JP2008274298A - Catalyst for manufacturing polyester and polyester made thereby - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst for manufacturing a polyester capable of manufacturing polyester polymer good in color and transparency and little in the content of acetaldehyde. <P>SOLUTION: This catalyst for manufacturing a polyester is a reaction product of (A) titanium compound component, (B) phosphorus compound component, and (C) alkaline earth metal compound component, and the reaction molar ratio of the titanium compound component in terms of titanium atom to the alkaline earth metal compound component in terms of this atom (mM), (mTi)/(mM) is in the range of (2:1)-(1:3). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a polyester production catalyst, and more particularly to a polyester production catalyst capable of producing a polyester polymer having good hue and transparency and low acetaldehyde content.

  Polyester is excellent in mechanical strength, heat resistance, transparency, and gas barrier properties, and is suitably used as a material for films, sheets, fibers, etc., as well as materials for beverage filling containers such as juices, soft drinks, and carbonated beverages. ing.

  Usually, polyester is produced from dicarboxylic acid such as terephthalic acid and aliphatic diols such as ethylene glycol as raw materials. Specifically, first, a low-order condensate (ester low polymer) is formed by an esterification reaction of an aromatic dicarboxylic acid and an aliphatic diol, and then this low-order condensate is formed in the presence of a polycondensation catalyst. It is deglycolized (liquid phase polycondensation) to increase the molecular weight. In some cases, solid state polycondensation is performed to further increase the molecular weight.

  In the polyester production method, an antimony compound, a germanium compound, or the like is conventionally used as a polycondensation catalyst. However, polyethylene terephthalate produced using an antimony compound as a catalyst is inferior to polyethylene terephthalate produced using a germanium compound as a catalyst in terms of transparency and heat resistance. It is also desired to reduce the acetaldehyde content in the resulting polyester.

  Moreover, since the germanium compound is quite expensive, there is a problem that the production cost of the polyester is increased. For this reason, in order to reduce the production cost, a process of recovering and reusing the germanium compound scattered during the polycondensation has been studied.

  By the way, titanium is known to be an element having an action of promoting ester polycondensation reaction, and titanium alkoxide, titanium tetrachloride, titanyl oxalate, orthotitanic acid and the like are known as polycondensation catalysts. Many studies have been conducted in order to use a titanium compound as a polycondensation catalyst.

  However, when a conventional titanium-based catalyst is used as a polycondensation catalyst, there is a problem that the obtained polyester is remarkably colored in yellow although it is more active than antimony compounds and germanium compounds.

  In order to solve the above-mentioned coloring problem, it is generally performed to add a cobalt compound to polyester to suppress yellowing. Certainly, the hue (b value) of the polyester can be improved by adding a cobalt compound, but the problem that the melting heat stability of the polyester is lowered and the polymer is easily decomposed by adding the cobalt compound. There is.

  Further, as other titanium compounds, use of titanium hydroxide as a catalyst for producing a polyester (for example, see Patent Document 1) and use of α-titanic acid as a catalyst for producing a polyester (for example, see Patent Document 2). It is disclosed. However, in the former method, powdering of titanium hydroxide is not easy. On the other hand, in the latter method, α-titanic acid is easily changed in quality, so its storage and handling are not easy. In addition, it is difficult to obtain a polymer having a good color tone (b value).

  Further, a product obtained by reacting a titanium compound with trimellitic acid is used as a catalyst for producing a polyester (see, for example, Patent Document 3), and a titanium compound and a phosphite are reacted. The use of the obtained product as a catalyst for polyester production is disclosed (for example, see Patent Document 4).

  Certainly, according to these methods, although the melt heat stability of the polyester is improved to some extent, the color tone of the obtained polymer is not sufficient, and therefore further improvement of the polymer color tone is desired.

  Furthermore, it has also been proposed to use a complex of a titanium compound and a phosphorus compound as a catalyst for polyester production (see, for example, Patent Document 5). Certainly, this method also improves the heat stability of melting to some extent, but the color tone of the resulting polymer is not sufficient.

  A catalyst obtained by reacting a titanium compound with an alkaline earth metal compound has also been proposed (see, for example, Patent Document 6). However, even with this method, the hue of the polyester is not sufficient.

Japanese Patent Publication No. 48-2229 Japanese Patent Publication No. 47-26597 Japanese Patent Publication No.59-46258 JP 58-38722 A JP 7-138354 A JP 2000-109552 A

  The object of the present invention is to improve the hue of a polyester polymer, which cannot be solved by any of the above prior arts, and for producing a polyester capable of producing a polyester polymer having good hue and transparency and low acetaldehyde content. It is to provide a catalyst.

  In order to solve the above-mentioned problems, the present inventors diligently studied a polycondensation catalyst used in the production of polyester. As a polycondensation catalyst, a titanium compound and a phosphorus compound are combined with a specific alkaline earth metal compound. As a result, it was found that high-quality polyester with high catalytic activity can be produced, and the present invention has been completed.

及び、前記一般式（Ｉ）のチタン化合物（１）と下記一般式（ＩＩ）で表される芳香族多価カルボン酸

又はその無水物とを反応させて得られたチタン化合物（２）、
から選ばれた少なくとも一種からなるチタン化合物成分と、
（Ｂ）下記一般式（ＩＩＩ）で表されるリン化合物（３）

の少なくとも一種からなるリン化合物成分と、
（Ｃ）下記一般式（ＩＶ）で表されるアルカリ土類金属化合物（４）

の少なくとも一種からなるアルカリ土類金属化合物成分と、
の反応生成物からなり、前記チタン化合物成分のチタン原子換算モル量（ｍＴｉ）と、前記アルカリ土類金属化合物成分のアルカリ土類金属原子換算モル量（ｍＭ）に対する反応モル比（ｍＴｉ）／（ｍＭ）が、（２：１）〜（１：３）の範囲内にある、ポリエステル製造用触媒によって達成することができる。 That is, the object of the present invention is to
(A) Titanium compound (1) represented by the following general formula (I)

And an aromatic polyvalent carboxylic acid represented by the titanium compound (1) of the general formula (I) and the following general formula (II)

Or a titanium compound (2) obtained by reacting with an anhydride thereof,
A titanium compound component consisting of at least one selected from
(B) Phosphorus compound (3) represented by the following general formula (III)

A phosphorus compound component consisting of at least one of
(C) Alkaline earth metal compound (4) represented by the following general formula (IV)

An alkaline earth metal compound component comprising at least one of
The reaction molar ratio (mTi) / () of the titanium compound component relative to the molar amount of titanium atom (mTi) and the alkaline earth metal compound component relative to the molar amount of alkaline earth metal atom (mM). mM) can be achieved with a catalyst for the production of polyesters in the range of (2: 1) to (1: 3).

  According to the present invention, a polyester production catalyst having high polymerization activity can be provided, and a polyester can be produced with higher catalytic activity than germanium compounds and antimony compounds conventionally used as polycondensation catalysts. Can do. In addition, the polyester produced with the catalyst of the present invention is excellent in hue as compared with the case where an antimony compound is used as a polycondensation catalyst, and in particular, polyethylene terephthalate has excellent transparency in addition to the hue in the molded product, and is also acetaldehyde. Since the content is small, it is useful as a material for molded containers such as bottles.

Hereinafter, the present invention will be described in detail.
In the present invention, the catalyst for producing a polyester includes a reaction product of the titanium compound component, the phosphorus compound component, and the alkaline earth metal compound component. Hereinafter, the polyester production catalyst of the present invention is efficiently obtained. The manufacturing method will be described.

  As a titanium compound used for the synthesis of the catalyst, it is desirable to use a titanium compound (1) represented by the following general formula (I), specifically, titanium tetrabutoxide, titanium tetraisopropoxide, titanium tetra Examples thereof include alkyl titanates such as titanium tetraalkoxides, octaalkyltrititanates and hexaalkyldititanates exemplified by propoxide and titanium tetraethoxide. Among them, phosphorus compound components used in the present invention It is preferable to use titanium tetraalkoxides that have good reactivity with the titanium, and it is particularly preferable to use titanium tetrabutoxide.

  Further, after reacting this titanium compound (1) with an aromatic polyvalent carboxylic acid represented by the following general formula (II) or its anhydride to form a titanium compound (2), a phosphorus compound component, an alkaline earth You may make it react with a metal compound component.

  The aromatic polyvalent carboxylic acid represented by the above general formula (II) or its anhydride is generally obtained by removing the titanium compound (1) of the above general formula (I) which is unstable to moisture and heat in a solvent. There is no particular limitation on the amount added, but it is preferably 0.5 to 4.0 times the molar amount relative to the titanium atom, and 1.0 to 2.0 times the molar amount is added. Is more preferable. When it is within this range, the above stabilizing effect is exhibited to the maximum, and there is no problem in the quality of the finally obtained polyester.

  Here, as the aromatic polyvalent carboxylic acid or its anhydride, phthalic acid, trimellitic acid, hemimellitic acid, pyromellitic acid and their anhydrides can be preferably used. These may be used alone or in combination of two or more compounds. In particular, the reactivity with the titanium compound (1) is good, and the resulting polyester production catalyst has a high affinity with the polyester. It is preferable to use trimellitic anhydride.

  The reaction between the titanium compound (1) and the aromatic polyvalent carboxylic acid or anhydride thereof is carried out by mixing the aromatic polyvalent carboxylic acid or anhydride in a solvent and dissolving part or all of the mixture in the solvent. The titanium compound (1) is dropped into this mixed solution and heated at a temperature of 0 to 200 ° C. for at least 30 minutes, preferably at a temperature of 30 to 150 ° C. for 40 to 90 minutes. The reaction pressure at this time is not particularly limited, and normal pressure is sufficient. The solvent can be appropriately selected from those capable of dissolving a part or all of the aromatic polyvalent carboxylic acid or its anhydride, but preferably ethanol, ethylene glycol, trimethylene glycol, tetra It is selected from methylene glycol, benzene, xylene and the like.

  The titanium compound (2) which is a reaction product obtained by this reaction may be directly subjected to a reaction with a phosphorus compound component and an alkaline earth metal compound component, or this may be used with acetone, methyl alcohol and / or ethyl acetate, etc. After being recrystallized and purified by the above, it may be reacted with a phosphorus compound component or an alkaline earth metal compound component.

  Moreover, as a phosphorus compound component, it is desirable to use the phosphorus compound (3) represented by the following general formula (III).

  Here, when q in the formula is 0, for example, phenylphosphonic acid, methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, isopropylphosphonic acid, butylphosphonic acid, tolylphosphonic acid, xylylphosphonic acid, biphenylphosphonic acid Naphthylphosphonic acid, anthrylphosphonic acid, 2-carboxyphenylphosphonic acid, 3-carboxyphenylphosphonic acid, 4-carboxyphenylphosphonic acid, 2,3-dicarboxyphenylphosphonic acid, 2,4-dicarboxyphenylphosphonic acid 2,5-dicarboxyphenylphosphonic acid, 2,6-dicarboxyphenylphosphonic acid, 3,4-dicarboxyphenylphosphonic acid, 3,5-dicarboxyphenylphosphonic acid, 2,3,4-tricarboxyphenyl Phosphonic acid, 2,3,5-trical Examples thereof include xylphenylphosphonic acid, 2,3,6-tricarboxyphenylphosphonic acid, 2,4,5-tricarboxyphenylphosphonic acid, and 2,4,6-tricarboxyphenylphosphonic acid. Arylphosphonic acids are preferred.

  When q is 1, for example, monomethyl phosphate, monoethyl phosphate, monopropyl phosphate, mono-n-butyl phosphate, monohexyl phosphate, monoheptyl phosphate, monononyl phosphate, monodecyl phosphate, monododecyl phosphate, monophenyl Phosphate, monobenzyl phosphate, mono (4-methylphenyl) phosphate, mono (4-ethylphenyl) phosphate, mono (4-propylphenyl) phosphate, mono (4-dodecylphenyl) phosphate, monotolyl phosphate, monoxylyl phosphate Monobiphenyl phosphate, mononaphthyl phosphate, monoanthryl phosphate, and the like.

  Further, as the alkaline earth metal compound component, it is desirable to use an alkaline earth metal compound (4) represented by the following general formula (IV), specifically magnesium formate, magnesium acetate, magnesium propionate, butyric acid Preferred examples include magnesium, magnesium benzoate, calcium formate, calcium acetate, calcium propionate, calcium butyrate, calcium benzoate and the like.

  The catalyst of the present invention can be obtained by reacting the titanium compound component, the phosphorus compound component, and the alkaline earth metal compound component as described above. At this time, it is easy to heat the glycol as a reaction medium. Can be manufactured.

  Examples of the glycol used here include ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol, and cyclohexanedimethanol. For the glycol used for the production of the catalyst for polyester production, the obtained catalyst is used. It is preferable to use the same glycol as the polyester to be produced.

  In addition, in mixing and reacting each of the above components, a method of simultaneously mixing the titanium compound component, the phosphorus compound component, the alkaline earth metal compound component and the glycol, the titanium compound component, the phosphorus compound component, A method of preparing each glycol solution of the alkaline earth metal compound component and then mixing, and further mixing a glycol solution of two types of components among the titanium compound component, phosphorus compound component, and alkaline earth metal compound component, and then Any method of mixing the remaining one kind of compound glycol solution may be used, but the titanium compound component glycol solution and the alkaline earth metal compound component glycol solution are mixed, and then the phosphorus compound component glycol solution is mixed. It is preferable to manufacture by the method of mixing.

  The reaction temperature is usually at room temperature, since the reaction is insufficient or the reaction takes an excessively long time. Therefore, the reaction is usually preferably performed at a temperature of 50 ° C. to 200 ° C., and the reaction time is 1 It is preferable to complete in minutes to 4 hours. For example, when ethylene glycol is used as the glycol, 50 ° C. to 150 ° C. is preferable, and when hexamethylene glycol is used, 100 ° C. to 200 ° C. is a preferable range, and the reaction time is more preferably 30 minutes to 2 hours. Become. If the reaction temperature is too high or the time is too long, the catalyst will deteriorate, which is not preferable.

  Moreover, when making this catalyst react, it is preferable that the mixture ratio of a phosphorus compound component is 1 or more and less than 4 as a molar ratio of the phosphorus atom with respect to a titanium atom, and also it is preferable that it is 1.5 or more and less than 3. If it is less than 1, the unreacted titanium compound component increases, and the color tone of the resulting polymer is deteriorated. On the other hand, if it is 4 or more, the presence of excess unreacted phosphorus compound component increases, and the polycondensation reaction activity is lowered.

  Further, in the reaction of the present catalyst, the blending ratio of the alkaline earth metal compound component is preferably 0.5 or more and less than 3 as the molar ratio of the alkaline earth metal atom to the titanium atom, and more preferably 1 or more and 2 or less. Preferably there is. If it is less than 0.5 as in the case of the phosphorus compound component, the presence of the unreacted titanium compound component increases and the color tone of the obtained polymer deteriorates. Conversely, if it is 4 or more, the presence of excess unreacted alkaline earth metal compound component increases, which promotes thermal decomposition of the polyester polymer and also promotes coloring of the polyester polymer.

  In addition, the glycol solution containing the catalyst composition of the present invention produced by heating a titanium compound component, a phosphorus compound component, and an alkaline earth metal compound component using glycol as a medium is a catalyst for producing a polyester without separation. After the precipitate reaction product is separated by means such as centrifugal sedimentation or filtration, the separated reaction product is separated with a recrystallization agent such as acetone, methyl alcohol and / or water. After recrystallization and purification, the purified product may be used as a catalyst for polyester production.

In producing a polyester using the catalyst of the present invention, it is preferable to use it as a catalyst in an amount of 1 to 50 ppm in terms of titanium metal atoms in the finally obtained polyester polymer. More preferably, it is used in an amount of
And as a metal atom in the polyester obtained, metal atoms other than titanium and phosphorus are preferably 10 ppm or less, more preferably 5 ppm or less in terms of metal element concentration.

  In addition, the said product should just exist at the time of a polycondensation reaction. Therefore, the catalyst may be added in any step such as a raw material slurry preparation step, an esterification step, a transesterification step, or a liquid phase polycondensation step. Further, the entire amount of the catalyst may be added at once, or may be added in a plurality of times.

  In addition, in the polycondensation reaction, a phosphorus stabilizer such as trimethyl phosphate may be added at any stage in the polyester production, if necessary, and further, an antioxidant, an ultraviolet absorber, a flame retardant, a fluorescent whitening agent, a matting agent, Agents, color adjusters, antifoaming agents and other additives may be added.

  Furthermore, in order to help improve the hue of the polyester obtained, in the production stage of the reactive polyester, organic blue pigments such as azo, triphenylmethane, quinoline, anthraquinone, phthalocyanine, etc. and other than inorganic It is also possible to add the color adjusting agent.

Next, the manufacturing method of the polyester using the catalyst for polyester manufacturing of this invention is demonstrated.
Polyesters such as aromatic polyesters can be produced by polycondensation of an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic glycol.

  Here, as the aromatic dicarboxylic acid, for example, terephthalic acid, phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid or an ester-forming derivative thereof can be used.

  As the aliphatic glycol, for example, ethylene glycol, trimethylene glycol, propylene glycol, tetramethylene glycol, neopentyl glycol, hexanemethylene glycol, and dodecamethylene glycol can be used.

  Along with aromatic dicarboxylic acids, aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid and decanedicarboxylic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, etc., or ester-forming derivatives thereof can be used as raw materials. In addition to aliphatic diols, alicyclic glycols such as cyclohexanedimethanol, bisphenols, hydroquinones, aromatic diols such as 2,2-bis (4-β-hydroxyethoxyphenyl) propane, and the like can be used as raw materials. .

  Furthermore, polyfunctional compounds such as trimesic acid, trimethylolethane, trimethylolpropane, trimethylolmethane, and pentaerythritol can be used as a raw material.

  First, when producing a polyester using the above raw materials, an aromatic dicarboxylic acid and an aliphatic glycol are directly esterified, or an ester-forming derivative of an aromatic dicarboxylic acid and an aliphatic glycol are esterified. After an exchange reaction or an addition reaction of an alkylene oxide to an aromatic dicarboxylic acid to obtain an oligomer, a polycondensation reaction is carried out using the polyester polycondensation catalyst of the present invention.

  For example, the direct esterification method specifically prepares a slurry containing an aromatic dicarboxylic acid and an aliphatic glycol. Such a slurry usually contains 1.1 to 1.6 mol, preferably 1.2 to 1.4 mol, of aliphatic glycol per mol of aromatic dicarboxylic acid. This slurry is continuously supplied to the esterification reaction step.

  The esterification reaction is preferably carried out in a single stage without allowing the reactants to circulate, or a method in which two or more esterification reaction groups are connected in series, both under conditions where the aliphatic glycol is refluxed. The water produced by the reaction is removed from the system with a rectification column.

  The reaction conditions in the case of carrying out esterification continuously in one stage without allowing the reactants to circulate are usually a reaction temperature of 240 to 280 ° C., preferably 250 to 270 ° C., and a reaction pressure of normal pressure to 0.00. The reaction is carried out under the condition of 3 MPa, and the reaction is desirably carried out until the esterification rate is usually 90% or more, preferably 95% or more.

By this esterification step, an esterification reaction product (oligomer) of aromatic dicarboxylic acid and aliphatic glycol is obtained, and the degree of polymerization of this oligomer is about 4-10.
The oligomer obtained in the esterification step as described above is then supplied to a polycondensation (liquid phase polycondensation) step.

  Next, in the liquid phase polycondensation step, in the presence of the polycondensation catalyst described above, the oligomer obtained in the esterification step is heated under reduced pressure to a temperature not lower than the melting point of the polyester (usually 240 to 280 ° C.). To polycondense. This polycondensation reaction is desirably carried out while distilling off unreacted aliphatic glycol and aliphatic glycol generated by polycondensation outside the reaction system.

  The polycondensation reaction may be performed in one tank or may be performed in a plurality of tanks. For example, when the polycondensation reaction is performed in two stages, the polycondensation reaction in the first tank has a reaction temperature of 245 to 290 ° C., preferably 260 to 280 ° C., and a pressure of 100 to 1 kPa, preferably 50 to The polycondensation reaction is carried out under the condition of 2 kPa, and the polycondensation reaction in the final second tank is a reaction temperature of 265 to 300 ° C., preferably 270 to 290 ° C., and a reaction pressure of usually 1000 to 10 Pa, preferably 500 to 30 Pa. Done under.

  In this way, a polyester can be produced using the catalyst for producing a polyester of the present invention. The polyester obtained in this polycondensation step is usually extruded in a molten state, cooled, and then granulated (chips). And The intrinsic viscosity of the obtained polyester is 0.40 to 0.80 dL / g, preferably 0.50 to 0.70 dL / g.

The polyester obtained by the above polycondensation reaction can be further subjected to a solid phase polycondensation reaction as necessary.
When the granular polyester supplied to the solid phase polycondensation reaction is preliminarily crystallized by heating to a temperature lower than the temperature in the case of performing solid phase polycondensation, It is preferable because the fusion between the granular polyesters and / or the inner wall of the reaction vessel can be suppressed during the polymerization reaction.

  Such a precrystallization step can be performed by heating the granular polyester in a dry state to a temperature of usually 120 to 200 ° C., preferably 130 to 180 ° C. for 1 minute to 4 hours. Such pre-crystallization can also be performed by heating the granular polyester at a temperature of 120 to 200 ° C. for 1 minute or more in a steam atmosphere, a steam-containing inert gas atmosphere, or a steam-containing air atmosphere. .

  The precrystallized polyester desirably has a crystallinity of 20 to 50%. The so-called polyester solid-phase polycondensation reaction does not proceed by this precrystallization treatment, and the intrinsic viscosity of the precrystallized polyester is almost the same as the intrinsic viscosity of the polyester after polycondensation. The intrinsic viscosity difference before and after the formation is usually 0.06 dL / g or less.

  The solid phase polycondensation step comprises at least one stage, a temperature of 190 to 230 ° C., preferably 195 to 225 ° C., and a pressure of 200 kPa to 1 kPa, preferably from normal pressure to 10 kPa, under conditions of nitrogen, argon, It is performed under an inert gas atmosphere such as carbon dioxide. Nitrogen gas is desirable as the inert gas used.

The granular polyester obtained through such a solid-phase polycondensation step may be subjected to water treatment as necessary. This water treatment is carried out by treating the granular polyester with water, steam, steam-containing inert gas, steam-containing. It is performed by contacting with air or the like.
The production process of the polyester as described above can be performed by any of a batch type, a semi-continuous type, and a continuous type.

  The terephthalic acid or its ester-forming derivative is used in an amount of 80 mol% or more, preferably 90 mol% or more, based on 100 mol% of the aromatic dicarboxylic acid, and ethylene glycol or its ester-forming derivative. The derivative is preferably used in an amount of 80 mol% or more, preferably 90 mol% or more with respect to 100 mol% of the aliphatic glycol.

  In particular, polyethylene terephthalate that performs solid-phase polycondensation is often used in bottles and the like, and therefore has an intrinsic viscosity of 0.70 to 1.00 dL / g and a cyclic trimer in polyethylene terephthalate. It is preferable that the content is 0.5 wt% or less and the acetaldehyde content is 5 ppm or less.

  In addition, since the cyclic trimer and acetaldehyde in polyethylene terephthalate are usually reduced in the solid phase polycondensation step, the intrinsic viscosity of the melt condensation before the solid phase polycondensation and the conditions of the solid phase polycondensation should be adjusted. It can respond.

  In addition, the polyester obtained using the catalyst for producing a polyester of the present invention specifically has a haze of the body portion of a preform molded body obtained by molding usually 10% or less, preferably 0 to 5%. In addition, the content of acetaldehyde can be 30 ppm or less, preferably 25 ppm or less.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention does not receive limitation at all by this. In addition, each value described in the Example was calculated | required according to the following method.

(1) Intrinsic viscosity:
After heating and dissolving 0.6 g of a polyester sample in 50 cc of o-chlorophenol, the solution once cooled was calculated from the solution viscosity measured at 35 ° C. using an Ubbelohde viscometer.

(2) Hue (Col):
The granular polymer sample was heat-treated in a dryer at 160 ° C. for 90 minutes to crystallize, and then measured with a CM-7500 type color machine manufactured by Color Machine Co., Ltd. In addition, about the sample after a solid phase polycondensation reaction, it measured similarly and calculated | required except not performing the heat processing process of 160 degreeC x 90 minutes.

(3) Diethylene glycol content:
The content of diethylene glycol (hereinafter abbreviated as DEG) was determined by decomposing the sample with hydrazine hydrate and measuring it using gas chromatography (model “263-70” manufactured by Hitachi, Ltd.).

(4) Haze:
After starting the injection molding of the preform for bottle formation, sample one from the fifth shot onwards, sample the central part in the length direction of the preform body, and make turbidity by Nippon Denshoku Industries Co., Ltd. It calculated | required using the total (HD-1001DP).

(5) Acetaldehyde content:
The content of acetaldehyde (hereinafter abbreviated as AA) was obtained by freeze-pulverizing the sample, placing it in a vial, holding it at 150 ° C. for 60 minutes, and using headspace gas chromatography manufactured by Hitachi, Ltd.

(6) Metal content concentration analysis (in catalyst):
The concentration of titanium and phosphorus atoms in the catalyst was determined by setting the dried sample in a scanning electron microscope (SEM; Model S570, manufactured by Hitachi Instruments Service Co., Ltd.) and connecting it to an energy dispersive X-ray microanalyzer (XMA; Horiba, Ltd.) It was determined by quantitative analysis using EMAX-7000 manufactured by Seisakusho.

(7) Metal content concentration analysis (in polyester polymer)
The residual catalyst metal concentration in the polyester was determined by heating and melting a granular polymer sample on an aluminum plate, then creating a test molded body having a flat surface with a compression press machine, and producing a fluorescent X-ray apparatus (3270E manufactured by Rigaku Corporation). Type).

(8) Cyclic trimer amount (Cy-3):
The amount of cyclic trimer (hereinafter abbreviated as Cy-3) is obtained by pulverizing a sample with a pulverizer, weighing a certain amount thereof, and dissolving it in a small amount of hexafluoroisopropanol / chloroform mixed solution. The solution was diluted with chloroform to a constant concentration (50 g / liter). The sample solution was subjected to gel permeation chromatography (GPC; ALC / GPC244 type manufactured by Waters) to separate the low molecular weight region and its peak was detected, and the calibration obtained from the Cy-3 standard sample Determined based on line.

[Example 1]
Preparation of titanium compound components:
A 2 liter three-necked flask equipped with a function capable of mixing and stirring the solution was prepared, and 919 g of ethylene glycol and 80 g of trimellitic anhydride were placed therein and mixed and stirred. Then, 71 g of titanium tetrabutoxide was slowly added gradually. A transparent ethylene glycol solution of a titanium compound was obtained.
Hereinafter, this solution is abbreviated as “TB solution”. When the titanium concentration of this solution was measured using fluorescent X-rays, it was 1.02 wt%.
Preparation of alkaline earth metal compound components:
A 2 liter three-necked flask equipped with a function of heating and mixing and stirring was prepared, and 28.3 g of magnesium acetate tetrahydrate was added to 400 g of ethylene glycol and heated to 100 ° C. Hereinafter, this solution is abbreviated as “M1 solution”.
Preparation of phosphorus compound component:
A 2 liter three-necked flask equipped with a function of heating and mixing and stirring was prepared, and 256 g of ethylene glycol was placed therein and heated to 100 ° C. while stirring. When that temperature was reached, 34.5 g of monolauryl phosphate was added and dissolved by heating, mixing and stirring to obtain a clear solution. Hereinafter, this solution is abbreviated as “P1 solution”.
Preparation of catalyst for polyester production:
310 g of the previously prepared “TB solution” is slowly and slowly added to the “M1 solution” that is heated and controlled at 100 ° C. under stirring. After the entire amount is added, the mixture is stirred and held at a temperature of 100 ° C. for 1 hour. A mixed solution of a titanium compound and an alkaline earth metal compound was prepared. Furthermore, after adding the whole amount of the “P1 solution” prepared as described above, the mixture was stirred and held at a temperature of 100 ° C. for 1 hour. The blending ratio of “P1 solution”, “M1 solution” and “TB solution” at this time is such that the molar concentration ratio of titanium atom, phosphorus atom and alkaline earth metal atom is adjusted to 1: 2: 2. The obtained solution is hereinafter abbreviated as “TMP1-2 / 2 catalyst”.

[Example 2]
In Example 1, the preparation of the phosphorus compound component was changed from monolauryl phosphate to monobutyl phosphate, except that a “P2 solution” was prepared as described below and used for catalyst preparation. The reaction was carried out according to the procedure. The “P2 solution” was prepared as follows.
137 g of ethylene glycol was heated to 100 ° C. with stirring, and when this temperature was reached, 28.3 g of monobutyl phosphate was added and dissolved by heating, mixing and stirring to obtain a “P2 solution” which is a transparent solution. .
In the preparation of a catalyst for polyester production, 435 g of TB solution was used, and the blending ratio of “P2 solution”, “M1 solution” and “TB solution” was a molar concentration ratio of titanium atom: phosphorus atom: alkaline earth metal atom. Is adjusted to 1: 2: 2, and the obtained solution is hereinafter abbreviated as “TMP2-2 / 2 catalyst”.

[Example 3]
In Example 1, as the preparation of the phosphorus compound component, the addition amount of monolauryl phosphate was changed, and as described below, a “P3 solution” was prepared for catalyst preparation, and the ratio was changed as follows: The reaction was carried out using basically the same apparatus and procedure except that. The “P3 solution” was prepared as follows.
194 g of ethylene glycol was heated to 100 ° C. while stirring, and when this temperature was reached, 31.3 g of monolauryl phosphate was added and dissolved by heating, mixing and stirring to obtain a transparent “P3 solution”. .
In the preparation of the catalyst for polyester production, 375 g of TB solution was used, and the blending ratio of “P3 solution”, “M1 solution”, and “TB solution” was a molar concentration ratio of titanium atom: phosphorus atom: alkaline earth metal atom. Is adjusted to 1: 1.5: 2, and the resulting solution is hereinafter abbreviated as “TMP1-1.5 / 2 catalyst”.

[Example 4]
In Example 2, as the preparation of the phosphorus compound component, the addition amount of monobutyl phosphate was changed to prepare “P4 solution” for catalyst preparation as follows, and the ratio was changed as follows: The reaction was carried out using basically the same apparatus and procedure except that. The “P4 solution” was prepared as follows.
While stirring, 227 g of ethylene glycol was heated to 100 ° C., and when this temperature was reached, 33.0 g of monobutyl phosphate was added, heated, mixed, stirred and dissolved to obtain “P4 solution” which is a transparent solution.
In preparing the catalyst for polyester production, 340 g of TB solution was used, and the blending ratio of “P4 solution”, “M1 solution”, and “TB solution” was the molar concentration of titanium atom: phosphorus atom: alkaline earth metal atom. The ratio was adjusted to 1: 3: 2, and the obtained solution is hereinafter abbreviated as “TMP2-3 / 2 catalyst”.

[Example 5]
Preparation of alkaline earth metal compound components:
A 2 liter three-necked flask equipped with a function of heating and mixing and stirring was prepared, and 28.3 g of magnesium acetate tetrahydrate was added to 687.5 g of ethylene glycol and heated to 100 ° C. Hereinafter, this solution is abbreviated as “M2 solution”.
Preparation of catalyst for polyester production:
22.5 g of titanium tetrabutoxide was slowly added to the above-mentioned “M2 solution” controlled to 100 ° C. under stirring, and after adding the entire amount, stirring was maintained at a temperature of 100 ° C. for 1 hour. A mixed solution of alkaline earth metal compounds was prepared. Further, the whole amount of the “P1 solution” prepared in Example 1 was added thereto, and then stirred and held at a temperature of 100 ° C. for 1 hour. The blending ratio of “P1 solution”, “M2 solution” and titanium tetrabutoxide at this time is such that the molar concentration ratio of titanium atom, phosphorus atom, and alkaline earth metal atom is adjusted to 1: 2: 2. The obtained solution is hereinafter abbreviated as “TMP3 / 2/2 catalyst”.

[Example 6]
Polyester production:
In a reactor in which 225 parts of oligomers have been retained in advance, 179 parts of high-purity terephthalic acid and 95 parts of ethylene glycol were mixed under conditions of 255 ° C. and normal pressure in a nitrogen atmosphere under stirring. The prepared slurry was supplied at a constant rate, and the esterification reaction was completed for 4 hours while water and ethylene glycol generated in the reaction were distilled out of the system to complete the reaction. The esterification rate at this time was 98% or more, and the polymerization degree of the produced oligomer was about 5 to 7.
225 parts of the oligomer obtained by this esterification reaction was transferred to a polycondensation reaction tank, and 0.832 parts of the catalyst (TMP1-2 / 2) solution obtained in Example 1 was added as a polycondensation catalyst. Subsequently, the reaction temperature in the system is increased from 255 to 280 ° C., and the reaction pressure is gradually increased and reduced from normal pressure to 60 Pa, respectively, and the polycondensation reaction is carried out while removing water and ethylene glycol generated in the reaction from the system. went.
The progress of the polycondensation reaction was confirmed without monitoring the load on the stirring blades in the system, and the reaction was terminated when the desired degree of polymerization was reached. Thereafter, the reaction product in the system was continuously extruded in a strand form from the discharge part, cooled and cut to obtain about 3 mm granular pellets. The polycondensation reaction time at this time was 110 minutes. The quality of the obtained polyethylene terephthalate is shown in Table 1.

[Example 7]
In Example 6, the same operation was performed except that the catalyst (TMP2-2 / 2) solution prepared in Example 2 was used as the polycondensation catalyst, and the input amount was 0.593 parts. The quality of the obtained polyethylene terephthalate is shown in Table 1.

[Example 8]
In Example 6, the same operation was performed except that the polycondensation catalyst was changed to the catalyst (TMP1-1.5 / 2) solution prepared in Example 3 and the input amount was 0.413 parts. The quality of the obtained polyethylene terephthalate is shown in Table 1.

[Example 9]
In Example 6, the same operation was performed except that the polycondensation catalyst was changed to the catalyst (TMP2-3 / 2) solution prepared in Example 4 and the input amount was 2.277 parts. The quality of the obtained polyethylene terephthalate is shown in Table 1.

[Example 10]
In Example 6, the same operation was carried out except that the polycondensation catalyst was changed to the catalyst (TMP3 / 2/2) solution prepared in Example 5. The quality of the obtained polyethylene terephthalate is shown in Table 1.

[Example 11]
In Example 6, in addition to the prepared catalyst solution (TMP1-2 / 2), the same operation was performed except that 0.3 ppm of terazole blue as a toning agent was added on the basis of the amount of the obtained polymer. It was. The quality of the obtained polyethylene terephthalate is shown in Table 1.

[Example 12]
In Example 1, the preparation of the phosphorus compound component was changed from monolauryl phosphate to phenylphosphonic acid, except that a “PH1 solution” was prepared as described below and used for catalyst preparation. The reaction was carried out according to the procedure. The “PH1 solution” was prepared as follows.
270 g of ethylene glycol was heated to 100 ° C. with stirring, and when this temperature was reached, 20.5 g of phenylphosphonic acid was added and dissolved by heating, mixing and stirring to obtain a “PH1 solution” which is a transparent solution. It was.
In the preparation of a catalyst for polyester production, 310 g of “TB solution” was used, and the blending ratio of “PH1 solution”, “M1 solution”, and “TB solution” was titanium atoms, phosphorus atoms, alkaline earth metal atoms. The molar concentration ratio was adjusted to 1: 2: 2, and the obtained solution is hereinafter abbreviated as “TMPH1-2 / 2 catalyst”.

[Example 13]
In Example 1, the preparation of the phosphorus compound component was changed from phenylphosphonic acid to butylphosphonic acid, and a “PH2 solution” was prepared as described below and used for catalyst preparation. The reaction was carried out according to the procedure. The “PH2 solution” was prepared as follows.
147 g of ethylene glycol was heated to 100 ° C. with stirring, and when this temperature was reached, 18 g of butylphosphonic acid was added and dissolved by heating, mixing and stirring to obtain a “PH2 solution” which is a transparent solution.
In the preparation of a catalyst for polyester production, 435 g of “TB solution” was used, and the blending ratio of “PH2 solution”, “M1 solution”, and “TB solution” was titanium atoms, phosphorus atoms, alkaline earth metal atoms. The molar concentration ratio was adjusted to 1: 2: 2, and the obtained solution is hereinafter abbreviated as “TMPH2-2 / 2 catalyst”.

[Example 14]
In Example 12, as the preparation of the phosphorus compound component, the amount of phenylphosphonic acid added was changed, the “PH3 solution” was prepared as follows, and the catalyst was adjusted, and the ratio was changed as follows: The reaction was carried out using basically the same apparatus and procedure except for the above. The “PH3 solution” was prepared as follows.
210 g of ethylene glycol was heated to 100 ° C. with stirring, and when this temperature was reached, 15.4 g of phenylphosphonic acid was added and dissolved by heating, mixing and stirring to obtain a “PH3 solution” which is a transparent solution. .
In the preparation of the catalyst for polyester production, 375 g of the TB solution was used, and the blending ratio of “PH3 solution”, “M1 solution” and “TB solution” was a molar concentration of titanium atom: phosphorus atom: alkaline earth metal atom. The ratio was adjusted to 1: 1.5: 2, and the obtained solution is hereinafter abbreviated as “TMPH1-1.5 / 2 catalyst”.

[Example 15]
In Example 12, as the preparation of the phosphorus compound component, the amount of phenylphosphonic acid added was changed, the “PH4 solution” was prepared as follows, and the catalyst was adjusted, and the ratio was changed as follows: The reaction was carried out using basically the same apparatus and procedure except for the above. The “PH4 solution” was prepared as follows.
229 g of ethylene glycol was heated to 100 ° C. with stirring, and when this temperature was reached, 30.8 g of phenylphosphonic acid was added and dissolved by heating, mixing and stirring to obtain a “PH4 solution” which is a transparent solution. .
In preparing the catalyst for polyester production, 340 g of TB solution was used, and the blending ratio of “PH4 solution”, “M1 solution” and “TB solution” was a molar concentration of titanium atom: phosphorus atom: alkaline earth metal atom. The ratio was adjusted to 1: 3: 2, and the obtained solution is hereinafter abbreviated as “TMPH1 / 3/2 catalyst”.

[Example 16]
In Example 5, the same operation was performed except that the “PH1” solution was used instead of the “P1 solution” as the phosphorus compound component to be added to the mixed solution of the titanium compound and the alkaline earth metal compound. At this time, the mixing ratio of “PH1 solution”, “M2 solution” and titanium tetrabutoxide is adjusted such that the molar concentration ratio of titanium atom, phosphorus atom and alkaline earth metal atom is 1: 2: 2. The obtained solution is hereinafter abbreviated as “TMPH3 / 2/2 catalyst”.

[Example 17]
In Example 6, the same operation was carried out except that the polycondensation catalyst was changed to the catalyst (TMPH1-2 / 2) solution prepared in Example 12. The quality of the obtained polyethylene terephthalate is shown in Table 1.

[Example 18]
In Example 6, the same operation was performed except that the catalyst (TMPH2-2 / 2) solution prepared in Example 13 was used as the polycondensation catalyst, and the input amount was 0.593 parts. The quality of the obtained polyethylene terephthalate is shown in Table 1.

[Example 19]
In Example 6, the same operation was performed except that the polycondensation catalyst was changed to the catalyst (TMPH1-1.5 / 2) solution prepared in Example 14 and the input amount was 0.413 parts. The quality of the obtained polyethylene terephthalate is shown in Table 1.

[Example 20]
In Example 6, the same operation was performed except that the polycondensation catalyst was changed to the catalyst (TMPH1-3 / 2) solution prepared in Example 15 and the input amount was 2.277 parts. The quality of the obtained polyethylene terephthalate is shown in Table 1.

[Example 21]
The same operation as in Example 6 was performed except that the catalyst (TMPH3 / 2/2) solution prepared in Example 16 was used as the polycondensation catalyst. The quality of the obtained polyethylene terephthalate is shown in Table 1.

[Example 22]
In Example 11, the same operation was performed except that the catalyst (TMPH1-2 / 2) solution prepared in Example 12 was changed as the polycondensation catalyst. The quality of the obtained polyethylene terephthalate is shown in Table 1.

[Comparative Example 1]
In Example 6, the polycondensation catalyst was changed to a 1.3% concentration ethylene glycol solution of antimony trioxide, the amount charged was 4.83 parts, and a 25% ethylene glycol solution of trimethyl phosphate was further added as a stabilizer. The same operation was performed except that 121 parts were added. The quality of the obtained polyethylene terephthalate is shown in Table 1.

[Comparative Example 2]
In Example 6, the same operation was performed except that the polycondensation catalyst was changed to the “TB solution” prepared in Example 1 and the input amount was 0.258 parts. The quality of the obtained polyethylene terephthalate is shown in Table 1.

  As is clear from Examples 6 to 22 and Comparative Examples 1 and 2 above, the catalyst of the present invention is excellent in the polycondensation reaction, can be produced in a smaller amount than the conventional antimony compound catalyst, and also has a hue. It can be seen that this is a significant improvement over the antimony catalyst.

[Examples 23 to 30, Comparative Examples 3 to 4]
In Examples 6, 7, 10, 11, 17, 18, 21, 22, and Comparative Examples 1 and 2, the obtained granular polyethylene terephthalate was treated at 160 ° C. for 10 minutes in a high-speed stirring fluidized crystallizer. Then, the sample was semi-crystallized and then crystallized and dried at 160 ° C. for 4 hours under a nitrogen flow to perform preliminary crystallization. Subsequently, the polyethylene terephthalate is transferred to a packed column type solid phase polymerization reaction column, and subjected to solid phase polycondensation at 215 ° C. for 22 to 25 hours under a nitrogen flow so that the intrinsic viscosity of each polyethylene terephthalate becomes 0.760 dL / g. The reaction time was adjusted. The quality of these polyethylene terephthalates obtained is shown in Table 2.

Further, a preform molded body was molded by the following method using these solid phase polycondensed polyethylene terephthalate.
5 kg of polyethylene terephthalate is dried using a shelf-type dryer for 10 hours or more under conditions of 160 ° C., normal pressure and inflow of N 2. )), Cylinder temperature 275 ° C., screw rotation speed 160 rpm, primary pressure time 3.0 seconds, mold cooling temperature 10 ° C., cycle 30 seconds, outer diameter about 28 mm, inner diameter about 19 mm, length 136 mm, barrel A cylindrical preform having a thickness of 4 mm and a weight of about 56 g was injection molded. The center part of the trunk portion of the obtained preform was sampled, and its intrinsic viscosity, haze, AA content, and Cy-3 amount were measured. These results are also shown in Table 2.

  According to the present invention, a polyester production catalyst having high polymerization activity can be provided, and a polyester can be produced with higher catalytic activity than germanium compounds and antimony compounds conventionally used as polycondensation catalysts. Can do. In addition, the polyester produced with the catalyst of the present invention is excellent in hue as compared with the case where an antimony compound is used as a polycondensation catalyst, and in particular, polyethylene terephthalate has excellent transparency in addition to the hue in the molded product, and is also acetaldehyde. Since the content is small, it is useful as a material for molded containers such as bottles.

Claims (10)

(A) Titanium compound (1) represented by the following general formula (I)

And an aromatic polyvalent carboxylic acid represented by the titanium compound (1) of the general formula (I) and the following general formula (II)

Or a titanium compound (2) obtained by reacting with an anhydride thereof,
A titanium compound component consisting of at least one selected from
(B) Phosphorus compound (3) represented by the following general formula (III)

A phosphorus compound component consisting of at least one of
(C) Alkaline earth metal compound (4) represented by the following general formula (IV)

An alkaline earth metal compound component comprising at least one of
The reaction molar ratio (mTi) / () of the titanium compound component relative to the molar amount of titanium atom (mTi) and the alkaline earth metal compound component relative to the molar amount of alkaline earth metal atom (mM). mM) in the range of (2: 1) to (1: 3).   In the reaction product of the titanium compound component, the phosphorus compound component, and the alkaline earth metal compound component, the titanium atom equivalent molar amount (mTi) of the titanium compound component and the phosphorus atom equivalent molar amount (mP) of the phosphorus compound component The catalyst for polyester production according to claim 1, wherein the reaction molar ratio (mTi) :( mP) is in the range of (1: 1) to (1: 4).   The reaction molar ratio (mTi) / (mM) to the alkaline earth metal atom equivalent molar amount (mM) of the alkaline earth metal compound component is in the range of (1: 1) to (1: 2). Item 3. The catalyst for producing a polyester according to item 1 or 2.   The catalyst for polyester production according to any one of claims 1 to 3, wherein the titanium compound (1) of the formula (I) is selected from titanium tetraalkoxides, octaalkyltrititanates and hexaalkyldititanates.   The aromatic polyvalent carboxylic acid of the formula (II) or its anhydride is selected from phthalic acid, trimellitic acid, hemimellitic acid and pyromellitic acid or their anhydrides. The catalyst for polyester production according to Item.   The catalyst for polyester production according to any one of claims 1 to 5, wherein the phosphorus compound (3) of the formula (III) is selected from monoarylphosphonic acids and monoalkylphosphates.   The alkaline earth metal compound (4) of the formula (IV) is composed of magnesium formate, magnesium acetate, magnesium propionate, magnesium butyrate, magnesium benzoate, calcium formate, calcium acetate, calcium propionate, calcium butyrate and calcium benzoate. The catalyst for polyester production according to any one of claims 1 to 6, which is selected.   A polyester produced using the catalyst according to claim 1 and containing 1 to 50 ppm of titanium element.   The polyester according to claim 8, wherein the polyester is polyethylene terephthalate.   The polyester according to claim 8 or 9, having an intrinsic viscosity of 0.70 to 1.00 dL / g, a cyclic trimer content of 0.5 wt% or less, and an acetaldehyde content of 5 ppm or less.