JP2004217887A - Catalyst for producing polyester and method for producing polyester by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst for producing a polyester excellent in thermal stability without requiring a long time for its polycondensation reaction, and a method for producing the polyester in a good productivity by using such catalyst. <P>SOLUTION: This catalyst for producing the polyester contains (1) a titanium atom, (2) a silicon atom and (3) at least 1 kind of an atom selected from beryllium, magnesium, calcium, zinc, strontium, barium, boron, aluminum, potassium, manganese, cobalt, germanium, antimony and phosphorus, and the method for producing the polyester by using the catalyst is provided. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

  The present invention relates to a polyester production catalyst and a method for producing a polyester using the catalyst, specifically, a polyester production catalyst capable of polycondensing an aromatic dicarboxylic acid and a diol at a high polymerization rate, And a method for producing a polyester having excellent properties by using the catalyst.

  Conventionally, polyester typified by polyethylene terephthalate has excellent mechanical strength, chemical stability, gas barrier properties and hygiene properties, and is relatively inexpensive and lightweight, so that various packaging materials such as bottles and films are used. Or as a fiber or the like.

  Conventionally, these polyesters are conventionally produced mainly using an antimony compound as a polycondensation catalyst, but there is a problem of foreign matter / haze due to antimony metal precipitation, or a large amount of a catalyst such as 300 to 400 ppm is required for the antimony compound. It is strongly desired that a catalyst having high activity is required.

  On the other hand, as a method for producing a polyester resin containing no antimony compound, many methods using a titanium compound as a polycondensation catalyst have been proposed, but there is a problem that thermal stability is lacking.

  As a titanium compound used as a polycondensation catalyst, for example, the following titanium compounds have been proposed.

  Co-precipitate produced by simultaneous hydrolysis precipitation of a titanium compound and a metal compound of a metal selected from the group of IA, IIA, VIIIA, IB, IIB, IIIB and IVB, alone or as a mixture It is known to use, and specifically, a coprecipitate obtained by simultaneously hydrolyzing tetraisopropoxytitanium and an alkoxy compound of, for example, aluminum with water in anhydrous ethanol is used as a catalyst. (See Patent Document 1).

A solid obtained by dehydrating and drying a hydrolyzate obtained by hydrolyzing a mixture of a titanium halide and a compound of at least one element selected from elements other than titanium or a precursor of this compound. It is known to use a titanium-containing compound in the form of, specifically, a coprecipitate obtained by dropwise addition and hydrolysis of titanium tetrachloride in an aqueous solution of magnesium hydroxide as a catalyst by dehydration and drying. It is shown that it is used (see Patent Document 2).
JP 2002-503274 A JP-A-2001-064378

  However, according to studies by the present inventors, the method using a catalyst comprising these titanium compounds has a disadvantage that the time required for the polycondensation reaction is long, and the obtained polyester resin has a thermal property represented by an acid value. Due to the problem of lack of stability, it has been found that it is not yet satisfactory as an industrial production method. Therefore, there is a strong need for alternative catalysts that can produce higher quality polyesters with better activity.

  The present invention has been made in view of the above circumstances, and has the disadvantage that the polycondensation reaction caused by the conventional catalyst requires a long time, and the resulting polyester resin lacks thermal stability and is inferior in quality. Another object of the present invention is to provide a polyester production catalyst which can be eliminated, and a method for producing a polyester having excellent properties with good productivity by using such a catalyst.

  The present inventors have made intensive studies in view of the above problems, and as a polycondensation catalyst, require a titanium atom and a silicon atom as essential, and further beryllium, magnesium, calcium, zinc, strontium, barium, boron, aluminum, gallium, A catalyst containing at least one atom selected from the group consisting of manganese, cobalt, germanium, antimony, and phosphorus is highly active as a catalyst for polyester production, and the polyester resin produced using this catalyst has extremely high quality. And found that the present invention was completed.

  That is, the gist of the present invention is (1) titanium atom, (2) silicon atom, and (3) beryllium, magnesium, calcium, zinc, strontium, barium, boron, aluminum, gallium, manganese, cobalt, germanium, antimony and A polyester production catalyst containing at least one atom selected from the group consisting of phosphorus, and an esterification reaction or a dicarboxylic acid component containing an aromatic dicarboxylic acid or an ester-forming derivative thereof and a diol component as main components. In the method for producing a polyester by polycondensation via a transesterification reaction, the present invention resides in a method for producing a polyester, which comprises using the catalyst for producing a polyester.

  By using the polyester production catalyst of the present invention, a polyester having excellent properties can be produced with good productivity, and thus the industrial value of the present invention is high.

  Hereinafter, the present invention will be described in detail.

  The polyester production catalyst according to the present invention comprises at least (1) a titanium atom, (2) a silicon atom, and (3) beryllium, magnesium, calcium, zinc, strontium, barium, boron, aluminum, gallium, manganese, cobalt, It contains at least one atom selected from the group consisting of germanium, antimony and phosphorus.

The total amount of titanium atoms and at least one atom selected from the group consisting of beryllium, magnesium, calcium, zinc, strontium, barium, boron, aluminum, gallium, manganese, cobalt, germanium, antimony and phosphorus with respect to silicon atoms is usually The former: the latter is 95: 5 to 5:95, preferably 90:10 to 5:95, and more preferably 90:10 to 30:70. If the amount of silicon used is too large, the catalytic activity may be reduced. If the amount is too small, the dispersion of the active ingredient tends to be insufficient.
Further, at least one atomic weight selected from the group consisting of beryllium, magnesium, calcium, zinc, strontium, barium, boron, aluminum, gallium, manganese, cobalt, germanium, antimony and phosphorus with respect to the titanium atom is the former: 99 : 1 to 1:99, preferably 95: 5 to 5:95, more preferably 95: 5 to 40:60, particularly preferably 95: 5 to 50:50.

  The polyester production catalyst of the present invention may contain other metal elements as long as its performance is not impaired, but it is preferable that the catalyst consist essentially of only the above elements (1) to (3).

The catalyst for producing polyester of the present invention comprises (I) a titanium compound, (II) a silicon compound and (III) beryllium, magnesium, calcium, zinc, strontium, barium, boron, aluminum, gallium, manganese, cobalt, germanium, antimony and It is produced using a compound of at least one element selected from the group consisting of phosphorus.

  (I) Specific examples of the titanium compound include titanium tetrachloride such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide; titanium trihalide such as titanium trichloride; Titanium halides such as titanium halide and titanium monohalide, alkoxytitanium such as tetrabutoxytitanium and tetraisopropoxytitanium, and organic titanium compounds such as acetylacetonate salt of titanium are used. Of these, titanium halide is particularly preferred.

  (II) Specific examples of the silicon compound include silicate compounds such as tetramethoxysilane, tetrabutoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraphenoxysilane, and tetrabenzyloxysilane; tetrachlorosilane; Silicon halide compounds such as chlorosilane, silicon carboxylate such as silicon acetate, disiloxane, trisiloxane, dimethyldisiloxane, hexamethyldisiloxane, polydimethylsiloxane, hexamethoxydisiloxane, siloxane compound such as polymethoxysiloxane, Silanol compounds such as silanol, silanediol and phenylsilanetriol, and silanolate compounds such as sodium triphenylsilanolate are used. Of these, silicate compounds and silicon halide compounds are particularly preferred. As the silicate compound, an alkoxysilane compound is preferable.

(III) beryllium, magnesium, calcium, zinc, strontium, barium,
As the compound of at least one element selected from the group consisting of boron, aluminum, gallium, manganese, cobalt, germanium, antimony and phosphorus, preferably at least one compound selected from the group consisting of magnesium, zinc, aluminum and phosphorus And particularly preferably a magnesium compound. These compounds may be any compounds as long as these counter ions do not adversely affect the polycondensation reaction. Specific examples thereof include hydroxides, nitrates, halides, carbonates, carboxylate salts, alkoxides, and acetylacetate. Nart and the like can be used. Of these, preferred are carboxylate, alkoxide and halide of the above elements.
Examples of the method for producing the polyester production catalyst of the present invention include: A method obtained by adjusting the pH of a mixture of a solvolysate of a titanium compound, a silicon compound and a compound of (III), B. A method in which a titanium compound is added to a solvent in which a silicon compound and a compound of (III) are dissolved or suspended, C.I. A method in which a solvent is added to a mixture of a titanium compound, a silicon compound and a compound of (III), A method of adding a solvent in which a silicon compound and a compound of (III) are dissolved or suspended in a titanium compound can be used. Among them, A. The solvolysate of the titanium compound of the above, the one obtained by adjusting the pH of the mixture with the silicon compound and the compound of (III) tend to obtain a catalyst in which these atoms are highly dispersed, In particular, a polyester resin having high activity as a catalyst for producing polyester, and a polyester resin produced using this catalyst is extremely excellent in quality, and thus is preferable.
The product is substantially a solvolysis product of a titanium compound, a solvolysis product of a silicon compound and a compound of (III), and more preferably the hydrolysis is hydrolysis.

  The method for obtaining the solvolysate of the titanium compound is not particularly limited as long as the conditions under which the titanium compound is solvolyzed are employed.For example, 1) a method of adding the titanium compound in a solvent, 2) a solvent in the titanium compound 3) A method of passing a gas containing a titanium compound vapor in a solvent, 4) A method of passing a gas containing a solvent in a titanium compound, 5) A gas containing a titanium compound and a solvent A method of bringing a gas into contact is exemplified.

  Examples of the solvent used for solvolysis include water, alcohols such as methanol, ethanol, isopropanol, and butanol, 1,2-butanediol, 2,3-butanediol, 1,3-butanediol, and 1,4-butane. Diol, 1,3-pentanediol, 2,4-pentanediol, 1,2-cyclohexanediol, 3-methyl-1,3-butanediol, 2,3-dimethyl-2,3-butanediol, 2-methyl Examples thereof include diols such as -2,4-pentanediol and glycols such as ethylene glycol and hexylene glycol. Preferably, water is used.

The method of mixing the solvolyzed product of the titanium compound with the silicon compound and the compound of (III) is not particularly limited. For example, 1) separately adding the silicon compound and the compound of (III) to the solvolyzed product of the titanium compound 2) a method of simultaneously adding a silicon compound and a compound of (III) to a solvolysate of a titanium compound, 3) a method of adding a solvolysate of a titanium compound to a silicon compound and a compound of (III), 4) A method in which a solvolyzed product of a titanium compound is added to a silicon compound, and then the compound of (III) is added. 5) A mixture of the solvolyzed product of a titanium compound with a silicon compound and a compound of (III). And the like. Of these, the methods 1) and 2) are preferred. It is particularly preferable to use a solvolyzed product of a titanium compound in order to appropriately disperse the active ingredient.
Conditions for obtaining the mixture of the solvolysate of the titanium compound with the silicon compound and the compound of (III) are usually 100 ° C. or lower, preferably 0 to 70 ° C.

As mentioned above, the catalyst for polyester production of the present invention is preferably obtained by adjusting the pH of a mixture of a solvolysate of a titanium compound, a silicon compound and a compound of (III), and the final pH is 4 or more. Preferably, the form is not specified, but it is substantially a solvolysate of the above mixture, and substantially a hydrolyzate when the solvent is water.
The form of the catalyst obtained by solvolysis depends on the type of the compound and the solvolysis conditions and is not necessarily clear.For example, when the solvolysis is hydrolysis, the form of the hydroxide containing an oxide is Presumed.

  Examples of the pH-adjusting preparation include hydroxides such as ammonia, sodium, potassium, and magnesium, carbonates, bicarbonates, oxalates, urea, and basic organic compounds. Of these, ammonia is preferred. The pH adjuster may be added as it is to the solvent-decomposed solution or suspension thereof, or may be added by dissolving in a solvent such as water. However, it is preferable to add the pH adjuster by dissolving in a solvent such as water. The final pH of the pH-adjusted mixture (solvolysis solution or suspension thereof) is preferably 4 or more, and more preferably 6 or more. The addition of the pH adjusting agent is preferably performed at 70 ° C. or lower.

The obtained solvolysis product can be subjected to solid-liquid separation, if necessary, and then subjected to operations such as washing, drying, baking, and pulverization. As the washing liquid, water or an organic solvent such as ethanol can be used. When the solvolysis is hydrolysis, water is preferred.
The above A. ~ D. The solvolysate obtained by adjusting the pH of the mixture obtained by the above method, preferably a solvolysate of a titanium compound, a mixture with a silicon compound and a compound of (III), is directly used as a polyester. Although it is possible to use it as a production catalyst, the solvolysate after washing can be dried if necessary, and is a solid obtained by drying the solvolysate. preferable. Drying can be performed under normal pressure or reduced pressure. The drying temperature is not particularly limited, but is preferably 30 ° C. or more and less than 200 ° C., and drying is preferably performed promptly. The solid after drying is preferably ground. The average particle size of the solid after pulverization is usually 200 μm or less, preferably 100 μm or less, particularly 50 μm or less, and the lower limit is usually 1 nm or more, preferably 10 nm or more. On the other hand, the solid obtained by drying can be further calcined. The sintering is usually performed at a temperature of 200 to 500 ° C., and the sintering takes the form of a composite oxide. The firing time is about 1 minute to 100 hours.

The catalyst for polyester production of the present invention, which is a solid obtained by drying the solvolysate, is mixed with ethylene glycol at a concentration of 0.4% by weight, and then mixed with 40 W, 39 kHz, It is preferable from the viewpoint of polymerizability that the average particle size of the solid substance is reduced by 10% or more by performing the ultrasonic treatment for 1 minute, and it is more preferable that the average particle diameter is reduced by 20% or more. The upper limit of the reduction rate is not limited, but is usually 50% or less. The solvolysate of the titanium compound, the solvolysate obtained by adjusting the pH of the mixture with the silicon compound and the compound of (III) can be used by mixing these solvolytes if necessary. . Mixing can be carried out at any stage such as after solvolysis, after solid-liquid separation, after drying, after baking, and before pulverization, and the timing of mixing is not particularly limited. Examples of the mixing method include a method of mixing the solvolyzed product after solvolysis in a solvent and a method of mixing in a solid state after drying.

Preferred embodiments of the polyester production catalyst of the present invention include a solvolyzed product of a titanium compound and a solvolyzed product obtained by adjusting the pH of a mixture of a silicon compound and a compound of (III) to 4 or more. After being separated from the solvent, washed, dried and pulverized.

As an example of the catalyst for polyester production of the present invention obtained as described above, those represented by the following formula (1) can be mentioned.
(1) Formula TiaSibMc (OH) xOy (where M is an element selected from the group consisting of beryllium, magnesium, calcium, zinc, strontium, barium, boron, aluminum, gallium, manganese, cobalt, germanium, antimony, and phosphorus) A, b, and c indicate the atomic ratio of each element, x and y indicate the atomic ratio of a hydroxyl group and oxygen necessary to satisfy the valence of each component. good.)
Specifically, TiaSibMgC (OH) 4 (a + b) + 2c-2yOy is mentioned.

  The method for producing the polyester of the present invention is a method for producing a polyester by polycondensing a dicarboxylic acid component having an aromatic dicarboxylic acid or an ester-forming derivative thereof and a diol component through an esterification reaction or a transesterification reaction. In the production method, the above-mentioned catalyst for producing polyester is used, and the catalyst for producing polyester is preferably used as a polycondensation catalyst.

In the present invention, specific examples of the aromatic dicarboxylic acid or its ester-forming derivative include terephthalic acid, phthalic acid, isophthalic acid, dibromoisophthalic acid, sodium sulfoisophthalate, phenylenedioxydicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylketonedicarboxylic acid, 4,4'-diphenoxyethanedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, Aromatic dicarboxylic acids such as 6-naphthalenedicarboxylic acid or alkyl esters having about 1 to 4 carbon atoms of these aromatic dicarboxylic acids such as dimethyl terephthalate and dimethyl 2,6-naphthalenedicarboxylic acid, and halides And two of these On or as an ingredient. Of these, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and their ester-forming derivatives are preferred, and terephthalic acid and their ester-forming derivatives are particularly preferred.

The dicarboxylic acid component other than the aromatic dicarboxylic acid and its ester-forming derivative includes, for example, alicyclic dicarboxylic acids such as hexahydroterephthalic acid and hexahydroisophthalic acid, and succinic acid, glutaric acid, and adipic acid. Aliphatic dicarboxylic acids such as pimelic acid, suberic acid, azelaic acid, sebacic acid, undecadicarboxylic acid, dodecadicarboxylic acid, and the number of carbon atoms of these alicyclic dicarboxylic acids and aliphatic dicarboxylic acids
Alkyl esters, and halides and the like.

  Examples of the diol component include ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, decamethylene glycol, neopentyl glycol, 2-ethyl-2-butyl-1, Aliphatic diols such as 3-propanediol, diethylene glycol, polyethylene glycol and polytetramethylene ether glycol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethylol, 1,4-cyclohexanedimethylol , Alicyclic diols such as 2,5-norbornane dimethylol, and xylylene glycol, 4,4'-dihydroxybiphenyl, 2,2-bis (4'-hydroxy Aromatic diols such as phenyl) propane, 2,2-bis (4′-β-hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, bis (4-β-hydroxyethoxyphenyl) sulfonic acid, and Examples thereof include an ethylene oxide adduct and a propylene oxide adduct of 2,2-bis (4′-hydroxyphenyl) propane, and two or more of these may be used as a component. Among these, ethylene glycol and tetramethylene glycol are preferred, and ethylene glycol is particularly preferred.

Furthermore, for example, hydroxycarboxylic acids and alkoxycarboxylic acids such as glycolic acid, p-hydroxybenzoic acid and p-β-hydroxyethoxybenzoic acid, and stearyl alcohol, benzyl alcohol, stearic acid, benzoic acid, t-butylbenzoic acid , Monofunctional components such as benzoyl benzoic acid, and trifunctional or higher polyfunctional components such as tricarballylic acid, trimellitic acid, trimesic acid, pyromellitic acid, gallic acid, trimethylolethane, trimethylolpropane, glycerol, and pentaerythritol; One or more of these may be used as a copolymerization component. The process for producing the polyester of the present invention is a process for producing a polyester by esterification, melt polycondensation and, if necessary, subsequent solid phase polycondensation, and is basically based on a conventional polyester production process. That is, the dicarboxylic acid component and the diol component are reacted in an esterification reaction tank at a temperature of usually 240 to 280 ° C., preferably 250 to 270 ° C., usually 0.1 to 0, in the presence of an esterification catalyst if necessary. The esterification reaction is carried out for 1 to 10 hours under stirring at a pressure of 0.4 MPa, preferably 0.1 to 0.3 MPa, and the resulting polyester low molecular weight product as the esterification reaction product is transferred to the polycondensation tank. And in the presence of a polycondensation catalyst, usually at a temperature of 260 to 290 ° C., preferably 265 to 285 ° C., and gradually reduced from normal pressure to 1.3 × 10 ^{1 to} 1.3 × 10 ³ Pa. Preferably, the polycondensation is carried out by melt polycondensation for 1 to 20 hours with stirring under a reduced pressure of 6.7 × 10 ^{1 to} 6.7 × 10 ² Pa, and these are performed in a continuous system or a batch system.

Further, usually, the resin obtained by melt polycondensation is drawn out in a strand form from a discharge port provided at the bottom of the polycondensation tank, and cut with a cutter while cooling with water or after cooling with water, and is cut into a pellet, chip, or the like. Further, the granular material after the melt polycondensation is usually subjected to an inert gas atmosphere such as nitrogen, carbon dioxide, and argon, or a steam atmosphere, or a steam-containing inert gas atmosphere. After heating at a temperature of usually 60 to 180 ° C., preferably 150 to 170 ° C. to crystallize the surface of the resin granules, the mixture is heated under an inert gas atmosphere and / or 1.3 × 10 ^{1 to} 1.3. Under a reduced pressure of about × 10 ³ Pa, usually at a temperature just below the adhesion temperature of the resin to 80 ° C. lower, preferably 10 to 60 ° C. lower than the adhesion temperature, while flowing the particles so as not to stick together, etc. It is preferable that the solid phase polycondensation is carried out by heating for a time of usually 50 hours or less, and the solid phase polycondensation can further increase the degree of polymerization and reduce the reaction by-products such as acetaldehyde and low molecular oligomers. You can also.

Further, the resin obtained by the melt polycondensation or solid phase polycondensation as described above is usually subjected to a water treatment in which the resin is immersed in water at 40 ° C. or more for 10 minutes or more in order to deactivate the polycondensation catalyst. ,
Alternatively, a treatment such as a steam treatment in which the film is brought into contact with steam or a steam-containing gas at 60 ° C. or more for 30 minutes or more may be performed.
The time of addition of the polycondensation catalyst of the present invention may be at any time during slurry preparation with the raw material dicarboxylic acid component and diol component, at any stage of the esterification step, or at the initial stage of the melt polycondensation step. Good.
The method for adding the polyester production catalyst of the present invention may be in the form of powder, a solution or a slurry of a solvent such as ethylene glycol, and is not particularly limited.

The polyester production catalyst of the present invention is preferably added in an amount of 0.1 to 200 ppm as titanium with respect to the theoretical yield of the polyester resin. The polyester production catalyst of the present invention may be used in the presence of another polycondensation catalyst such as an antimony compound, a germanium compound, a cobalt compound, and a tin compound.
Further, in the present invention, an auxiliary agent and a stabilizer for preventing deterioration of the polyester can be used. Auxiliaries and stabilizers include phosphate esters such as trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, etc., methyl acid phosphate, ethyl acid phosphate, isopropyl acid. Examples include acidic phosphate esters such as phosphate, butyl acid phosphate, dibutyl phosphate, monobutyl phosphate, dioctyl phosphate, and phosphorus compounds such as phosphoric acid, phosphorous acid, and polyphosphoric acid.

  The auxiliaries and stabilizers can be supplied at the time of preparing the raw material slurry, at any stage of the esterification step and at the beginning of the melt polycondensation step. The auxiliaries and stabilizers are usually used in the range of 1 to 1000 ppm by weight of phosphorus based on the total polycondensation raw material. The temperature at which the solvolysis is carried out is usually 100C or lower, preferably 0-70C. The solvolysis time varies depending on the temperature, but is usually within 20 hours, preferably within 10 hours.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the following examples. In addition, the acid value used as an index of the intrinsic viscosity and the thermal stability used in Examples and Comparative Examples was measured as follows.
<Intrinsic viscosity ([η])> 0.50 g of a resin sample was mixed with phenol / 1,1,2,2-tetrachloroethane (weight ratio 1/1) at a concentration (c) of 1.0 g / dl. After dissolving at 110 ° C. for 20 minutes, the relative viscosity (η rel) with the undiluted solution was measured at 30 ° C. using an Ubbelohde capillary viscometer, and the ratio determined from the relative viscosity (η rel) -1. The ratio (ηsp / c) between the viscosity (ηsp) and the concentration (c) was determined. Similarly, when the concentration (c) was set to 0.5 g / dl, 0.2 g / dl, and 0.1 g / dl, The ratio (ηsp / c) was determined, and 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>
0.50 g of the resin sample was precisely weighed, collected in a test tube, added with 25 ml of benzyl alcohol, and dissolved by heating and stirring at 195 ° C. for 9 minutes. Thereafter, 2 ml of ethanol was added and the mixture was cooled. This solution was titrated with a 0.1N NaOH benzyl alcohol solution. The above operation was performed without using a polyester sample as a blank, and the acid value was calculated by the following formula.

Acid value (mol / ton) = (AB) × 0.1 × f / W The abbreviations are as follows.

A: amount of 0.1N NaOH required for titration (μl)
B: Blank titer (μl)
W: amount of polyester sample (g)
f: titer of 0.1N NaOH benzyl alcohol

<Average particle size>
The solid catalyst was mixed with ethylene glycol at a concentration of 0.4% by weight and measured with a laser diffraction / scattering particle size distribution analyzer LA-700 manufactured by Horiba, Ltd.

<Ultrasonic treatment>
The solid catalyst was mixed with ethylene glycol at a concentration of 0.4% by weight, and operated at 40 W, 39 kHz for 1 minute under the concentration conditions.

Example 1 <Preparation of catalyst>
300 ml of ion-exchanged water was weighed into a 1 L beaker, and after cooling the beaker in an ice bath, 20 ml of titanium tetrachloride (TiCl ₄ ) was added dropwise with stirring. The beaker was removed from the ice bath. 4.1 g of magnesium chloride hexahydrate (MgCl ₂ .6H ₂ O) was added and dissolved therein, and 22.2 g of tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ) was further added, followed by stirring and dispersion. Was. Subsequently, while stirring this beaker, 4N ammonia water was added dropwise until the pH of the liquid in the beaker became 7.4. The precipitate formed by the dropwise addition was filtered by suction, washed with water, dried at 80 ° C. under reduced pressure, and pulverized to 100 μm or less. The atomic ratio of Ti: Mg: Si prepared in this example is 60: 7: 33.

Example 2 <Molten polycondensation>
Melt polycondensation of the ethylene glycol solution of the catalyst produced in Example 1 in a reactor in which 156 g of an ethylene terephthalate low polymer produced by direct esterification using terephthalic acid and ethylene glycol as raw materials was dissolved at 260 ° C. It was added so as to be 50 ppm as a titanium atom with respect to the theoretical yield of the polyester resin at the time of completion. Then, while stirring the melt with a stirring blade, the temperature was gradually increased to 280 ° C. in 80 minutes, and the pressure of the reaction system was gradually decreased from normal pressure to 1.3 × 10 ² Pa in 60 minutes. After reaching 280 ° C. and a pressure of 1.3 × 10 ² Pa, the temperature and the pressure were kept constant.
112 minutes after the start of the pressure reduction, the stirring was stopped, and the polymerization 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-shaped polymer. This was cut into pellets. The time from the start of pressure reduction to the termination of polymerization (polymerization time), the intrinsic viscosity and the AV value of the obtained polymer are shown in Table 2 below.

Example 3 <Preparation of catalyst>
In Example 1, titanium tetrachloride (TiCl4) 4.1 ml, magnesium chloride hexahydrate (MgCl ₂ · 6H ₂ O) and 7.6 g, tetraethoxysilane _{(Si (OC 2 H 5)} 4)
Was changed to 40.8 g. The atomic ratio of Ti: Mg: Si prepared in this example is 14:14:72. When the average particle size of the obtained catalyst was measured, the results in Table 3 were obtained.

Example 4 <Molten polycondensation>
In Example 2, it carried out similarly except having used the ethylene glycol solution of the catalyst manufactured in Example 3 as a catalyst. Table 2 shows the obtained results.

Example 5 <Preparation of catalyst>
Example 3 was repeated in the same manner as in Example 3, except that water washing was changed to ethanol washing and 80 ° C. vacuum drying was changed to 40 ° C. vacuum drying. When the average particle size of the obtained catalyst was measured, the results in Table 3 were obtained.

Example 6 <Molten polycondensation>
In Example 2, a catalyst was prepared in the same manner as in Example 5, except that the ethylene glycol solution of the catalyst prepared in Example 5 was used, and titanium catalyst was added to the theoretical yield at the end of melt polycondensation so as to be 10 ppm as a titanium atom. . Table 2 shows the obtained results.

Example 7 <Preparation of catalyst>
In Example 5, titanium tetrachloride (TiCl4) 20.0 ml, zinc chloride 2.8g instead of magnesium chloride hexahydrate _{(MgCl 2 · 6H 2 O)} , tetraethoxysilane (Si (OC ₂ H _{5 4} ) The procedure was the same except that ₄ ) was changed to 22.2 g. The atomic ratio of Ti: Zn: Si prepared in this example is 60: 7: 33.

Example 8 <Molten polycondensation>
In Example 2, a catalyst was prepared in the same manner as in Example 7, except that the ethylene glycol solution of the catalyst prepared in Example 7 was used, and the catalyst was added in an amount of 10 ppm as a titanium atom with respect to the theoretical yield of the polyester resin at the end of the melt polycondensation. . Table 2 shows the obtained results.

Comparative Example 1 <Preparation of catalyst>
300 ml of ion-exchanged water was weighed into a 1 L beaker, and after cooling this beaker in an ice bath, 20.6 ml of titanium tetrachloride (TiCl ₄ ) was added dropwise with stirring. When stopped, the beaker was removed from the ice bath. 22.9 g of tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ) was added thereto, and the mixture was stirred and dispersed. Subsequently, while stirring this beaker, 4N ammonia water was added dropwise until the pH of the liquid in the beaker became 7.4. The precipitate formed by the dropwise addition was filtered by suction, washed with water, dried at 80 ° C. under reduced pressure, and pulverized to 100 μm or less. The Ti: Si atomic ratio prepared in this comparative example was 50:50, and the compound (III) was not used.

Comparative Example 2 <Preparation of catalyst>
300 ml of ion-exchanged water was weighed into a 1 L beaker, and after cooling the beaker in an ice bath, 35 ml of titanium tetrachloride (TiCl ₄ ) was added dropwise with stirring. The beaker was removed from the ice bath. 7.2 g of magnesium chloride hexahydrate (MgCl ₂ .6H ₂ O) was added thereto, and the mixture was stirred and dispersed. Subsequently, while stirring this beaker, 4N ammonia water was added dropwise until the pH of the liquid in the beaker became 7.4. The precipitate formed by the dropwise addition was filtered by suction, washed with water, dried at 80 ° C. under reduced pressure, and pulverized to 100 μm or less. The charged Ti: Mg atomic ratio of this comparative example is 90:10, and is an example in which the silicon compound (II) is not used. When the average particle size of the obtained catalyst was measured, the results in Table 3 were obtained.

Comparative Example 3 <Molten polycondensation>
Instead of the catalyst described in Example 1, an ethylene glycol solution of the catalyst prepared in Comparative Example 1 was added so as to be 50 ppm as a titanium atom with respect to the theoretical yield of the polyester resin at the end of the melt polycondensation. The procedure was performed in the same manner as in Example 1 except that the polymerization was stopped later. Table 2 shows the obtained results.

Comparative Example 4
Instead of the catalyst described in Example 1, an ethylene glycol solution of the catalyst prepared in Comparative Example 2 was added so that the theoretical yield of the polyester resin at the end of the melt polycondensation was 50 ppm as titanium atoms, and the pressure was reduced to 169 minutes. The procedure was performed in the same manner as in Example 1 except that the polymerization was stopped later. Table 2 shows the obtained results.

実施例２、４，６，８及び比較例３及び４の結果から明らかなように、本発明のポリエステル製造用触媒を使用することにより、重合速度が速く、又、得られるポリエステルの酸価が低く、結果としてポリエステルの熱安定が良好となる。

As is clear from the results of Examples 2, 4, 6, 8 and Comparative Examples 3 and 4, the use of the polyester production catalyst of the present invention makes it possible to increase the polymerization rate and reduce the acid value of the obtained polyester. Low, resulting in good thermal stability of the polyester.

Claims (11)

(1) a titanium atom, (2) a silicon atom, and (3) at least one selected from the group consisting of beryllium, magnesium, calcium, zinc, strontium, barium, boron, aluminum, gallium, manganese, cobalt, germanium, antimony, and phosphorus. A polyester production catalyst containing one kind of atom. At least (I) a solvolysate of a titanium compound, (II) a silicon compound, and (III) beryllium, magnesium, calcium, zinc, strontium, barium, boron, aluminum, gallium, manganese, cobalt, germanium, antimony and phosphorus. The catalyst for polyester production according to claim 1, which contains a solvolysate obtained by adjusting a mixture with a compound of at least one atom selected from the group consisting of: to a pH of 4 or more. The catalyst for producing a polyester according to claim 2, wherein the solvolysis is hydrolysis. The polyester production catalyst according to claim 2, wherein the titanium compound is a titanium halide. The polyester production catalyst according to any one of claims 2 to 4, wherein the compound (III) is a compound of at least one element selected from the group consisting of magnesium, zinc, aluminum, and phosphorus. The polyester production catalyst according to claim 5, wherein the compound (III) is a magnesium compound. The polyester production catalyst according to any one of claims 2 to 6, which is a solid product obtained by drying the solvolysis product. The polyester production catalyst according to claim 7, wherein the average particle size is 1 nm or more and 200 m or less. The polyester production catalyst according to any one of claims 1 to 8, which contains a magnesium atom and / or a zinc atom. The average particle diameter is reduced by 10% or more by subjecting the mixture to a 40 W, 39 kHz, 1 minute ultrasonic treatment after mixing with ethylene glycol at a concentration of 0.4% by weight. Catalyst for polyester production. When producing a polyester by polymerizing a dicarboxylic acid component having an aromatic dicarboxylic acid or an ester-forming derivative thereof as a main component and a diol component through an esterification reaction or a transesterification reaction, any one of claims 1 to 9 A method for producing a polyester, comprising using the catalyst for producing a polyester according to any of the above items.