, the improvement effect by the compound (3) described below tends to be insufficient.

  Details of the reason why the catalyst for producing a polyester of the present invention is more effective when the compound (3) is contained are unknown, but (1) from the group consisting of a group 4A compound, (2) magnesium, calcium, and zinc. When used in the polycondensation reaction as a collective catalyst containing all of the compound of at least one element selected, (3) the silicate compound, and the oxygen-containing organic solvent, It is thought that the dispersibility of the active ingredient of the catalyst for producing a polyester of the invention is improved by the compound (3), and the catalyst performance is further improved.

  Even when the catalyst for producing a polyester of the present invention contains the compound (3) as a preferred embodiment, the preparation of the catalyst is generally performed using the compound (1), the compound (2), the compound (3), and the oxygen-containing organic material. A method of mixing solvents is used. The mixing method of the compound (1), the compound (2), the compound (3), and the oxygen-containing organic solvent is not particularly limited. A batch method in which mixing is performed in a mixing tank in advance, a mixer in a pipe during liquid feeding, or the like. A continuous method in which mixing is carried out using is used, but usually a batch method is used. The mixing method of the compound (1), the compound (2), the compound (3), and the oxygen-containing organic solvent is not particularly limited, and examples thereof include the following methods (6) to (14). The methods (8), (10) and (12) are preferably used.

(6) Method of adding the compound (1) to the oxygen-containing organic solvent, and subsequently adding the compound (2) and then the compound (3)
(7) A method in which compound (1) is added to an oxygen-containing organic solvent, followed by addition of compound (3) and further compound (2)
(8) Method of adding the compound (3) to the oxygen-containing organic solvent, and subsequently adding the compound (2) and then the compound (1)
(9) A method in which compound (3) is added to an oxygen-containing organic solvent, followed by addition of compound (1) and further compound (2)
(10) A method in which compound (2) is added to an oxygen-containing organic solvent, followed by addition of compound (3) and further compound (1)
(11) A method in which compound (2) is added to an oxygen-containing organic solvent, followed by addition of compound (1) and further compound (3)
(12) A method in which compound (3) is added to an oxygen-containing organic solvent, followed by addition of a mixture of compound (2) and oxygen-containing organic solvent, and further a mixture of compound (1) and oxygen-containing organic solvent
(13) Method of simultaneously adding compound (1), compound (3) and compound (2) to an oxygen-containing organic solvent
(14) A method of adding a premixed compound (1) and compound (3) to an oxygen-containing organic solvent and subsequently adding the compound (2)

  The temperature condition for preparing the polyester production catalyst of the present invention, that is, the temperature condition for mixing each component is not particularly limited, but it is preferably 150 ° C. or less, more preferably 100 ° C. or less. Prepared. The higher the preparation temperature, the more easily the hydrolysis reaction occurs during mixing, and the effect of the present invention as a catalyst for producing a polyester tends to decrease. The lower limit of the preparation temperature is not particularly limited, but the viscosity of the oxygen-containing organic solvent tends to increase as the preparation temperature decreases, and the solubility and dispersibility of compound (1) and / or compound (2) are poor. Since it may be sufficient, it is usually prepared at 0 ° C. or higher, preferably 10 ° C. or higher.

  In the catalyst for producing a polyester of the present invention, when a magnesium compound is used as the compound (2) to form a slurry in which a solid is dispersed, the solid is preferably a hexagonal crystal. The hexagonal crystal preferably has a structure in which one atom of the group 4A derived from the compound (1) and / or one atom of the magnesium element derived from the compound (2) is solvated with six ethylene glycol molecules. When the catalyst for producing a polyester of the present invention has such a hexagonal crystal, the crystal takes a specific structure during the polycondensation reaction, thereby controlling the activity of the group 4A compound as a polycondensation reaction catalyst. It is considered that characteristics such as suppression of a decomposition reaction that causes coloring are better expressed.

  The polyester production catalyst of the present invention may contain a compound containing another metal element, for example, an antimony compound, a germanium compound, a cobalt compound, a tin compound, or the like as long as the performance is not impaired. However, since it is considered that the component effective as a catalyst for polyester production is prepared using the compound (1), the compound (2), and an oxygen-containing organic solvent, the compound (1), It is preferable to use only the compound (2) and the one containing an oxygen-containing organic solvent. Even when the compound (3) is further contained, the compound (1), the compound (2), the compound (3) and the oxygen-containing compound are used. It is preferable to use only those containing an organic solvent.

  The polyester production catalyst of the present invention comprises a dicarboxylic acid component mainly composed of an aromatic dicarboxylic acid and / or an ester-forming derivative thereof and a dihydric alcohol component through an esterification reaction and / or a transesterification reaction. It is suitably used as a polycondensation catalyst when producing polyester by condensation.

  The polyester production method of the present invention comprises a dicarboxylic acid component mainly composed of an aromatic dicarboxylic acid and / or an ester-forming derivative thereof and a dihydric alcohol component through an esterification reaction and / or a transesterification reaction. In the method for producing a polyester by condensation, the polyester production catalyst is preferably used in a polymerization reaction system.

  In the polyester production method of the present invention, examples of the aromatic dicarboxylic acid and / or its ester-forming derivative as the main component of the dicarboxylic acid component include terephthalic acid, phthalic acid, isophthalic acid, dibromoisophthalic acid, and sulfoisophthalic acid. Sodium, phenylenedioxydicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenylether dicarboxylic acid, 4,4′-diphenylketone dicarboxylic acid, 4,4′-diphenoxyethanedicarboxylic acid, 4,4 Carbon atoms of aromatic dicarboxylic acids such as' -diphenylsulfone dicarboxylic acid and 2,6-naphthalenedicarboxylic acid, or aromatic dicarboxylic acids such as terephthalic acid dimethyl ester and 2,6-naphthalenedicarboxylic acid dimethyl ester Degree of dialkyl ester, and Gen product, and the like. Among these, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and ester-forming derivatives thereof are preferable, and terephthalic acid and ester-forming derivatives thereof are particularly preferable.

  These aromatic dicarboxylic acids and / or ester-forming derivatives thereof may be used alone or in combination of two or more.

  Here, the main component means that the aromatic dicarboxylic acid and / or its ester-forming derivative is 80 mol% or more of the dicarboxylic acid component, preferably 90 mol% or more, and more preferably 95 mol% or more. Preferably, it is 98 mol% or more, and it is especially preferable.

  Examples of the dicarboxylic acid component other than the aromatic dicarboxylic acid and / or its ester-forming derivative include, for example, alicyclic dicarboxylic acids such as hexahydroterephthalic acid and hexahydroisophthalic acid, succinic acid, glutaric acid, Aliphatic dicarboxylic acids such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecadicarboxylic acid, dodecadicarboxylic acid, etc., and alicyclic dicarboxylic acids and aliphatic dicarboxylic acids having 1 to 4 carbon atoms Degree of dialkyl esters, halides and the like.

  Examples of the dihydric alcohol component include ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, decamethylene glycol, neopentyl glycol, 2-ethyl-2-butyl- Aliphatic dihydric alcohols such as 1,3-propanediol, diethylene glycol, polyethylene glycol, polytetramethylene ether glycol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethylol, 1,4 -Cycloaliphatic dihydric alcohols such as cyclohexane dimethylol and 2,5-norbornane dimethylol, and xylylene glycol, 4,4'-dihydroxybiphenyl, 2,2-bis ( Aromatic 2 such as' -hydroxyphenyl) propane, 2,2-bis (4'-β-hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, bis (4-β-hydroxyethoxyphenyl) sulfonic acid Examples thereof include a monohydric alcohol and an ethylene oxide adduct or a propylene oxide adduct of 2,2-bis (4′-hydroxyphenyl) propane. Among these, ethylene glycol and tetramethylene glycol are preferable, and ethylene glycol is particularly preferable.

  These dihydric alcohol components may be used individually by 1 type, and may use 2 or more types together.

  For the production of the polyester of the present invention, in addition to the dicarboxylic acid component and the dihydric alcohol component, for example, hydroxycarboxylic acids such as glycolic acid, p-hydroxybenzoic acid, p-β-hydroxyethoxybenzoic acid, and alkoxycarboxylic acids. Acids and monofunctional components such as stearyl alcohol, benzyl alcohol, stearic acid, benzoic acid, t-butylbenzoic acid, benzoylbenzoic acid, tricarballylic acid, trimellitic acid, trimesic acid, pyromellitic acid, gallic acid, trimethyl You may use 1 type (s) or 2 or more types, such as trifunctional or more polyfunctional components, such as a methylol ethane, a trimethylol propane, a glycerol, a pentaerythritol, as a copolymerization component.

  In the reaction between the dicarboxylic acid component and the dihydric alcohol, the proportion of the dihydric alcohol used relative to the dicarboxylic acid component is usually 1 to 3 moles.

  The method for producing the polyester of the present invention is not particularly limited except that the above-mentioned catalyst for producing the polyester of the present invention is used. The polyester is conventionally used for esterification, melt polycondensation and, if necessary, solid phase polycondensation. The manufacturing method can be used. A typical production example is shown below.

First, a dicarboxylic acid component and a dihydric alcohol component are usually converted into an esterification reaction vessel in the presence of an esterification catalyst as necessary, usually at a temperature of 240 to 280 ° C., preferably 250 to 270 ° C. and usually 0 at an absolute pressure. The esterification reaction is carried out for 1 to 10 hours with stirring under a pressure of 1 to 0.4 MPa, preferably 0.1 to 0.3 MPa. Subsequently, the obtained polyester low molecular weight product, which is an esterification reaction product, is transferred to a polycondensation tank, and in the presence of a polycondensation catalyst, it is usually at a temperature of 260 to 290 ° C, preferably 265 to 285 ° C, at normal pressure. The pressure is gradually reduced and finally the absolute pressure is usually 1.3 × 10 ^{1 to} 1.3 × 10 ³ Pa, preferably 6.7 × 10 ^{1 to} 6.7 × 10 ² Pa. Melt polycondensation for 20 hours. These may be performed by either a continuous method or a batch method.

Usually, the resin obtained by melt polycondensation is extracted in the form of a strand from the extraction port provided at the bottom of the polycondensation tank, and is cooled with water or after water cooling, and then cut with a cutter to form pellets, chips, etc. Further, the granule after the melt polycondensation can be subjected to solid phase polycondensation if necessary. In this case, for example, under an inert gas atmosphere such as nitrogen, carbon dioxide, argon, or the like, or under a water vapor atmosphere or a water vapor-containing inert gas atmosphere, a temperature of usually 60 to 180 ° C., preferably 150 to 170 ° C. The resin granule surface is crystallized by heating at a normal temperature, and the resin is usually used under an inert gas atmosphere and / or under a reduced pressure of about 1.3 × 10 ^{1 to} 1.3 × 10 ³ Pa in absolute pressure. The heat treatment is usually carried out for a period of 50 hours or less at a temperature lower than 80 ° C., preferably 10-60 ° C. lower than the adhesion temperature, so that the particles do not stick together, and is subjected to solid phase weighting. Can be condensed. By this solid phase polycondensation, the degree of polymerization can be further increased, and reaction by-products such as acetaldehyde and low-molecular oligomers can be reduced.

  Further, the resin obtained by melt polycondensation or solid phase polycondensation as described above may be further processed depending on the purpose such as deactivation of the polycondensation catalyst. For example, water treatment such as immersion in water of 40 ° C. or higher for 10 minutes or more, or water vapor treatment of contacting water vapor of 60 ° C. or higher or water vapor-containing gas for 30 minutes or more can be performed.

  In such a polyester production process, the addition time of the polyester production catalyst of the present invention is not particularly limited, and at the time of preparing a slurry with a raw dicarboxylic acid component and a dihydric alcohol component, any stage of the esterification process, Or any of the initial stages of a melt polycondensation process may be sufficient. In particular, it is preferably added after the esterification step is completed and before the initial stage of the melt polycondensation step, and more preferably before the start of the melt polycondensation.

  Moreover, the addition method in particular of the catalyst for polyester manufacture of this invention is not restrict | limited, For example, a required quantity may be added at once and you may add in multiple times as needed.

  The catalyst for producing a polyester of the present invention is added so that the metal atom derived from the compound (1) is usually in the range of 0.1 to 200 ppm, preferably in the range of 0.5 to 100 ppm, relative to the theoretical yield of the polyester resin. It is preferable to do.

  Moreover, in this invention, the adjuvant and stabilizer which prevent deterioration of polyester can be used further. Examples of auxiliary agents and stabilizers include phosphate esters such as trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, methyl acid phosphate, ethyl acid phosphate, isopropyl Acid phosphates such as acid phosphate, butyl acid phosphate, dibutyl phosphate, monobutyl phosphate and dioctyl phosphate, and phosphorus compounds such as phosphoric acid, phosphorous acid and polyphosphoric acid are preferably used.

  It is preferable to supply the auxiliary agent and the stabilizer at the initial stage of the raw material slurry preparation, any stage of the esterification process and the melt polycondensation process. Auxiliaries and stabilizers are usually used in the range of usually 1 to 1000 ppm based on the total polycondensation raw material as the weight of phosphorus atoms.

The polyethylene terephthalate of the present invention (hereinafter sometimes abbreviated as “PET”) is a titanium-containing PET having physical properties represented by the following (A), (B) and (C).
(A) When the titanium K absorption edge XAFS spectrum was measured, in the normalized XANES spectrum, the intensity of the peak having the maximum intensity among the peaks existing before the K absorption edge is P _A , and the maximum peak intensity after the K absorption edge Is P _B , and the peak intensity ratio is R = P _A / P _B , R is more than 0.2 (B) Terminal carboxyl group is less than 35 eq / ton (C) Intrinsic viscosity is 0.5 dl / g more than

Each physical property will be described below.
(A) R = P _A / P _B > 0.2
The titanium-containing PET of the present invention measures a titanium K absorption edge X-ray absorption edge fine structure analysis (titanium K absorption edge XAFS) spectrum, and may be abbreviated as a standardized X-ray near absorption edge structure (hereinafter referred to as XANES). maximum at some), K absorption edge before (of peaks are present in the low energy side) than the K-absorption edge, the higher energy side than the intensity P _a of the largest _intensity, K absorption edge after (K-edge) When the peak intensity is P _B and the peak intensity ratio is R = P _A / P _B , R exceeds 0.2. Here, normalization means that the intensity is corrected according to a standard method in a spectrum obtained by subtracting the background of XANES. The K absorption edge is differentiated from a conventionally known region near the K absorption edge of the normalized spectrum, and the K absorption edge is defined as the place where the differential coefficient is maximum. The absolute value of the energy was calibrated by setting the peak top energy of the maximum intensity among the peaks existing before the K absorption edge in the XANES spectrum of titanium metal as 3964.0 eV.

In the XANES spectrum, the peak giving the intensity P _A existing before the K absorption edge is assigned as a transition from 1s orbit to 3d orbit of titanium, and the peak intensity is usually weak because it is forbidden from dipoles. On the other hand, when the strain around the titanium coordination structure is larger than that of the hexacoordinate octahedron structure, the ratio of the 4p orbitals to the 3d orbitals increases as the strain increases. Then, transition from 1s to 4p orbitals increases the intensity P _A for a dipole allowed. That coordination structure from 6-coordinate octahedral structure displacement around titanium, intensity P _A as strain is increased so that the increase.

The titanium-containing PET of the present invention has a characteristic in which R is more than 0.2, preferably more than 0.25, more preferably more than 0.3, when the above intensity ratio is R = P _A / P _B. .

  Titanium in a specific state described above is considered to be derived from the catalyst used in the polycondensation reaction. That is, the activity of the polycondensation reaction of the titanium-containing catalyst in the polycondensation step is improved, and the decomposition reaction is suppressed to prevent by-production of terminal carboxyl groups. Accordingly, the titanium-containing PET of the present invention having such a specific state of titanium is considered to have high thermal stability and excellent hydrolysis resistance and color tone.

(B) Terminal carboxyl group <35 eq / ton The titanium-containing PET of the present invention has a small number of terminal carboxyl groups and a terminal carboxyl group of less than 35 eq / ton because the decomposition reaction is suppressed. The terminal carboxyl group is more preferably less than 30 eq / ton.

  As described above, PET having a high terminal carboxyl group, that is, 35 eq / ton or more tends to be poor in hydrolysis resistance and color tone, but if it is PET having a terminal carboxyl group of 35 eq / ton, hydrolysis resistance And excellent color tone.

(C) Intrinsic viscosity ≧ 0.5 dl / g
The intrinsic viscosity of the titanium-containing PET of the present invention is 0.5 dl / g or more from the viewpoint of mechanical strength, and is preferably in the range of 0.6 dl / g to 0.8 dl / g in consideration of moldability.

  The titanium-containing PET having the characteristics (A), (B) and (C) can be preferably produced by the method for producing a polyester of the present invention using the catalyst for producing a polyester of the present invention.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited by a following example. In addition, the measurement of the various physical-property values in an Example , a reference example, and a comparative example was performed as follows.

<X-ray crystal structure analysis of solids>
The obtained solid was centrifuged and washed with ethanol, and then the solid was observed with a microscope to take out a single crystal and analyze the X-ray structure. The measurement apparatus was Bruker Smart 1000, and the measurement conditions were X-ray output (MoKα) 50 kV, 40 mA, collimator diameter 0.5 phi, exposure time 30 seconds, and number of shots 1321.

<Intrinsic viscosity>
0.50 g of a polyester sample was dissolved in a mixed solvent of phenol / 1,1,2,2-tetrachloroethane (weight ratio 1/1) at a concentration (c) of 1.0 g / dl at 110 ° C. for 20 minutes. Then, the relative viscosity (ηrel) with the stock solution was measured at 30 ° C. using an Ubbelohde capillary viscosity tube, and the specific viscosity (ηsp) and concentration (c) determined from this relative viscosity (ηrel) -1 And the ratio (ηsp / c) when the concentration (c) is 0.5 g / dl, 0.2 g / dl, and 0.1 g / dl. From these values, the ratio (ηsp / c) when the concentration (c) was extrapolated to 0 was determined as the intrinsic viscosity [η] (dl / g).

<Acid value (terminal carboxyl group)>
0.50 g of a polyester sample was precisely weighed and collected in a test tube, 25 ml of benzyl alcohol was added, and the mixture was dissolved by heating and stirring at 195 ° C. for 9 minutes. Thereafter, 2 ml of ethanol was added and cooled. This solution was titrated with 0.1N NaOH benzyl alcohol solution. Moreover, said operation was performed without using a polyester sample as a blank, and the acid value was computed with the following formulas. The acid value corresponds to the terminal carboxyl group and is an index of the thermal stability of the resin. If the acid value is high, the thermal stability is poor.
Acid value (eq / ton) = (α−β) × 0.1 × f / W
Here, the abbreviations are as follows.
α: Amount of 0.1N NaOH required for titration (μl)
β: Blank titration (μl)
W: Amount of polyester sample (g)
f: 0.1N NaOH benzyl alcohol titer

<Color tone>
A polyester sample is filled into a cylindrical powder colorimetric cell having an inner diameter of 36 mm and a depth of 15 mm by grinding, and using a colorimetric color difference meter (“ZE-2000” manufactured by Nippon Denshoku Industries Co., Ltd.), Japanese Industrial Standards. The color coordinate b of Hunter's color difference formula in the Lab color system described in the 1970 edition (JIS Z8730 reference 1) is a simple average of values measured by rotating the cell 90 degrees by the reflection method at four points. As sought.

<Volume specific resistance>
15 g of a polyester sample was put into a test tube with a branch having an inner diameter of 20 mm and a length of 180 mm, and the inside of the tube was sufficiently purged with nitrogen, and then immersed in an oil bath at 160 ° C. After vacuum drying for a period of time, the temperature of the oil bath was raised to 285 ° C. to melt the polyester sample, and then air bubbles mixed together were removed by repeating nitrogen re-pressure and pressure reduction. In this melt, ^two stainless steel electrodes with an area of 1 cm ² were inserted in parallel at an interval of 5 mm (non-opposite back surface covered with an insulator), and after the temperature was stabilized, a resistance meter (manufactured by Hewlett-Packard Company) A DC voltage of 100 V was applied by “MODEL HP4329A”), and the resistance value at that time was defined as a volume specific resistance (Ω · cm).

<Acetaldehyde amount>
A polyester sample (5.0 g) is weighed accurately, sealed in a 50 ml internal volume cylinder with 10 ml of pure water under a nitrogen seal, and heated and extracted at 160 ° C. for 2 hours. The amount of acetaldehyde in the extract is determined by isobutyl alcohol. Was quantified by gas chromatography (“GC-14A” manufactured by Shimadzu Corporation) as an internal standard.

<Amount of foreign matter with particle size of 10 μm or more>
100 mg of a polyester sample was precisely weighed and dissolved in 10 ml of a mixed solvent of phenol / 1,1,2,2-tetrachloroethane (weight ratio 2/3) at 100 ° C. for 2 hours. The number of particles and the diameter in this solution were measured using a HIAC PC-320 type fine particle measuring apparatus manufactured by Pacific Scientific, and the number of particles having a particle size of 10 μm or more was determined. This was repeated three times to determine the average value, and the number of particles obtained was gradually reduced by the weight of the measured polyester, converted to the number of particles per gram of polyester, and defined as the amount of foreign matter.

<Measurement of XAFS>
XAFS XANES spectrum measurement was performed at the XAFS measurement beamline BL9A, Institute for Materials Structure Science, High Energy Accelerator Research Organization. An X-ray is dispersed using a Si (111) 2 crystal spectrometer, the incident X-ray intensity IO is an ion chamber of an optical path portion 17 cm in which a He / N ₂ = 70/30 mixed gas is enclosed, and the fluorescent X-ray If is Ar It detected using the ion chamber (lightle detector) for fluorescence XAFS measurement using gas. The XANES spectrum μ was obtained by dividing the fluorescent X-ray intensity by the incident X-ray intensity (μ = If / IO).

(analysis method)
The XANES spectrum is obtained by subtracting the background from a polynomial calculated by regression in an appropriate part of the region before the K absorption edge (near 4950-4975 eV), and then an appropriate normalized point after the K absorption edge (appropriate between 5000 and 5050 eV). (Normal point 1 point), or by dividing by a polynomial calculated by regression in an appropriate region after the K absorption edge (high energy side after 5010 eV). At this time, in the background region before the K absorption edge, the intensity is 0.01 or less, and the linear spectrum is as flat as possible. In addition, the maximum peak after normalization exists in a region within 50 eV after the K absorption edge (near 4980-5030 eV), and its strength exceeds 1.0 and is within 1.5. For this, a normalization point or fitting polynomial was selected such that the maximum peak intensity near the K absorption edge after normalization was within 1.5, without performing the measurement at the maximum peak intensity near the K absorption edge.

  In this analysis, a conventionally known region near the K absorption edge of the spectrum obtained by subtracting the background of the titanium K absorption edge XAFS spectrum was differentiated, and the place where the differential coefficient was the maximum was taken as the absorption edge. The absolute value of the energy was calibrated by setting the peak top energy of the maximum intensity among the peaks existing before the K absorption edge in the XANES spectrum of titanium metal as 3964.0 eV.

Here, the peak intensity of the peak having the maximum intensity among the peaks existing before the K absorption edge, that is, on the low energy side is P _A , and the peak intensity of the peak having the maximum intensity after the absorption edge, that is, on the high energy side, is P and by _B, it was determined these peak intensity ratio _{R = P} a / P _B.

Reference Example 1 (Ti / Mg / ethylene glycol system)
<Preparation of catalyst>
200 ml of ethylene glycol was weighed into a 500 ml flask, and 1.6 g of magnesium acetate tetrahydrate was added to the flask and stirred to dissolve the magnesium acetate tetrahydrate in ethylene glycol. Thereafter, 0.7 g of tetrabutoxy titanium was added dropwise with stirring (Ti / Mg = 1/4: molar ratio). After completion of dropping, the mixture was stirred at room temperature (25 ° C.) for 1 hour.
The outline of catalyst preparation and the results of X-ray crystal structure analysis are shown in Table 1.

<Melting polycondensation>
Using terephthalic acid and ethylene glycol as raw materials, 156 g of an ethylene terephthalate low polymer produced by a direct esterification method was dissolved at 260 ° C. Thereafter, the catalyst solution prepared as described above was added to 5 ppm as a titanium atom with respect to the theoretical yield of the obtained polyester.
Next, while stirring the melt with a stirring blade, the temperature is raised stepwise to 280 ° C. over 80 minutes, and the pressure of the reaction system is lowered stepwise from normal pressure to absolute pressure 1.3 × 10 ² Pa over 60 minutes. After reaching a temperature of 280 ° C. and an absolute pressure of 1.3 × 10 ² Pa, the temperature and pressure were kept constant.

After 141 minutes from the start of pressure reduction, the agitation was stopped and the polycondensation reaction was stopped by introducing nitrogen gas into the system. Thereafter, the polymer was extracted from the reaction vessel and cooled with water to obtain a strand polymer. This was cut into pellets and evaluated.

  Table 4 shows the measurement results of the time from the start of decompression to the termination of the polycondensation reaction (polycondensation reaction time), the intrinsic viscosity, acid value, color coordinate b as the color tone, volume resistivity, and amount of foreign matter. Show.

<Solid phase polycondensation>
Subsequently, the polyester resin chip obtained above was dried in an inert oven (Yamato Scientific DN410I) for 2 hours at 160 ° C. under a nitrogen flow of 30 N liters / minute, and then heated at 210 ° C. for 10 hours. Solid phase polycondensation was performed.

  Subsequently, the obtained resin was put into a reactor, dried at 160 ° C. for 2 hours and 30 minutes under a reduced pressure of 6.0 × 10 Pa, and then remelted by heating at 290 ° C. for 15 minutes. The remelted polymer was extracted from the reactor into a strand, cooled with water, and pelletized with a cutter. Table 4 shows the intrinsic viscosity of the obtained polyester resin pellets and the measurement results of the amount of acetaldehyde.

Example 1 (Ti / Mg / Si / ethylene glycol system)
<Preparation of catalyst>
200 ml of ethylene glycol was weighed into a 500 ml flask, and 2.2 g of tetraethoxysilane was added dropwise while stirring the flask. After completion of the addition, the mixture was stirred at room temperature for 30 minutes. Thereafter, 0.4 g of magnesium acetate tetrahydrate was added, and the mixture was further stirred at room temperature for 30 minutes. After completion of stirring, 0.7 g of tetrabutoxy titanium was added dropwise with stirring (Ti / Si / Mg = 1/5/1: molar ratio). After completion of the dropwise addition, the mixture was stirred for 1 hour at room temperature.
The outline of catalyst preparation and the results of X-ray crystal structure analysis are shown in Table 1.
<Melting polycondensation>
A polycondensation reaction and evaluation were carried out in the same manner as in Reference Example 1 except that the catalyst prepared as described above was used and the polycondensation reaction time was 135 minutes. The results are shown in Table 4.
<Solid phase polycondensation>
The polycondensation reaction and evaluation were carried out in the same manner as in Reference Example 1. The results are shown in Table 4.

Example 2 (Ti / Mg / Si / ethylene glycol system)
<Preparation of catalyst>
In Example 1 , a catalyst was prepared in the same manner as in Example 1 except that magnesium acetate tetrahydrate was changed to 1.3 g (Ti / Si / Mg = 1/5/3: molar ratio).
An outline of catalyst preparation is shown in Table 1.
<Melting polycondensation>
The polycondensation reaction and evaluation were carried out in the same manner as in Reference Example 1 except that the catalyst prepared as described above was used and the polycondensation reaction time was 131 minutes. The results are shown in Table 4.
<Solid phase polycondensation>
The polycondensation reaction and evaluation were carried out in the same manner as in Reference Example 1. The results are shown in Table 4.

Example 3 (Ti / Mg / Si / ethylene glycol system)
<Preparation of catalyst>
In Example 2 , a catalyst (Ti / Si / Mg = 1/5/3: molar ratio) was obtained in the same manner as in Example 2 except that the order of adding magnesium acetate tetrahydrate and tetrabutoxy titanium was reversed. Was prepared.
An outline of catalyst preparation is shown in Table 1.
<Melting polycondensation>
The polycondensation reaction and evaluation were carried out in the same manner as in Reference Example 1 except that the catalyst prepared as described above was used and the polycondensation reaction time was 136 minutes. The results are shown in Table 4.
<Solid phase polycondensation>
The polycondensation reaction and evaluation were carried out in the same manner as in Reference Example 1. The results are shown in Table 4.

Example 4 (Ti / Mg / Si / ethylene glycol system)
<Preparation of catalyst>
200 ml of ethylene glycol was weighed into a 500 ml flask, and 1.6 g of magnesium acetate tetrahydrate was added to the flask while stirring, and stirred at room temperature for 30 minutes after the addition. Thereafter, 0.4 g of tetraethoxysilane was added dropwise, and after completion of the addition, the mixture was further stirred at room temperature for 30 minutes. After the completion of stirring, 0.7 g of tetrabutoxytitanium was added dropwise with stirring (Ti / Si / Mg = 1/4: molar ratio). After completion of dropping, the mixture was stirred at 70 ° C. for 1 hour.
The outline of catalyst preparation and the results of X-ray crystal structure analysis are shown in Table 1.
<Melting polycondensation>
The polycondensation reaction was performed in the same manner as in Reference Example 1 except that the catalyst prepared as described above was added so as to be 6 ppm as a titanium atom with respect to the theoretical yield of the obtained polyester, and the polycondensation reaction time was 157 minutes. And the evaluation was carried out. The results are shown in Table 4.
<Solid phase polycondensation>
The polycondensation reaction and evaluation were carried out in the same manner as in Reference Example 1. The results are shown in Table 4.

Example 5 (Ti / Zn / Si / ethylene glycol system)
<Preparation of catalyst>
In Example 4 , a catalyst was prepared in the same manner as in Example 4 except that magnesium acetate tetrahydrate was changed to 0.6 g of methoxyethoxyzinc (Ti / Si / Zn = 1/1/2: molar ratio). did.
An outline of catalyst preparation is shown in Table 1.
<Melting polycondensation>
The polycondensation reaction was performed in the same manner as in Reference Example 1 except that the catalyst prepared as described above was added to 5 ppm as a titanium atom with respect to the theoretical yield of the resulting polyester, and the polycondensation reaction time was 134 minutes. And the evaluation was carried out. The results are shown in Table 4.
<Solid phase polycondensation>
The polycondensation reaction and evaluation were carried out in the same manner as in Reference Example 1. The results are shown in Table 4.

Example 6 (Ti / Ca / Si / ethylene glycol system)
<Preparation of catalyst>
In Example 4 , magnesium acetate tetrahydrate was changed to 1.1 g of calcium acetate monohydrate (Ti / Si / Ca = 1/1/2: molar ratio) in the same manner as in Example 4. A catalyst was prepared.
An outline of catalyst preparation is shown in Table 1.
<Melting polycondensation>
The polycondensation reaction and evaluation were carried out in the same manner as in Reference Example 1, except that 5 ppm of the catalyst prepared as described above was added as a titanium atom with respect to the theoretical yield of the obtained polyester, and the polycondensation reaction time was 136 minutes. did. The results are shown in Table 4.
<Solid phase polycondensation>
The polycondensation reaction and evaluation were carried out in the same manner as in Reference Example 1. The results are shown in Table 4.

Comparative Example 1 (Ti / Si / ethylene glycol system)
<Preparation of catalyst>
200 ml of ethylene glycol was weighed into a 500 ml flask, and 2.2 g of tetraethoxysilane was added dropwise while stirring the flask. After completion of the addition, the mixture was stirred at room temperature for 30 minutes. Thereto, 0.7 g of tetrabutoxy titanium was added dropwise with stirring (Ti / Si = 1/5: molar ratio). After completion of the dropwise addition, the mixture was stirred for 1 hour at room temperature to obtain a colorless and transparent catalyst solution.
A summary of catalyst preparation is shown in Table 2.
<Melting polycondensation>
A polycondensation reaction and evaluation were carried out in the same manner as in Reference Example 1 except that the catalyst prepared as described above was used and the polycondensation reaction time was 111 minutes. The results are shown in Table 5.
<Solid phase polycondensation>
The polycondensation reaction and evaluation were carried out in the same manner as in Reference Example 1. The results are shown in Table 5.

Comparative Example 2 (Ti / Si / ethylene glycol system)
<Preparation of catalyst>
Comparative Example 1 is the same as Comparative Example 1 except that tetraethoxysilane was changed to 0.4 g (Ti / Si = 1/1: molar ratio) and the order of adding tetraethoxysilane and tetrabutoxytitanium was reversed. A catalyst was prepared in the same manner.
A summary of catalyst preparation is shown in Table 2.
<Melting polycondensation>
The polycondensation reaction and evaluation were carried out in the same manner as in Reference Example 1 except that the catalyst prepared as described above was used and the polycondensation reaction time was 117 minutes. The results are shown in Table 5.
<Solid phase polycondensation>
The polycondensation reaction and evaluation were carried out in the same manner as in Reference Example 1. The results are shown in Table 5.

Comparative Example 3 (Ti / Si / ethylene glycol system)
<Preparation of catalyst>
In Comparative Example 2, a catalyst was prepared in the same manner as in Comparative Example 2, except that the order of adding tetraethoxysilane and tetrabutoxytitanium was reversed.
A summary of catalyst preparation is shown in Table 2.
<Melting polycondensation>
The polycondensation reaction and evaluation were carried out in the same manner as in Reference Example 1 except that the catalyst prepared as described above was used and the polycondensation reaction time was 112 minutes. The results are shown in Table 5.
<Solid phase polycondensation>
The polycondensation reaction and evaluation were carried out in the same manner as in Reference Example 1. The results are shown in Table 5.

Comparative Example 4 (Ti / Si / ethylene glycol system + Mg + P)
<Preparation of catalyst>
A catalyst was prepared in the same manner as in Comparative Example 1. A summary of catalyst preparation is shown in Table 1.
<Preparation of other solutions>
A magnesium acetate solution was prepared by the following method. 200 ml of ethylene glycol was weighed into a 500 ml flask, and 2.2 g of magnesium acetate tetrahydrate was added while stirring the flask. After completion of the addition, the mixture was stirred at room temperature for 30 minutes to obtain a colorless and transparent solution.
A normal phosphoric acid solution was prepared by the following method. 50 ml of ethylene glycol was weighed into a 100 ml flask, and 0.8 g of normal phosphoric acid was added dropwise while stirring the flask. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour to obtain a colorless and transparent solution.
<Melting polycondensation>
In Reference Example 1, 7 ppm as the magnesium atom relative to the theoretical yield of the polyester capable of obtaining the magnesium acetate solution in the reactor, and 3 ppm as the phosphorus atom relative to the theoretical yield of the polyester capable of obtaining the normal phosphoric acid solution. The polycondensation reaction and evaluation were carried out in the same manner as in Reference Example 1 except that the catalyst solution was added and the polycondensation reaction time was 125 minutes. The results are shown in Table 5.
<Solid phase polycondensation>
The polycondensation reaction and evaluation were carried out in the same manner as in Reference Example 1. The results are shown in Table 5.

Comparative Example 5 (Ti + Si)
<Preparation of other solutions>
A tetrabutoxy titanium solution was prepared by the following method. 100 ml of ethylene glycol was weighed into a 200 ml flask, and 0.7 g of tetrabutoxy titanium was added dropwise while stirring the flask. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour to obtain a colorless and transparent solution.
A tetraethoxysilane solution was prepared by the following method. 100 ml of ethylene glycol was weighed into a 200 ml flask, and 2.2 g of tetraethoxysilane was added dropwise while stirring the flask. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour to obtain a partially suspended solution.
<Melting polycondensation>
In Reference Example 1, instead of introducing the catalyst solution into the reactor, 5 ppm as a titanium atom with respect to the theoretical yield of polyester from which an ethylene glycol solution of tetrabutoxytitanium can be obtained, and an ethylene glycol solution of tetraethoxysilane can be obtained. A polycondensation reaction and evaluation were carried out in the same manner as in Example 1 except that the amount was separately added so as to be 15 ppm as a silicon atom with respect to the theoretical yield of polyester, and the polymerization time was 132 minutes.
A summary of the compounds used is shown in Table 2, and the results are shown in Table 5.
<Solid phase polycondensation>
The polycondensation reaction and evaluation were carried out in the same manner as in Reference Example 1. The results are shown in Table 5.

Comparative Example 6 (Ti + Mg)
<Preparation of other solutions>
The tetrabutoxy titanium solution used was prepared in Comparative Example 5.
As the magnesium acetate solution, the one prepared in Comparative Example 4 was used.
<Melting polycondensation>
In Reference Example 1, instead of introducing the catalyst solution into the reactor, 5 ppm as titanium atoms with respect to the theoretical yield of the polyester from which an ethylene glycol solution of tetrabutoxytitanium was obtained, and the ethylene glycol solution of magnesium acetate tetrahydrate Except that the polycondensation reaction time was set to 150 minutes, separately with a 7.5 ppm (Ti / Mg = 1/3: molar ratio) magnesium atom relative to the theoretical yield of the polyester obtained. The polycondensation reaction and evaluation were carried out in the same manner as in Reference Example 1.
A summary of the compounds used is shown in Table 2, and the results are shown in Table 5.
<Solid phase polycondensation>
The polycondensation reaction and evaluation were carried out in the same manner as in Reference Example 1. The results are shown in Table 5.

Comparative Example 7 (Ti / Si)
<Preparation of catalyst>
In a 500 ml beaker, 40 g of ethanol was added, and 6 g of tetraethoxysilane and 7.5 g of tetraisopropoxytitanium (Ti / Si = 1/1: molar ratio) were added separately while stirring at room temperature. Further, a mixed solution of 18 g of distilled water and 40 g of ethanol was dropped into this. After stirring at 25 ° C. for 1 hour, the resulting precipitate was separated from the supernatant by centrifugation at 5000 rpm for 5 minutes. The obtained precipitate was washed once with distilled water, and the precipitate was separated by centrifugal sedimentation at 5000 rpm for 5 minutes. The separated precipitate was dried under reduced pressure at 70 ° C. for 3 hours using a rotary evaporator and then pulverized to 100 μm or less. Further, 0.15 part by weight of the pulverized solid was added to 100 parts by weight of ethylene glycol, heated at 198 ° C. for 15 minutes, and then cooled to 100 ° C. in 60 minutes to obtain a catalyst solution.
An outline of catalyst preparation is shown in Table 3. This precipitate did not have a clear crystal structure.
<Melting polycondensation>
The polycondensation reaction and evaluation were carried out in the same manner as in Reference Example 1 except that the catalyst prepared as described above was added so that the titanium atom was 10 ppm relative to the theoretical yield of the polyester obtained, and the polymerization time was 197 minutes. Carried out. The results are shown in Table 5.
<Solid phase polycondensation>
The polycondensation reaction and evaluation were carried out in the same manner as in Reference Example 1. The results are shown in Table 5.

Comparative Example 8 (Ti / Mg)
<Preparation of catalyst>
In a 500 ml beaker, 40 g of ethanol was added, and 5 g of diethoxymagnesium and 4 g of tetraisopropoxytitanium (Ti / Mg = 1/3: molar ratio) were added separately while stirring at room temperature. Further, a mixed solution of 18 g of distilled water and 40 g of ethanol was dropped into this. After stirring at 25 ° C. for 1 hour, the resulting precipitate was separated from the supernatant by centrifugation at 5000 rpm for 5 minutes. The obtained precipitate was washed once with distilled water, and the precipitate was separated by centrifugal sedimentation at 5000 rpm for 5 minutes. The separated precipitate was dried under reduced pressure at 70 ° C. for 3 hours using a rotary evaporator and then pulverized to 100 μm or less. Further, 0.15 part of the pulverized solid was added to 100 parts of ethylene glycol, heated at 198 ° C. for 15 minutes, and then cooled to 100 ° C. in 60 minutes to obtain a catalyst solution.
An outline of catalyst preparation is shown in Table 3. This precipitate did not have a clear crystal structure.
<Melting polycondensation>
The catalyst solution prepared as described above was added in the same manner as in Reference Example 1 except that the titanium atom was added to 10 ppm as a titanium atom with respect to the theoretical yield of the resulting polyester, and the polycondensation reaction time was 237 minutes. Condensation reaction and evaluation were carried out. The results are shown in Table 5.
<Solid phase polycondensation>
The polycondensation reaction and evaluation were carried out in the same manner as in Reference Example 1. The results are shown in Table 5.

Comparative Example 9 (Ti + Mg + Si)
<Preparation of other solutions>
The tetrabutoxy titanium solution used was prepared in Comparative Example 5.
As the magnesium acetate solution, the one prepared in Comparative Example 4 was used.
The tetraethoxysilane solution used was prepared in Comparative Example 5.
<Melting polycondensation>
Instead of introducing the catalyst solution into the reactor in Reference Example 1, 5 ppm as titanium atoms and the ethylene glycol solution of magnesium acetate tetrahydrate with respect to the theoretical yield of the polyester from which an ethylene glycol solution of tetrabutoxytitanium can be obtained. 7.5 ppm as a magnesium atom with respect to the theoretical yield of the obtained polyester, and further 15 ppm as a silicon atom with respect to the theoretical yield of the polyester from which an ethylene glycol solution of tetraethoxysilane can be obtained (Ti / Si / Mg = 1/5/3). : Molar ratio), and the polycondensation reaction and evaluation were carried out in the same manner as in Reference Example 1 except that the polymerization time was 150 minutes.
A summary of the compounds used is shown in Table 3, and the results are shown in Table 5.
<Solid phase polycondensation>
The polycondensation reaction and evaluation were carried out in the same manner as in Reference Example 1. The results are shown in Table 5.

Comparative Example 10 (Ti / Mg / Si)
<Preparation of catalyst>
200 ml of degassed and dehydrated n-heptane was introduced into a dry, nitrogen-substituted reaction vessel, and then 38 g of magnesium chloride and 273 g of tetrabutoxytitanium were added and reacted at 90 ° C. for 2 hours. After completion of the reaction, the temperature was lowered to 40 ° C., and then 48 g of methylhydropolysiloxane (20 centistokes) was introduced and reacted at 40 ° C. for 3 hours. The produced solid component was washed with n-heptane, n-heptane was removed by decantation, and then dried under reduced pressure at room temperature.
A summary of catalyst preparation is shown in Table 3. This solid component did not have a clear crystal structure.
<Melting polycondensation>
The polycondensation reaction and evaluation were carried out in the same manner as in Reference Example 1 except that the catalyst prepared as described above was used and the polycondensation reaction time was 81 minutes. The results are shown in Table 5.

Comparative Example 11 (Ti / Mg)
<Preparation of catalyst>
In a dry, nitrogen-substituted reaction vessel, 10 g of diethoxymagnesium was weighed under nitrogen, and then 60 ml of degassed and dehydrated heptane was added. While stirring at room temperature, 18 g of tetrabutoxy titanium was slowly added. After stirring at 95 ° C. for 3 hours, heating was stopped and the reaction solution was cooled to room temperature.
A summary of catalyst preparation is shown in Table 3. This solid component did not have a clear crystal structure.
<Melting polycondensation>
The polycondensation reaction and evaluation were carried out in the same manner as in Reference Example 1 except that the catalyst prepared as described above was used and the polycondensation reaction time was 101 minutes. The results are shown in Table 5.

From the results of Reference Example 1, Examples 1 to 6 and Comparative Examples 1 to 11, the following is clear.

Reference Example 1 is an example using Compound (1) and Compound (2) but not using Compound (3). Although the acetaldehyde content after solid phase polycondensation was high, the other physical properties showed good results.

Example 1 is an example using compound (1), compound (2), and compound (3). All physical properties showed good results.

Example 2 is an example of increasing the amount of the compound than in Example 1 (2), all the physical properties are shown good results.

Example 3 is an example in which the compounds (1) to (3) were mixed in a different order from Example 2, and all the physical properties showed good results.

In Example 4 , the amount of compound (2) and compound (3) to be used and the order of addition were changed, and although the color coordinate b value was slightly deteriorated, other physical properties showed good results.

Example 5 is an example in which a zinc compound was used as the compound (2) instead of the magnesium compound. Although the volume resistivity and the amount of acetaldehyde were slightly high, other physical properties showed good results.

Example 6 is an example in which a calcium compound was used as the compound (2) instead of the magnesium compound. Although the amount of acetaldehyde was slightly high, other physical properties showed good results.

Comparative Example 1 is an example in which compound (2) is not used in Example 1 . The volume specific resistance value and the color coordinate b value were high.

Comparative Example 2 and Comparative Example 3 are examples in which the ratio of compound (1) to compound (3) is the same as in Examples 4 to 6 , but compound (2) is not used. In all examples, the volume resistivity value was high.

In Comparative Example 4, the ratio of the compound (1) to the compound (3) is the same as that in Examples 1 to 3 , but the compound (2) is not contained in the catalyst, and it is equivalent to the compound (2). This is an example in which a magnesium acetate solution is added separately. The color coordinate b value showed a high value.

Comparative Example 5 is an example in which compound (1) and compound (3) were added separately without using compound (2). The amount added was the same as in Examples 1 to 3 , but the volume resistivity value and the amount of acetaldehyde were high.

Comparative Example 6 is an example in which compound (1) and compound (2) were added separately without using compound (3). The amount added was the same as in Examples 2 and 3 , but the color coordinate b value and the amount of acetaldehyde were high.

  Comparative Example 7 is an example in which a known composite oxide obtained by mixing and hydrolyzing compound (1) and compound (3) was used as a catalyst. The obtained polyester contained many foreign matters having a size of 10 μm or more.

  Comparative Example 8 is an example in which a known composite oxide obtained by mixing and hydrolyzing compound (1) and compound (2) was used as a catalyst. The obtained polyester contained many foreign matters having a size of 10 μm or more.

  The results of Comparative Example 7 and Comparative Example 8 indicate that many foreign substances are generated by using a known composite oxide as a catalyst.

Comparative Example 9 is an example in which compound (1), compound (2), and compound (3) were added separately. The amount added was the same as in Examples 2 and 3 , but the color coordinate b value of the polyester obtained and the amount of acetaldehyde were high.

  Comparative Example 10 is an example in which a compound (1), a compound (2), and a compound (3) were mixed and reacted, and then a known solid that was dried and solidified without hydrolysis was used as a catalyst. The obtained polyester had a large amount of foreign matter having a size of 10 μm or more and a high value of the color coordinate b value.

  Comparative Example 11 is an example in which a compound (1) and a compound (2) were mixed and reacted, and then a known solid that was dried and solidified without hydrolysis was used as a catalyst. The obtained polyester had a large amount of foreign matter having a size of 10 μm or more and a high value of the color coordinate b value.

  The results of Comparative Example 10 and Comparative Example 11 indicate that a large amount of foreign matter is generated in the obtained polyester when a known solid obtained by drying and solidifying without hydrolysis is used as a catalyst.

Example 7 (Ti / Mg / Si / ethylene glycol system)
The catalyst prepared as in Example 1 was melted in the same manner as in Example 1 except that the amount of titanium atom was 20 ppm with respect to the theoretical yield of polyester, and the polycondensation reaction time was 112 minutes. Polycondensation was performed, and the intrinsic PET, terminal carboxyl group measurement, and XAFS measurement were performed on the obtained PET. The results are shown in Table 6.

Example 8 (Ti / Mg / Si / ethylene glycol system)
The catalyst prepared in the same manner as in Example 4 was melted in the same manner as in Example 4 except that 20 ppm of titanium atoms was added to the theoretical yield of the polyester, and the polycondensation reaction time was 113 minutes. Polycondensation was performed, and the intrinsic PET, terminal carboxyl group measurement, and XAFS measurement were performed on the obtained PET. The results are shown in Table 6.

Comparative Example 12 (Ti / Si / ethylene glycol system)
The catalyst prepared in the same manner as in Comparative Example 1 was melted in the same manner as in Comparative Example 1 except that the catalyst was added so that the titanium yield was 20 ppm with respect to the theoretical yield of the polyester, and the polycondensation reaction time was 109 minutes. Polycondensation was performed, and the intrinsic PET, terminal carboxyl group measurement, and XAFS measurement were performed on the obtained PET. The results are shown in Table 6.

Comparative Example 13 (Ti / Si / ethylene glycol system + Mg + P)
A catalyst prepared in the same manner as in Comparative Example 4 was obtained with 20 ppm as a titanium atom relative to the theoretical yield of the polyester to obtain a catalyst, and 28 ppm as a magnesium atom with respect to the theoretical yield of the polyester from which a magnesium acetate solution was obtained. The resulting polyester was melt polycondensed in the same manner as in Comparative Example 4 except that the polycondensation reaction time was 115 minutes with respect to the theoretical yield of the polyester obtained. Carboxyl group measurement and XAFS measurement were performed. The results are shown in Table 6.

  From Table 6, using the polyester production catalyst of the present invention, the titanium-containing PET of the present invention having the above physical properties (A), (B), (C) and excellent in various properties can be produced. I understand.

Claims (7)

At least (1) a group 4A compound (hereinafter referred to as “compound (1)”), (2) a compound of at least one element selected from the group consisting of magnesium, calcium, and zinc (hereinafter referred to as “compound (2)”) (3) A catalyst for producing a polyester comprising a silicate compound (hereinafter referred to as “compound (3)”) and an oxygen-containing organic solvent , wherein the compound (1) is alkoxytitanium. A polyester production catalyst , wherein the oxygen-containing organic solvent is ethylene glycol . The polyester production catalyst according to claim 1, which is prepared at 150 ° C or lower. The catalyst for producing a polyester according to claim 1 or 2 , wherein the compound (2) is a magnesium compound. 4. The catalyst for producing a polyester according to claim 3 , comprising a hexagonal crystal in which one atom of the group 4A element derived from the compound (1) and / or one magnesium element derived from the compound (2) is solvated with six molecules of ethylene glycol. . The catalyst for producing a polyester according to any one of claims 1 to 4 , wherein the compound (3) is an orthosilicate compound. Content of the compound (1) and the compound (2) is, 4A group elements: magnesium, calcium, and total zinc element (molar ratio), 95: 5 to 5: of claims 1 to 5 in the range of 95 The catalyst for polyester production according to any one of the above. A polyester is produced by subjecting a dicarboxylic acid component mainly composed of an aromatic dicarboxylic acid and / or an ester-forming derivative thereof and a dihydric alcohol component to a polycondensation reaction through an esterification reaction and / or a transesterification reaction. In this case, a polyester production method using the polyester production catalyst according to any one of claims 1 to 6 .