JP2006265536A - Process for continuous production of polyester, polyester prepolyer granule and polyester - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a production method which can produce a high-molecular weight and high quality polyester for a container material in a relatively short period of solid phase polycondensation time without using a complex melt polycondensation reaction apparatus. <P>SOLUTION: The process for continuous production of polyester comprising an esterification process, a melt polycondensation process, a granulation process and a solid phase polycondensation process comprises adding succesively catalysts 1 and 2 which satisfy the followings (1)-(3) as a catalyst at optional two different locations prior to the granulation process and setting intrinsic viscosities of polyester prepolymer granules obtained by the granulation process and a polyester obtained by the solid phase polycondensation process to be respectively 0.18-0.35 dL/g and ≥0.70 dL/g. The above (1)-(3) are (1) an active ratio of catalyst 1 (K1) is ≥0.5, (2) an active ratio of catalyst 2 (K2) is less than 0.6 and (3) K1>K2 (an active ratio of catalyst is an indicator of a proportion of esterification reaction catalyst activity to the sum of an esterification reaction catalyst activity of a catalyst and a transesterification reaction catalyst activity of a catalyst). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for continuously producing polyester, and a production intermediate of the method, a relatively low molecular weight polyester prepolymer granular material suitable for solid phase polycondensation, and a polyester obtained by solid phase polycondensation thereof. About. In particular, the present invention relates to a continuous production method capable of simplifying a melt polycondensation reaction apparatus and producing polyester at a high speed.

  Polyesters typified by polyethylene terephthalate are excellent in mechanical properties, thermal properties, electrical properties, etc., so they are widely used in molded products such as fibers, films, sheets, bottles, etc. is doing.

  High molecular weight polyesters used as container materials for bottles and the like are usually subjected to melt polycondensation, solid phase polymerization through esterification and / or transesterification of dicarboxylic acid and / or its ester-forming derivative and diol. Manufactured by condensation.

  In the current mainstream production method, a relatively high molecular weight polyester prepolymer is obtained by melt polycondensation, and this is produced by solid-phase polycondensation. In order to obtain a relatively high molecular weight polyester prepolymer, In the final stage of melt polycondensation, a horizontal plug flow reactor equipped with a complicated stirring blade is used. Further, the solid phase polycondensation reaction usually takes a long time of more than 10 hours. In contrast, as a method for efficiently producing polyester without using an apparatus having a complicated structure as a melt polycondensation reaction vessel, for example, a polyester prepolymer having a relatively low molecular weight is obtained by melt polycondensation, and this is used as a solid phase. A method for producing a polyester used in the polycondensation process has also been proposed (see, for example, Patent Document 1). However, even in this case, it is still insufficient in that a relatively long solid phase polycondensation time is required.

  Patent Document 2 discloses that the solid-phase polycondensation rate depends on the amount of catalyst and the content of carboxyl end groups of the prepolymer. The amount of carboxyl end groups of the prepolymer is determined based on terephthalic acid and ethylene glycol in the esterification reaction. The amount of ethylene glycol added in excess of the initial charge at a later stage of the reaction, or the catalyst is added after partial vacuum is applied to the polycondensation process. However, this method is difficult to apply to a continuous production method of polyester, and is not always satisfactory in terms of polymerization rate.

  On the other hand, antimony compounds, germanium compounds, titanium compounds and the like have been known as catalysts for proceeding with polycondensation reactions, and tungsten compounds such as tungsten salts have been known as catalysts having a high polycondensation reaction rate. (For example, refer to Patent Document 3). However, even when a tungsten compound is used as a catalyst, the polymerization rate is still insufficient from the viewpoint of more efficient production.

By the way, the polycondensation reaction proceeds mainly by two kinds of reactions, ie, an esterification reaction between a carboxylic acid and an alcohol, and an ester exchange reaction (alcohol exchange reaction) between an ester bond and an alcohol. No attention has been paid to the relationship between the catalytic activity of the ester exchange reaction and the catalyst activity, and no technique has been known for improving the solid-phase polycondensation rate by adjusting the catalytic activity.
Japanese National Patent Publication No. 10-512608 JP-A-55-133421 Japanese Patent Publication No. 44-19554

  The present invention makes it possible to produce a high-molecular-weight, high-quality polyester having practicality as a container material or the like in a relatively short solid-phase polycondensation time without using a complicated melt polycondensation reaction apparatus, resulting in low cost. It is an object of the present invention to provide a method for producing polyester efficiently.

  It is another object of the present invention to provide a polyester prepolymer having a relatively low molecular weight suitable for the solid phase polycondensation.

As a result of intensive studies in view of the above problems, the inventors of the present invention produced a polyester prepolymer having a relatively low molecular weight by melt polycondensation, and a catalyst for producing a high molecular weight polyester by solid-phase polycondensation of the prepolymer. The present invention has found that the solid-phase polycondensation rate can be improved by adding two or more catalysts having a specific relationship in a specific range within a specific range to a specific stage of the polyester production process in a specific order. Reached.
That is, the gist of the present invention is (a) an esterification step in which an oligomer is obtained by esterifying a dicarboxylic acid component mainly composed of terephthalic acid and a diol component mainly composed of ethylene glycol, and (b) obtained. A melt polycondensation step in which a polyester prepolymer is obtained by subjecting the obtained oligomer to a melt polycondensation reaction, (c) a granulation step in which the obtained polyester prepolymer is granulated to obtain polyester prepolymer granules, and (d) obtained. In a method for continuously producing a polyester having a solid phase polycondensation step of obtaining a polyester by subjecting a polyester prepolymer granule to a solid phase polycondensation reaction, at least 2 satisfying the following (1) to (3) as a catalyst: Seed catalyst 1 and catalyst 2 are added sequentially to any two different locations prior to the granulation step (c), and in step (c) The intrinsic viscosity of the resulting polyester prepolymer granules is 0.18 dL / g or more and 0.35 dL / g or less, and the intrinsic viscosity of the polyester obtained in the solid phase polycondensation step (d) is 0.70 dL / g or more. (1) Activity ratio (K1) of catalyst 1 is 0.5 or more (2) Activity ratio (K2) of catalyst 2 is less than 0.6 (3) K1> K2
(Here, the catalyst activity ratio is an index of the ratio of the esterification reaction catalyst activity to the total of the esterification reaction catalyst activity and the transesterification catalyst activity of the catalyst, and is defined by the method described in the specification.) )
Exist.
Another gist is that the intrinsic viscosity is 0.18 dL / g or more and 0.35 dL / g or less, the terminal carboxyl group concentration is 30 equivalents / ton or less, the average particle size is 0.1 mm or more and 2.0 mm or less, tungsten element, And at least one element selected from an antimony element, a germanium element and a titanium element.

  According to the method of the present invention, a high-molecular-weight, high-quality polyester having utility as a container material such as a bottle is produced in a short solid-phase polycondensation time without using a complicated melt polycondensation reaction apparatus. As a result, it becomes possible to produce polyester efficiently at low cost.

  The description of the constituent requirements described below is an example (representative example) of an embodiment of the present invention, and is not specified by these contents.

  The method for continuously producing the polyester of the present invention comprises: (a) an esterification step in which an oligomer is obtained by esterifying a dicarboxylic acid component containing terephthalic acid as a main component and a diol component containing ethylene glycol as a main component; ) A melt polycondensation step for obtaining a polyester prepolymer by subjecting the obtained oligomer to a melt polycondensation reaction, (c) a granulation step for granulating the obtained polyester prepolymer to obtain polyester prepolymer granules, (d) It is premised on having a solid phase polycondensation step of obtaining a polyester by subjecting the obtained polyester prepolymer granules to a solid phase polycondensation reaction. Usually, prior to the step (a), a dicarboxylic acid component and a diol A slurrying step of mixing the components to obtain a slurry; Also, between the slurrying step and the step (a), a slurry transfer step for transferring the slurry to the esterification step, and between the steps (a) and (b), the oligomer obtained in the step (b) is melted. Between the oligomer transfer process which transfers to a condensation process, and the process (c) and (d), it has the prepolymer transfer process which transfers the obtained polyester prepolymer to a granulation process.

  In addition, each said transfer process connects each process before and behind with piping, and transfers the mixture and / or product (henceforth abbreviated as a product hereafter) of a front process to a back process continuously. Is done. As a method of transferring continuously, the pre-process, the transfer process and the post-process are installed in order, and the product of the pre-process is transferred using the height difference, and the pre-process is relatively higher than the post-process. Examples include a method of transferring the product using the pressure difference between the preceding and succeeding steps in the transfer step, a method of transferring the product of the previous step by installing a pump in the subsequent step, and the like. Among them, the method of transferring using a pump is preferable because it can accurately control the transfer amount and speed of the product in the previous step. In order to remove insoluble impurities and precipitates having a large particle size, a filter or the like can be installed in the transfer process.

  In the present invention, the dicarboxylic acid component containing terephthalic acid as a main component refers to a dicarboxylic acid component in which 95 mol% or more is a terephthalic acid component with respect to all dicarboxylic acid components used in the production of polyester, preferably 97 More than mol%. When the content of the terephthalic acid component is less than the above range, the heat resistance as a molded body such as a heat-resistant bottle tends to be inferior when the obtained polyester is formed into a molded body. Moreover, the diol component which has ethylene glycol as a main component means that an ethylene glycol component is 95% or more with respect to all the diol components used when manufacturing polyester, Preferably it is 97 mol% or more.

  Here, as the dicarboxylic acid component other than terephthalic acid, for example, phthalic acid, isophthalic acid, dibromoisophthalic acid, sodium sulfoisophthalate, phenylenedioxydicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 4,4′- Diphenyl ether dicarboxylic acid, 4,4′-diphenyl ketone dicarboxylic acid, 4,4′-diphenoxyethane dicarboxylic acid, 4,4′-diphenylsulfone dicarboxylic acid, aromatic dicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, hexa Alicyclic dicarboxylic acids such as hydroterephthalic acid and hexahydroisophthalic acid, and fats such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecadicarboxylic acid, and dodecadicarboxylic acid Group dicarboxylic acid, and the like.

In addition to diethylene glycol, diol components other than ethylene glycol include, for example, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, decamethylene glycol, neopentyl glycol, 2-ethyl-2- Aliphatic diols such as butyl-1,3-propanediol, polyethylene glycol, polytetramethylene ether glycol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethylol, 1,4-cyclohexane Alicyclic diols such as dimethylol and 2,5-norbornane dimethylol, and xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4′-hydroxy) Diol) propane, 2,2-bis (4′-β-hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, bis (4-β-hydroxyethoxyphenyl) sulfonic acid, and the like, and An ethylene oxide adduct or a propylene oxide adduct of 2,2-bis (4′-hydroxyphenyl) propane may be mentioned.
Trifunctional or higher functional compounds, for example, polycarboxylic acids such as trimellitic acid and pyromellitic acid and their anhydrides, and polyols such as trimethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol, hexanetriol, etc. In addition, it may be used as a copolymerization component as necessary for the purpose of adjusting the physical properties of polyesters from which hydroxycarboxylic acids such as malic acid and citric acid can be obtained.

In the production method of the present invention, at least two kinds of catalysts 1 and 2 satisfying the following (1) to (3) as catalysts are sequentially added to any two different places prior to the granulation step (c). There is a need.
(1) Activity ratio (K1) of catalyst 1 is 0.5 or more (2) Activity ratio (K2) of catalyst 2 is less than 0.6 (3) K1> K2
Here, the catalyst activity ratio is defined below.

<Activity ratio definition>
The catalyst activity ratio (K) is an index of the ratio of esterification reaction catalyst activity to the total of esterification reaction catalyst activity and transesterification reaction catalyst activity, and is calculated by the following formula.
K = 2 × (AV0−AV1) / (TEV0−TEV1)

  Here, AV0, TEV0, AV1, and TEV1 are respectively defined as follows.

(i) The target polyester raw material oligomer (however, the total terminal group concentration is 1600 ± 160 equivalent / ton and the terminal carboxy group concentration is 900 ± 100 equivalent / ton) is made into a molten state at a temperature of 270 ° C. The catalyst is added, the pressure is gradually reduced while stirring, and a melt polycondensation reaction is performed at 1.33 kPaA (10 torr). Here, kPaA indicates that the absolute pressure is expressed in kPa. Incidentally, it is practically difficult to adjust the total end group concentration and the terminal carboxy group concentration of the raw material oligomer to a single value, and the fluctuation of the catalyst activity ratio defined by the present invention due to slight fluctuation of the value is Since it can be ignored, the allowable variation is indicated by ± as described above.
(Ii) The time when 1.33 kPaA is reached is taken as the 0th minute, and samples at the 0th and 20th minutes are collected.
(Iii) The terminal carboxy group concentration and the total terminal group concentration are measured for both the 0th and 20th minute samples, and are denoted as AV0, TEV0, AV1, and TEV1, respectively.
AV0: Terminal carboxy group concentration of the 0th minute sample TEV0: Total terminal group concentration of the 0th minute sample AV1: Terminal carboxy group concentration of the 20th minute sample TEV1: Total terminal group concentration of the 20th minute sample

  The catalyst concentration of the raw material oligomer is adjusted for each catalyst type so that the intrinsic viscosity at 20 minutes falls within the range of 0.18 to 0.28 dL / g. In addition, it is practically difficult to adjust the intrinsic viscosity to a single value, and it is considered that the fluctuation of the catalyst activity ratio defined in the present invention due to slight fluctuation of the value is negligible. The inherent viscosity allowed to pass was 0.18 to 0.28 dL / g.

TEV (equivalent / ton) is calculated by the following formula.
Mn = (Intrinsic viscosity (dL / g) × 10000 / 7.55) ^{(1 / 0.685)}
TEV (equivalent / ton) = 2 × 1000 × 1000 / Mn
Here, Mn is a number average molecular weight. AV (equivalent / ton) is measured by titration.

<Addition position>
In the present invention, the sequential addition of at least two kinds of catalyst 1 and catalyst 2 to any two different locations prior to the granulation step (c) means that at least the catalyst 1 and the catalyst 2 are prior to the granulation step (c). As long as the catalyst 1 is added in this order from any different location, that is, as long as the catalyst 1 is added to the upstream side of the addition location of the catalyst 2, it is added to the same step, for example, at different positions in a plurality of esterification steps. May be added to different steps. Among them, the catalyst 1 is added to the esterification step (a), and the catalyst 2 is added to the step of transferring the oligomer obtained in the esterification step (a) to the melt polycondensation step (b) or subsequent steps. preferable. By adding the catalyst 1 and the catalyst 2 in this order, it becomes easy to obtain a polyester prepolymer having a low terminal carboxyl group concentration, and as a result, the solid-phase polycondensation rate tends to increase.
The activity ratio K1 of the catalyst 1 is 0.5 or more, preferably 0.55 or more, more preferably 0.60 or more, and particularly preferably 0.65 or more. On the other hand, the higher the value of K1, the better, but the upper limit is usually 1.0. If K1 is less than 0.5, the terminal carboxyl group concentration of the polyester prepolymer obtained after the melt polycondensation step is increased, and the solid phase polycondensation reaction rate is decreased, which is not preferable.
The activity ratio K2 of the catalyst 2 is less than 0.6, but preferably less than 0.55. The lower limit is usually 0.2, preferably 0.3. The activity ratio K2 of the catalyst 2 is related to the transesterification reaction activity effective for the solid phase polycondensation reaction. If K2 is 0.6 or more, the solid phase polycondensation reaction rate is decreased, which is not preferable.

  Further, the activity ratio K1 of the catalyst 1 and the activity ratio K2 of the catalyst 2 need to be in a relationship of K1> K2. When K1 ≦ K2, the feature of the present invention that the reaction rate in the solid phase polycondensation step is high is not exhibited, which is not preferable.

The catalyst 1 is not particularly limited as long as it has an activity ratio K1 of 0.5 or more and satisfies K1> K2, and examples thereof include a tungsten compound and a titanium compound. Among these, a tungsten compound is preferable.
Examples of the tungsten compound include paratungstic acid, metatungstic acid, tungstic acid, silicotungstic acid, phosphotungstic acid, and salts thereof. Examples of the salt include alkali metal salts such as ammonium salt, sodium salt, and potassium salt. Is mentioned. Among these, ammonium metatungstate, ammonium paratungstate, sodium tungstate, and tungstic acid are preferable, and ammonium metatungstate and ammonium paratungstate are particularly preferable.

Examples of titanium compounds include tetra-n-propyl titanate, tetra-i-propyl titanate, tetra-n-butyl titanate, tetra-n-butyl titanate tetramer, tetra-t-butyl titanate, acetyl-tri-i-propyl. Examples include tetraalkoxy titanates such as titanate, titanium acetate, titanium oxalate, and titanium chloride. Among them, tetra-i-propyl titanate and tetra-n-butyl titanate are preferable, and tetra-n-butyl titanate is particularly preferable.
Although the usage-amount of the catalyst 1 cannot generally be said with a catalyst seed | species, what is necessary is just to select suitably the density | concentration of the metallic element derived from the catalyst 1 in the polyester obtained normally from 0.5 weight ppm-500 weight ppm. The lower limit of the concentration is preferably 1 ppm by weight, and the upper limit is preferably 300 ppm by weight, more preferably 200 ppm by weight, and particularly preferably 100 ppm by weight. When two or more kinds of compounds containing different metals are used in combination as the catalyst 1, the concentration of the metal element is the total concentration of the different metal elements.

The catalyst 2 is not particularly limited as long as it has an activity K2 of less than 0.6 and satisfies K1> K2. For example, germanium compounds and antimony compounds are preferably used.
Examples of the germanium compound include germanium dioxide, germanium tetroxide, germanium hydroxide, germanium oxalate, germanium tetraethoxide, germanium tetra-n-butoxide, and among these, germanium dioxide is preferable. Examples of the antimony compound include diantimony trioxide, antimony pentoxide, antimony acetate, methoxyantimony, and the like, among which antimony trioxide is preferable.

Each of the catalyst 1 and the catalyst 2 may be a single compound or a combination of two or more compounds. Moreover, what combined the said 1 or more types of catalyst component and the other 1 or more types of promoter component may be used. Furthermore, the catalyst 2 may be a promoter component. Examples of the promoter component include alkali metal compounds, alkaline earth metal compounds, and silicon compounds.
In addition, the catalyst 2 is preferably a combination of a titanium compound and one or more promoter components. Among them, a titanium element and a silicon element, a titanium element and a magnesium element, or a titanium element, a magnesium element, and a phosphorus element. A catalyst containing three elements is preferred. Titanium compounds in this case include tetra-n-propyl titanate, tetra-i-propyl titanate, tetra-n-butyl titanate, tetra-n-butyl titanate tetramer, tetra-t-butyl titanate, titanium acetate, titanium oxalate, Examples include potassium titanium oxalate, sodium titanium oxalate, potassium titanate, sodium titanate, titanium chloride, titanium chloride-aluminum chloride mixture, among others, tetra-n-propyl titanate, tetra-i-propyl titanate, tetra-n- Titanium alkoxides such as butyl titanate are preferred. The co-catalyst components include silicate compounds such as tetramethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraphenoxysilane, and tetrabenzyloxysilane, silicon carboxylates such as silicon acetate, disiloxane, trisiloxane, and the like. Polysiloxane which is a hydrolyzate of siloxane compounds such as siloxane, dimethyldisiloxane and hexamethyldisiloxane, silanol compounds such as silanol, silanediol and phenylsilanetriol, silanolate compounds such as sodium tolphenylsilanol, or silicate compounds Examples thereof include silicon compounds such as alkoxysiloxane compounds and magnesium compounds such as magnesium acetate.

  The catalyst 2 is preferably a combination of an alkali metal compound and / or an alkaline earth metal compound and a phosphorus compound, and among them, a catalyst containing a magnesium element and a phosphorus element is preferable. Examples of the alkali metal compound and / or alkaline earth metal compound in this case include lithium acetate, sodium acetate, potassium acetate, potassium hydroxide, magnesium acetate, magnesium hydroxide, magnesium alkoxide, magnesium carbonate, calcium hydroxide, calcium acetate, Examples thereof include calcium carbonate. Examples of phosphorus compounds include orthophosphoric acid, orthophosphoric acid alkyl ester, ethyl acid phosphate, monoethyl acid phosphate, diethyl acid phosphate, dibutyl phosphate, triethylene glycol acid phosphate, phosphorous acid, phosphorous acid alkyl ester, and the like. Can be mentioned. Among these, a combination of magnesium acetate and ethyl acid phosphate and / or dibutyl phosphate is preferable.

Although the usage-amount of the catalyst 2 cannot generally be said depending on a catalyst seed | species, the density | concentration of the metal element derived from the catalyst 2 in the polyester obtained should just be suitably selected from 1 weight ppm-500 weight ppm normally. The lower limit of the concentration is preferably 5 ppm by weight, and the upper limit is preferably 300 ppm by weight, more preferably 250 ppm by weight.
When two or more kinds of compounds containing different metals are used in combination as the catalyst 2, the concentration of the metal element is the total concentration of the different metal elements.
In addition, in the manufacturing method of this invention, as long as the catalysts 1 and 2 are used, you may use the phosphorus compound etc. as a stabilizer.

  In the polyester production method of the present invention, the intrinsic viscosity of the polyester prepolymer obtained in the melt polycondensation step (b) is 0.18 dL / g or more and 0.35 dL / g or less. The lower limit is preferably 0.19 dL / g, more preferably 0.20 dL / g, and the upper limit is preferably 0.33 dL / g, preferably 0.32 dL / g. If it is less than the lower limit, it is disadvantageous in that the time required for the reaction in the solid phase polycondensation process, which is a subsequent process, becomes longer.If the upper limit is exceeded, the polycondensation reactor in the melt polycondensation process has plug flow properties. Therefore, complicated and expensive equipment such as a horizontal reactor is required, which is not suitable for the purpose of the present invention.

  Further, the terminal carboxyl group concentration of the polyester prepolymer is preferably 30 equivalent / ton or less, more preferably 20 equivalent / ton or less. If it is too large, the solid phase polycondensation rate tends to be slow. The lower limit is preferably as small as possible, and is therefore 0 equivalent / ton.

In the polyester production method of the present invention, the average particle size of the polyester prepolymer granules used in the solid phase polycondensation step is usually 0.1 mm or more and 2.0 mm or less. The lower limit is preferably 0.15 mm, more preferably 0.2 mm, and the upper limit is preferably 1.5 mm, more preferably 1.3 mm. If it is too small, the solid-phase polycondensation rate is fast, but it is powdery and handling properties such as transfer and metering are remarkably inferior. If it is too large, the specific surface area of the granular material tends to be small and the solid phase polycondensation rate may be small.
In addition, the intrinsic viscosity obtained according to the above is preferably 0.18 dL / g or more and 0.35 dL / g or less, the terminal carboxyl group concentration is 30 equivalents / ton or less, and the average particle size is 0.1 mm or more and 2.0 mm or less. A polyester prepolymer granular material comprising a tungsten element derived from the catalysts 1 and 2 and at least one element selected from an antimony element, a germanium element, and a titanium element is novel, and the polyester of the present invention It is useful as an intermediate product in the continuous production method.

  The intrinsic viscosity of the polyester obtained through the solid phase polycondensation step (d) of the present invention is 0.70 dL / g or more, preferably 0.75 dL / g or more. The upper limit is usually 1.10 dL / g, preferably 1.00 dL / g or less. If it is less than the lower limit, the mechanical strength of a molded article such as a bottle made from this material is inferior, which is not preferable. On the other hand, if the upper limit is exceeded, the melt viscosity may be too high during molding of the molded body, which may cause molding defects.

The method for continuously producing the polyester of the present invention comprises the steps of selecting the catalyst and supplying the catalyst, adjusting the reaction temperature, the reaction pressure, the reaction time, etc., and the intrinsic viscosity of the polyester prepolymer granules and the solid phase polycondensation step. The polyester is obtained in accordance with a known polyester production method except that the intrinsic viscosity of the polyester is as described above.
Hereinafter, manufacturing conditions will be described.
In the present invention, a raw material slurry is usually prepared by mixing a dicarboxylic acid component and a diol component. The raw slurry is prepared by mixing a dicarboxylic acid component containing terephthalic acid as a main component with a diol component containing ethylene glycol as a main component, a copolymer component used as necessary, and the molar ratio of the diol component to the dicarboxylic acid component. Is prepared as 1.0 to 2.0. This molar ratio is preferably 1.05 to 1.8, and more preferably 1.1 to 1.6.

  Subsequently, the prepared raw material slurry is transferred to an esterification step equipped with one or a plurality of esterification reaction tanks, and is subjected to an esterification reaction under normal pressure to pressure and under heating to obtain an oligomer which is a low molecular weight polyester. (Esterification process (a)).

As the reaction conditions in the esterification reaction, in the case of a single esterification reaction tank, the temperature and pressure are usually about 240 to 290 ° C., usually about 0 to 400 kPaG (0 to 4 kg / cm ² G), and under stirring. The reaction time is about 1 to 10 hours. In the case of a plurality of esterification reaction tanks, the reaction temperature in the first stage esterification reaction tank is usually 240 to 270 ° C., preferably 245 to 265 ° C., and the pressure is usually 5 to 300 kPaG (0.05 To 3 kg / cm ² G), preferably 10 to 200 kPaG (0.1 to ² kg / cm ² G), and the reaction temperature in the final stage is usually 250 to 290 ° C., preferably 255 to 280 ° C., and the pressure is usually 0 to 150 kPaG (0 to 1.5 kg / cm ² G), preferably 0 to 130 kPaG (0 to 1.3 kg / cm ² G). Here, kPaG represents relative pressure with respect to atmospheric pressure in kPa units.

  In the present invention, the esterification rate of the oligomer as the esterification reaction product (the ratio of the esterified by reacting with the diol component among all the carboxyl groups of the raw dicarboxylic acid component) is preferably 90% or more, More preferably, it is 94% or more.

  Subsequently, the obtained oligomer is transferred to a melt polycondensation step equipped with a polycondensation reaction tank and subjected to a melt polycondensation reaction under reduced pressure and heating (melt polycondensation step (b)). The melt polycondensation can be usually carried out in a single reaction tank of a complete mixing type equipped with a stirring blade.

  In the present invention, since the intrinsic viscosity of the polyester prepolymer obtained by melt polycondensation is as low as 0.35 dL / g or less, horizontal plug flow type second and third stages equipped with stirring blades that have been widely used in the past are used. No polycondensation reaction tank is required, and the melt polycondensation process is simplified and the equipment cost is reduced.

  The reaction conditions in the melt polycondensation are a temperature of 260 to 290 ° C, preferably 270 to 280 ° C, and a pressure of 100 to 0.01 kPaA, preferably 50 to 0.1 kPaA. The reaction time <residence time> is adjusted so that the intrinsic viscosity of the polyester prepolymer granules obtained by granulating the polyester prepolymer obtained in the melt polycondensation step is within the scope of the present invention. What is necessary is just to change with temperature and pressure, but it is usually about 0.5 to 3 hours.

  The polyester prepolymer obtained by the melt polycondensation is usually extracted in the form of a strand from an extraction port provided at the bottom of the polycondensation reaction tank, and is cooled with water or after water cooling, and then cut with a cutter to form polyester prepolymer particles. Let it be the body. Alternatively, while discharging and cooling into the water from the extraction port provided at the bottom of the polycondensation reaction tank, it is cut with a cutter that has a rotation axis in a direction substantially parallel to the discharge direction and is installed adjacent to the leading end of the extraction port. To make polyester prepolymer granules. Or it can also grind | pulverize with a grinder and it can also be set as the granule of a desired average particle diameter.

The polyester prepolymer granules obtained in the granulation step (c) are crystallized by being fluidized in a known method as necessary, for example, in an inert gas stream at 120 to 180 ° C. for 0.5 to 12 hours. After the drying treatment, a solid phase polycondensation reaction is performed (solid phase polycondensation reaction step (d)).
That is, in the solid phase polycondensation reaction in the method of the present invention, the lower limit of the temperature is usually 200 ° C., preferably 205 ° C., more preferably 208 ° C., and the upper limit of the temperature is 5 ° C. lower than the melting point of the polyester. It is preferably carried out in an inert gas atmosphere at a temperature 8 ° C. lower than the melting point, more preferably 10 ° C. lower than the melting point. Here, the melting point of the polyester means the highest temperature side in the DSC curve when the polyester is heated from 0 ° C. to 300 ° C. at a rate of 20 ° C./min using a differential scanning calorimeter. It is the temperature corresponding to the apex of the endothermic peak. The inert gas is a gas that has an oxygen concentration of 0.1% by volume or less, preferably 0.05% by volume or less, and does not substantially react with polyester. Examples of the gas that does not substantially react with the polyester include nitrogen, helium, neon, argon, xenon, carbon dioxide and the like, and nitrogen is preferably used mainly from the viewpoint of economy.

  If the solid phase polycondensation temperature is too low, the solid phase polycondensation rate is decreased, which is not preferable. If the solid phase polycondensation temperature is too high, the polyester particles are fused during the solid phase polycondensation, which is not preferable. When the average particle size of the polyester prepolymer particles is 1.0 mm or less, solid phase polycondensation is preferably performed in a fluidized bed. The solid phase polycondensation time may be set according to the target intrinsic viscosity so that the intrinsic viscosity of the obtained polyester is 0.70 dl / g or more, and is usually about 1 to 50 hours. The average particle size after the solid phase polycondensation is generally almost the same as the average particle size of the prepolymer before the solid phase polycondensation.

  The polyester obtained by the production method of the present invention can be formed into a bottle used for beverages or the like by stretch blow molding after forming a preform by injection molding or extrusion molding. Moreover, it can be made into a bottle by direct blow molding.

  In addition, the polyester obtained by the production method of the present invention can be used for various applications such as packaging materials by forming into a film or sheet by extrusion molding or stretch molding. Moreover, it can be set as a fiber by extrusion and stretch molding.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example, unless the summary is exceeded.

  In addition, various measurement methods in Examples and catalyst activity ratio measurements, methods for preparing catalyst activity ratio measurement raw material oligomers, and methods for preparing catalysts used in the examples are summarized below.

<Intrinsic viscosity IV (dL / g)>
About 0.25 g of a sample was dissolved in about 25 mL of a mixed solvent of phenol / 1,1,2,2-tetrachloroethane (weight ratio 1/1) to a concentration of 1.00 g / dL, and then 30 Cool and hold at 0 ° C, and measure the number of seconds of dropping only the sample solution and solvent with a concentration of 1.00 g / dL using a fully automatic solution viscometer ("2CH type DJ504" manufactured by Sentec Co., Ltd.) did.

IV = ((1 + 4 KHηsp) ^0.5 −1) / (2 KHC)
Here, ηsp = η / η0−1, η is the number of seconds that the sample solution is dropped, η0 is the number of seconds that the solvent is dropped, C is the sample solution concentration (g / dL), and KH is the Huggins constant. KH adopted 0.33.

  The dissolution conditions of the sample were 120 ° C. for 30 minutes when the sample was a prepolymer, and 140 ° C. for 30 minutes for the polyester after solid phase polycondensation.

<Esterification reaction rate (%)>
The sample is pulverized in a mortar, 1.0 g of the sample is precisely weighed in a beaker, 40 ml of dimethylformamide is added thereto, and the mixture is dissolved by heating at 180 ° C. for 20 minutes with stirring. Wash the walls and cool to room temperature. This solution was titrated with a 0.1N potassium hydroxide methanol solution using a complex pH electrode “EA-120” with a potentiograph “E-536 type” automatic titrator manufactured by Metrohm. A 0.1N potassium hydroxide methanol solution was prepared and standardized by the method of JIS K8006. The titration amount [A (ml)] obtained from the inflection point of the obtained titration curve, the factor [f1] of 0.1N potassium hydroxide methanol solution prepared, standardized and calculated by the above method, and the sample weight From [W (g)], the amount of free terminal carboxyl group [AV (equivalent / ton)] was determined by the following formula.

AV (equivalent / ton) = {A × f 1 × (1/10)} / W
Next, 0.3 g of a sample pulverized in a mortar is precisely weighed into an Erlenmeyer flask, and 20 ml of 0.5N KOH ethanol solution is added with a whole pipette, and further 10 ml of pure water is added, and a reflux condenser is set. The sample was hydrolyzed by heating and refluxing for 2 hours on a plate heater at 200 ° C. with occasional stirring. The sample solution at this time is transparent. After allowing to cool, titration was performed with 0.5N aqueous hydrochloric acid using phenolphthalein as an indicator. Here, the 0.5N KOH ethanol solution and the 0.5N hydrochloric acid aqueous solution were prepared and standardized by the method of JIS K8006. Also, phenolphthalein was used in which 1 g was dissolved in 90 ml of ethanol and the volume was adjusted to 100 ml with pure water. Moreover, it titrated also in the blank state which does not put a sample on the same conditions. In this case, the sample titration [Vs (ml)], the blank titration [Vb (ml)], the factor [f2] of the 0.5N hydrochloric acid aqueous solution prepared, standardized and calculated by the above method, and the sample From the weight [W (g)], the amount of carboxyl groups derived from all carboxylic acids [SV (equivalent / ton)] was determined by the following formula.

SV (equivalent / ton) = {(Vb-Vs) * f2 * (1/2)} / W
Next, the esterification rate (%) was determined from the obtained AV (equivalent / ton) and SV (equivalent / ton) by the following formula.

Esterification rate (%) = {(SV-AV) / SV} × 100
<Polyester terminal carboxyl group concentration (equivalent / ton)>
After pulverizing the sample, it was dried at 140 ° C. for 15 minutes in a hot air dryer, and 0.1 g was accurately weighed from the sample cooled to room temperature in a desiccator, taken into a test tube, 3 ml of benzyl alcohol was added, The solution was dissolved at 195 ° C. for 3 minutes while blowing dry nitrogen gas, and then 5 ml of chloroform was gradually added and cooled to room temperature. One to two drops of phenol red indicator were added to this solution, and titrated with a 0.1N sodium benzyl alcohol solution with stirring while blowing dry nitrogen gas, and the process was terminated when the color changed from yellow to red. Further, as a blank, the same operation was performed without a polyester resin sample, and the acid value was calculated by the following formula.

Terminal carboxyl group concentration (equivalent / ton) = (A−B) × 0.1 × f / W
[Where A is the amount of benzyl alcohol solution of 0.1N sodium hydroxide required for titration (μl), B is the amount of benzyl alcohol solution of 0.1N caustic soda required for titration with a blank ( μl), W is the amount (g) of the polyester resin sample, and f is the titer of a benzyl alcohol solution of 0.1N sodium hydroxide. ]
The titer (f) of 0.1N sodium hydroxide in benzyl alcohol solution was obtained by taking 5 ml of methanol in a test tube and adding 1 to 2 drops of phenol red ethanol solution as an indicator. Titrate with 0.4 ml of sodium benzyl alcohol solution to the color change point, then add 0.2 ml of 0.1N aqueous hydrochloric acid solution with known titer as standard solution, and add again benzyl hydrate of 0.1N sodium hydroxide. Titration to the color change point with an alcohol solution. (The above operation was performed while blowing dry nitrogen gas.) The titer (f) was calculated by the following equation.

Titer (f) = Titer of 0.1N aqueous hydrochloric acid × Amount of collected 0.1N aqueous hydrochloric acid (μl) / Titration of 0.1N sodium hydroxide in benzyl alcohol (μl)
<Average particle size of the polyester granules>
The value when the cumulative percentage in the cumulative distribution curve prepared by the dry sieving method described in JIS K0069 was 50% was defined as the average particle diameter.

<Measurement of catalyst activity ratio>
The “catalytic activity ratio (K)” is an index of the ratio of the esterification reaction catalytic activity to the total of the esterification reaction catalytic activity and the transesterification reaction catalytic activity,
K = 2 × (AV0−AV1) / (TEV0−TEV1)
Represented by Here, AV0, TEV0, AV1, and TEV1 are respectively defined as follows.

(I) The target polyester raw material oligomer (according to the following raw material oligomer preparation method. Total terminal group concentration is 1600 ± 160 equivalent / ton, terminal carboxyl group concentration is 900 ± 100 equivalent / ton) with stirring for 90 minutes. The temperature is raised from room temperature to 270 ° C. over a period of 30 minutes and held at 270 ° C. for 30 minutes to bring it into a molten state. The pressure is reduced to 33 kPaA (10 torr) and a melt polycondensation reaction is performed.
(Ii) The time when 1.33 kPaA is reached is taken as the 0th minute, and samples at the 0th and 20th minutes are collected.
(Iii) The terminal carboxyl group concentration and the total terminal group concentration are measured for both samples at 0 minutes and 20 minutes, and are defined as AV0, TEV0, AV1, and TEV1, respectively.
AV0: Terminal carboxy group concentration of the 0th minute sample TEV0: Total terminal group concentration of the 0th minute sample AV1: Terminal carboxy group concentration of the 20th minute sample TEV1: Total terminal group concentration of the 20th minute sample

  The catalyst concentration of the raw material oligomer is adjusted for each catalyst type so that the intrinsic viscosity at 20 minutes falls within the range of 0.18 to 0.28 dL / g.

TEV (equivalent / ton) is calculated by the following formula.
Mn = (Intrinsic viscosity (dL / g) × 10000 / 7.55) ^{(1 / 0.685)}
TEV (equivalent / ton) = 2 × 1000 × 1000 / Mn
It is calculated by the following formula. Here, Mn is a number average molecular weight.

  AV (equivalent / ton) is measured by the above-mentioned polyester terminal carboxyl group concentration measurement method.

(Method for preparing raw material oligomer for measuring catalyst activity ratio)
100 parts by weight of bis- (β-hydroxyethyl) terephthalate was charged in a reactor equipped with a stirrer, a separation tower, and a continuous extraction apparatus, melted in a nitrogen atmosphere, maintained at a temperature of 260 ° C. and a pressure of 100 kPaG, terephthalic acid: ethylene A glycol (= 1: 1.5 molar ratio) slurry is continuously charged at 30 parts by weight / hour so that the average residence time is 6 hours, and the esterification reaction is carried out while distilling off the water to be purified from the separation tower. The raw material oligomer was obtained by continuously extracting and cooling.

  The oligomer discharged from 20 to 25 hours after the start of slurry charging was cooled and pulverized, and subjected to a catalyst activity ratio measurement experiment.

  The oligomerization rate of this oligomer was 91.9%, the terminal carboxyl group concentration was 834 equivalent / ton, and the total end group concentration was 1620 equivalent / ton.

<Preparation of ethylene glycol solution of ammonium metatungstate>
To an Erlenmeyer flask weighing 29.168 g of ethylene glycol, 0.832 g of ammonium metatungstate concentrated aqueous solution (concentration of tungsten atoms is 40% by weight) was dropped and mixed thoroughly to obtain 1.1% by weight as tungsten atoms. An ethylene glycol solution of ammonium metatungstate having a concentration of 2 was prepared.

<Preparation of titanium-silica mixed catalyst>
While stirring, 2.2 g of tetraethoxysilane was dropped into a flask in which 200 mL of ethylene glycol was weighed and mixed well. A titanium-silica mixed catalyst in which 0.7 g of tetra-n-butyl titanate was added dropwise to this mixed solution while stirring, and again thoroughly mixed, so that the mixing ratio of titanium and silicon was 16:46 (weight ratio). Was prepared.

<Preparation of titanium-magnesium-phosphorus synthesis catalyst>
Put 60.72 g of magnesium acetate tetrahydrate into a 1 L Erlenmeyer flask with a stopper, add 360 g of absolute ethanol and stir for 30 minutes, then add 96.26 g of tetra-n-butyl titanate and stir for 20 minutes. To obtain a homogeneous solution. Next, with vigorous stirring, monoethyl acid phosphate (JAMP-2 manufactured by Johoku Chemical Industry Co., Ltd., purity 72.6% by weight, diethyl acid phosphate 14.5% by weight, containing orthophosphoric acid 13.0% by weight) is added. It was added over 30 minutes to obtain a slightly cloudy solution. This solution was transferred to a 1 L eggplant flask, and ethanol was distilled off under reduced pressure at an oil bath temperature of 80 ° C. until the content was 322.2 g. Next, 389.25 g of ethylene glycol was added under normal pressure of nitrogen and mixed for 15 minutes to prepare a uniform solution. Next, the low boiling point substance was removed by treating under reduced pressure of 1.33 kPa (10 Torr) for 40 minutes to obtain 508.0 g of a pale yellow polycondensation catalyst solution (titanium-magnesium-phosphorus synthesis catalyst). .
The pH of this solution was 5.4, and it was stable as a homogeneous solution. The concentrations of titanium, magnesium and phosphorus were 2.6 ppm by weight, 1.4 ppm by weight and 0.9 ppm by weight, respectively.

Example 1
A slurry preparation tank having an agitator, an ethylene glycol charging pipe and a terephthalic acid charging pipe; a pipe for transferring the slurry to the first esterification tank; an agitator, a separation tower, a raw material receiving port, a catalyst charging pipe and a reactant transfer pipe Completely mixed type first and second esterification reaction tanks; piping for transferring esterification reaction products (oligomers) to a melt polycondensation tank (provided with catalyst charging piping); stirrer, separation tower, oligomer receiving port, catalyst A polyester prepolymer was produced using a continuous production apparatus for a polyester prepolymer equipped with a fully mixed melt polycondensation tank having a feed pipe; a polyester prepolymer extraction pipe (provided with a catalyst feed pipe). All reactions were performed under a nitrogen atmosphere.

  First, 450 parts by weight of a raw material oligomer obtained according to the method for preparing a raw material oligomer for measuring the catalyst activity ratio is charged into a first esterification reaction tank and melted at a temperature of 262 ° C. In addition, ethylene glycol with respect to terephthalic acid was charged into a slurry preparation tank so as to have a molar ratio of 1.5, and stirred to obtain a slurry (slurry process). Then, under a pressure of 96 kPaG, a terephthalic acid phthalic acid / ethylene glycol (1: 1.5 molar ratio) slurry was continuously added to the first esterification tank at 135 parts by weight / hour so as to have an average residence time of 4.5 hours. Charged (slurry transfer process). At the same time, the ethylene glycol solution of ammonium metatungstate prepared above as catalyst 1 (concentration: 1.1% by weight as tungsten atoms) from the gas phase part of the first esterification reaction tank as tungsten against the resulting polyester An amount of 80 ppm by weight was continuously added, an esterification reaction was carried out while distilling off the water produced from the separation tower (esterification step), and the water was continuously extracted and transferred to the second esterification reaction tank. The esterification reaction was carried out in a second esterification reaction tank at a temperature of 260 ° C. and a pressure of 5 kPaG with a residence time of 1.5 hours (esterification process), and continuously transferred to a melt polycondensation tank through a transfer pipe (oligomer transfer process). ). Antimony with respect to polyester from which an ethylene glycol solution of diantimony trioxide (concentration: 1.8% by weight as antimony atom concentration) is obtained as catalyst 2 to the transfer pipe from the second esterification reaction tank to the polycondensation tank. As an amount, 209 ppm by weight was continuously added.

Reaction is performed at a pressure of 2.5 kPaA in a polycondensation tank, a temperature of 273 ° C. and a residence time of 1.0 hour (melt polycondensation process), and the resulting polyester prepolymer is extracted through a pipe (prepolymer transfer process) and cooled and solidified. did.
By crushing the solidified prepolymer with a sample mill (SK-M2 type manufactured by Kyoritsu Riko Co., Ltd.) and sieving it, an average particle diameter of 0.25 mm which passes 350 μm of JIS standard but does not pass 150 μm. A prepolymer granule was obtained (granulation step).

  An inert oven (IPHH-201M type manufactured by Tabai Espec Co., Ltd.) having an internal gas temperature of 180 ° C. with 18 g of this prepolymer granular body placed on a stainless steel bat having a bottom surface of 130 mm × 170 mm and a depth of 30 mm. ), And the crystallization treatment was performed for 2 hours at a flow rate of nitrogen of 50 NL / min and a temperature of 180 ° C. flowing through the inert oven. Here, NL is a gas volume (L) at 0 ° C. and 101.3 kPaG. 2 g of the crystallized polyester prepolymer granules are uniformly placed on the stainless steel bat, put in the inert oven having an internal gas temperature of 50 ° C., and the flow rate of nitrogen flowing through the inert oven is adjusted. 50 NL / min, the temperature was raised from 50 ° C. to 210 ° C. over 30 minutes, held at 210 ° C. for 20 minutes, then heated to 230 ° C. at a rate of 0.5 ° C./min and predetermined at 230 ° C. By maintaining the time, solid phase polycondensation was performed (solid phase polycondensation step).

  The intrinsic viscosity of the PET obtained when the solid-phase polycondensation time was 2 hours, with the retention time after reaching 230 ° C. being the solid-phase polycondensation time, was measured.

  Table 1 shows the catalyst activity ratio of the catalysts 1 and 2, the obtained polyester prepolymer, and the physical properties of the polyester after solid phase polycondensation.

(Example 2)
In Example 1, an ethylene glycol solution of orthophosphoric acid (concentration: 1.6% by weight as phosphorus atom) was added from the portion where antimony trioxide was added to the transfer pipe from the second esterification reaction tank to the polycondensation tank. The same procedure as in Example 1 was conducted except that an amount of 12 ppm by weight as phosphorus was continuously added to the polyester obtained from the upstream side. The results are shown in Table 1.

(Example 3)
In Example 1, the titanium-silica mixed catalyst prepared above in place of the ethylene glycol solution of diantimony trioxide was continuously added in an amount of 16 ppm by weight as titanium and 46 ppm by weight as silica with respect to the obtained polyester. The procedure was the same as in Example 1 except that the addition was performed. The results are shown in Table 1.

Example 4
In Example 3, instead of the ethylene glycol solution of ammonium metatungstate, an ethylene glycol solution of tetra-n-butyl titanate (concentration: 0.15% by weight as titanium atom) was used as titanium with respect to the resulting polyester at 4 ppm by weight. The same procedure as in Example 3 was conducted except that the amount to be added was continuously added. The results are shown in Table 1.

(Example 5)
In Example 1, it carried out like Example 1 except having changed the addition location of the ethylene glycol solution of diantimony trioxide to the gaseous-phase part of a 2nd esterification reaction tank. The results are shown in Table 1.

(Example 6)
In Example 1, it carried out similarly to Example 1 except having changed the addition location of the ethylene glycol solution of diantimony trioxide to the prepolymer extraction piping after melt polycondensation reaction. The results are shown in Table 1.

(Example 7)
In Example 6, instead of an ethylene glycol solution of ammonium metatungstate, an ethylene glycol solution of tetra-n-butyl titanate (concentration: 0.15% by weight as titanium atom) was used as titanium with respect to the obtained polyester as 8% by weight. The amount of ppm was continuously added, instead of ethylene glycol solution of diantimony trioxide, ethylene glycol solution of magnesium acetate tetrahydrate (concentration: 0.040 wt% as magnesium atom)) and ethyl acid phosphate 8 ppm by weight as magnesium and 6 ppm by weight as phosphorus with respect to the polyester prepolymer from which a mixed solution (magnesium acetate-ethyl acid phosphate mixed catalyst) of ethylene glycol solution (concentration: 0.030 wt% as phosphorus atom) is obtained. Except that the addition amounts continuously conducted in the same manner as in Example 6. The results are shown in Table 1.

(Example 8)
In Example 7, instead of the magnesium acetate-ethyl acid phosphate mixed catalyst, an ethylene glycol solution of magnesium acetate tetrahydrate (concentration: 0.030 wt% as magnesium atom) and an ethylene glycol solution of dibutyl phosphate (concentration: phosphorus atom) 0.040 wt% as a mixture (magnesium acetate-dibutyl phosphate mixed catalyst) is obtained, except that 4 wt ppm as magnesium and 5 wt ppm as phosphorus are continuously added to the polyester prepolymer. Was carried out in the same manner as in Example 7. The results are shown in Table 1.

Example 9
In Example 7, the addition amount of the ethylene glycol solution of tetra-n-butyl titanate added to the first esterification tank was changed to an amount of 4 ppm by weight as titanium with respect to the polyester obtained, and magnesium acetate-ethyl In place of the acid phosphate mixed catalyst, titanium, magnesium, and the polyester prepolymer from which the ethylene glycol diluted solution (concentration: 0.020% by weight as titanium atom) of the titanium-magnesium-phosphorus synthesis catalyst prepared above is obtained. The same operation as in Example 7 was conducted except that amounts of 4 ppm by weight, 2 ppm by weight, and 3 ppm by weight were successively added as phosphorus. The results are shown in Table 1.

(Comparative Example 1)
The same procedure as in Example 1 was conducted except that an ethylene glycol solution of diantimony trioxide was not added. The results are shown in Table 1.
Since no catalyst component corresponding to the catalyst 2 was added, the solid phase polycondensation reaction was slow.

(Comparative Example 2)
The same procedure as in Example 2 was performed except that an ethylene glycol solution of ammonium metatungstate was not added. The results are shown in Table 1.
Since the catalyst component corresponding to catalyst 1 was not added, the AV of the prepolymer was high, and the solid phase polycondensation reaction rate was low.

(Comparative Example 3)
In Example 1, the addition location of the ethylene glycol solution of ammonium metatungstate was replaced with the addition location of the ethylene glycol solution of diantimony trioxide of Example 1, and the addition location of the ethylene glycol solution of diantimony trioxide was changed to the meta of Example 1. The same procedure as in Example 1 was performed except that the addition location of the ethylene glycol solution of ammonium tungstate was changed. The results are shown in Table 1.
Although two types of catalysts were used, the addition order was different from that of the present invention, and in this example in which the activities of the catalyst 1 and the catalyst 2 were reversed, the solid phase polycondensation reaction rate was low.

(Comparative Example 4)
In Example 1, it carried out like Example 1 except having changed the ethylene glycol solution of diantimony trioxide to the ethylene glycol solution of tetra-n-butyl titanate. In this example in which the catalyst activity ratio of the catalyst component corresponding to the catalyst 2 is high, the solid phase polycondensation reaction rate was low.

* Catalyst W: Ammonium metatungstate Ti: Tetrabutyl titanate Sb: Antimony trioxide Ti / Si: Titanium-silica mixed catalyst Mg / EAP: Magnesium acetate-ethyl acid phosphate mixed catalyst Mg / DBP: Magnesium acetate-dibutyl phosphate mixed Catalyst Ti / Mg / P: Titanium-magnesium-phosphorus synthesis catalyst * addition position 1Es: First esterification tank 2Es: Second esterification tank MSP transfer pipe: Transfer from the second esterification tank to the melt polycondensation tank Piping PP transfer pipe: Prepolymer extraction pipe after melt polycondensation reaction While the present invention has been described in detail and with reference to particular embodiments, various changes and modifications may be made without departing from the spirit and scope of the invention. It will be apparent to those skilled in the art that they can be added.

  According to the present invention, a high-molecular-weight, high-quality polyester having utility as a packaging material such as bottles and films can be produced in a relatively short solid-phase polycondensation time without using a complicated melt polycondensation reaction apparatus. Can contribute to the improvement of polyester productivity.

Claims (10)

(A) an esterification step in which an oligomer is obtained by esterifying a dicarboxylic acid component containing terephthalic acid as a main component and a diol component containing ethylene glycol as a main component; and (b) a melt polycondensation reaction is performed on the obtained oligomer. A melt polycondensation step for obtaining a polyester prepolymer, (c) a granulation step for granulating the obtained polyester prepolymer to obtain a polyester prepolymer granule, and (d) a solid phase of the obtained polyester prepolymer granule. In a method for continuously producing a polyester having a solid phase polycondensation step for obtaining a polyester by polycondensation reaction, at least two kinds of catalysts 1 and 2 satisfying the following (1) to (3) are used as catalysts: The polyester pre-sequentially added to any two different places prior to the granulation step (c) and obtained in the step (c) Polyester characterized in that the intrinsic viscosity of the remer granule is 0.18 dL / g or more and 0.35 dL / g or less, and the intrinsic viscosity of the polyester obtained in the solid phase polycondensation step (d) is 0.70 dL / g or more. Continuous manufacturing method.
(1) Activity ratio (K1) of catalyst 1 is 0.5 or more (2) Activity ratio (K2) of catalyst 2 is less than 0.6 (3) K1> K2
(Here, the catalyst activity ratio is an index of the ratio of the esterification reaction catalyst activity to the total of the esterification reaction catalyst activity and the transesterification catalyst activity of the catalyst, and is defined by the method described in the specification.) )   The terminal carboxyl group concentration of the polyester prepolymer granules obtained in the granulation step (c) is 30 equivalents / ton or less, and the average particle size is 0.1 mm or more and 2.0 mm or less. The continuous manufacturing method of polyester as described.   The method for continuously producing a polyester according to claim 1 or 2, wherein the catalyst 1 is at least one compound selected from the group consisting of a tungsten compound and a titanium compound.   The continuous production of polyester according to claim 3, wherein the tungsten compound is at least one compound selected from the group consisting of paratungstic acid, metatungstic acid, tungstic acid, silicotungstic acid, phosphotungstic acid, and salts thereof. Method.   The method for continuously producing a polyester according to claim 3, wherein the titanium compound is at least one compound selected from the group consisting of tetra-n-butyl titanate and tetra-i-propyl titanate.   The method for continuously producing a polyester according to any one of claims 1 to 5, wherein the catalyst 2 is at least one compound selected from the group consisting of an antimony compound and a germanium compound.   The method for continuously producing a polyester according to any one of claims 1 to 5, wherein the catalyst 2 contains titanium element and silicon element, titanium element and magnesium element, or magnesium element and phosphorus element.   The addition location of the catalyst 1 is the esterification step (a), and the addition location of the catalyst 2 is the step of transferring the oligomer obtained in the esterification step (a) to the melt polycondensation step (b) or later. The method for continuously producing a polyester according to any one of claims 1 to 7, wherein:   Intrinsic viscosity is 0.18 dL / g or more and 0.35 dL / g or less, terminal carboxyl group concentration is 30 equivalent / ton or less, average particle size is 0.1 mm or more and 2.0 mm or less, tungsten element and antimony element, A polyester prepolymer granular material comprising at least one element selected from a germanium element and a titanium element. A polyester having an intrinsic viscosity of 0.70 dL / g or more obtained by subjecting the polyester prepolymer granules of claim 9 to a solid phase polycondensation reaction.