WO2009128318A1

WO2009128318A1 - Aromatic polyester resin and method of producing the same

Info

Publication number: WO2009128318A1
Application number: PCT/JP2009/055152
Authority: WO
Inventors: 賢鈴木; 淳治松村; 秀一松村
Original assignee: 大和製罐株式会社; 学校法人慶應義塾
Priority date: 2008-04-17
Filing date: 2009-03-17
Publication date: 2009-10-22
Also published as: JP5593219B2; JPWO2009128318A1

Abstract

Provided is an aromatic polyester resin which contains only a small amount of metallic impurities, exhibits relatively excellent thermal properties and mechanical properties and has a high molecular weight. Also provided is a method of producing an aromatic polyester resin having a high molecular weight through a process with low environmental burden wherein a hydrolase is employed as a polymerization catalyst. An aromatic polyester resin, which contains a low amount of metallic impurities, exhibits relatively excellent thermal properties and mechanical properties and has a high molecular weight, can be obtained by using a dicarboxylic acid component comprising terephthalic acid, naphthalenedicarboxylic acid or a derivative thereof and a diol component while selecting the kinds of the monomer components employed and the composition ratio thereof so that a polyester resin can be synthesized under such environment as not impairing the catalytic activity of a hydrolase, using as a polymerization catalyst a hydrolase capable of showing a sufficient catalytic activity for these components, and controlling the temperature conditions during the polycondensation or preliminarily preparing an ester oligomer and then using the same in polycondensation.

Description

Aromatic polyester resin and method for producing the same

Related applications

This application claims the priority of Japanese Patent Application No. 2008-107743 filed on Apr. 17, 2008, and is incorporated herein.

The present invention relates to a high molecular weight aromatic polyester resin having a low content of metal impurities and relatively excellent in thermal properties and mechanical properties, and a method for producing an aromatic polyester resin, which has a lower environmental impact. Related to improvements.

Polyesters most widely used industrially in modern society are aromatic polyesters represented by polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and the like. A major factor in which aromatic polyesters are widely used in this way is that they exhibit excellent thermal properties and mechanical properties due to the aromatic dicarboxylic acid skeleton.

Conventional aromatic polyester resins are generally produced by adding an aromatic dicarboxylic acid or a derivative thereof and a diol component and reacting with a heavy metal catalyst. Here, in order to obtain a high molecular weight polyester, it is necessary to make the ratio of the number of functional groups of carboxylic acid and alcohol present in the reaction system close to 1: 1. For this purpose, the polymerization proceeds while the excess of the diol charged excessively with respect to the dicarboxylic acid component is distilled out of the reaction system at a high temperature of 200 ° C. or higher and high vacuum, and finally the functional The high molecular weight is achieved by bringing the ratio of groups close to 1: 1, which is a feature of the above-mentioned industrial aromatic polyester resin production method.

However, with regard to such a conventional method for producing an aromatic polyester resin, for example, (1) energy-consuming type, (2) environmental pollution caused by metal catalyst residue, (3) mixed metal catalyst Many problems have been pointed out, such as the residue causing a decrease in the performance of the polyester resin.

One solution to these problems is to use an immobilized enzyme catalyst instead of a metal catalyst as a polymerization catalyst in the production of a polyester resin. This makes it possible to polymerize under relatively mild conditions, which not only results in an energy-saving manufacturing process, but also enables removal of catalyst residues, thus preventing environmental contamination and resin performance degradation. Can do. There have been many reports on a method for producing polyester using an enzyme as a polymerization catalyst, and an example of obtaining a high molecular weight resin that can be used as a structural material has also been reported (for example, see Non-Patent Document 1). However, most of the reports of polyesters produced using enzyme catalysts are aliphatic polyesters that are generally inferior in heat resistance and mechanical strength as compared with aromatic polyesters.

Although several methods for producing polyalkylene terephthalate, which is an aromatic polyester, using an enzyme catalyst have been reported (for example, see Non-Patent

Documents

2 and 3 and Patent Document 1), the average molecular weight of the obtained aromatic polyester is All are less than 20,000, and it is estimated that they are not usable as a structural material. As a cause of this, a hydrolase usually used as a polyester polymerization catalyst is one that degrades an ester bond originally composed of a fatty acid and an aliphatic alcohol, and therefore has a weak catalytic action on aromatic compounds. Therefore, it has been considered impossible to obtain a high molecular weight aromatic polyester resin.

On the other hand, with respect to polyalkylene isophthalate, which is a kind of aromatic polyester, a polyester resin having a relatively high molecular weight has been obtained by enzyme-catalyzed polymerization (see, for example, Non-Patent Document 4). However, this polyalkylene isophthalate resin is generally inferior in heat resistance as compared with the corresponding polyalkylene terephthalate resin and polyalkylene naphthalate resin. In addition, regarding aromatic polyester resins containing terephthalic acid or naphthalenedicarboxylic acid such as polyalkylene terephthalate and polyalkylene naphthalate in the polyester skeleton, examples of high molecular weight polymers obtained by enzyme-catalyzed polymerization are still reported. It has not been.

Patent No. 3690028

The present invention has been made to solve the above-mentioned problems, and its object is to have a high molecular weight aromatic polyester resin having a low content of metal impurities and relatively excellent thermal and mechanical properties. Another object of the present invention is to provide a method for producing a high molecular weight aromatic polyester resin by an environmentally low load process using a hydrolase as a polymerization catalyst.

In order to solve the above-mentioned problems, the present inventors have conducted intensive research. High-molecular-weight aromatic polyester with a low content of metal impurities and relatively excellent thermal and mechanical properties by an environmentally low-load synthetic process carried out under relatively mild conditions. It was found that a resin was obtained. More specifically, a hydrolase that exhibits sufficient catalytic activity for aromatic compounds is selected, and the catalytic activity of the hydrolase is selected by appropriately selecting the type of monomer component to be used and its blending ratio. After designing the composition of the polyester resin that can be synthesized in an environment that does not damage the resin, adjust the temperature conditions during polycondensation, or prepare an ester oligomer in advance and use it for polycondensation Thus, it has been found that a high molecular weight aromatic polyester which has been considered impossible in the past can be produced using a hydrolase, and the present invention has been completed.

That is, the aromatic polyester resin according to the present invention is obtained by polymerizing a dicarboxylic acid component and a diol component containing terephthalic acid or naphthalenedicarboxylic acid, or a derivative thereof by the catalytic action of a hydrolase, The average molecular weight is 20000 or more.

In addition, the aromatic polyester resin preferably has a melting point of less than 170 ° C. In the aromatic polyester resin, the hydrolase is preferably a lipase, and particularly preferably an immobilized lipase in which the lipase is immobilized on a carrier. The aromatic polyester resin preferably contains substantially no metal conventionally used as a polymerization catalyst for polyester production, such as antimony, titanium, germanium, aluminum, zinc, tin, zirconium, magnesium and manganese. is there.

Moreover, the method for producing an aromatic polyester resin according to the present invention uses a dicarboxylic acid component containing terephthalic acid or naphthalenedicarboxylic acid, or a derivative thereof, and a diol component, in the presence of a hydrolase, and has a weight average molecular weight. An ester oligomer production process for producing a chain or cyclic ester oligomer mixture of less than 20,000, and an ester oligomer mixture obtained by the above process are further polycondensed in the presence of a hydrolase to give a fragrance having a weight average molecular weight of 20000 or more. And a polyester resin polymerization step for producing a group polyester resin.

Further, in the method for producing an aromatic polyester resin, the ester oligomer production step comprises reacting terephthalic acid or naphthalenedicarboxylic acid, or a dicarboxylic acid component containing a derivative thereof and a diol component in the presence of a hydrolase. A first heating step of heating at 30 to 120 ° C. for 5 to 6000 minutes immediately after the start, wherein the polyester resin polymerization step is further performed at 70 to 180 ° C. in the presence of hydrolase after the first heating step. The second heating step is preferably performed for heating for ˜6000 minutes.

Moreover, the method for producing an aromatic polyester resin according to the present invention uses a dicarboxylic acid component containing terephthalic acid or naphthalenedicarboxylic acid, or a derivative thereof, and a diol component, in the presence of a hydrolase, and has a weight average molecular weight. An ester oligomer production process for producing a chain or cyclic ester oligomer mixture of less than 20,000, and a cyclic ester oligomer mixture obtained by the above process by separating and purifying cyclic ester oligomers to obtain a high purity cyclic ester oligomer mixture Polyester resin polymerization for producing an aromatic polyester resin having a weight average molecular weight of 20,000 or more by further polycondensation of the ester oligomer purification step and the high purity cyclic ester oligomer mixture obtained in the above step in the presence of a hydrolase Process and equipment And it is characterized in Rukoto.

Further, in the method for producing an aromatic polyester resin, the ester oligomer production step comprises converting a dicarboxylic acid component containing terephthalic acid or naphthalenedicarboxylic acid, or a derivative thereof, and a diol component in the presence of a hydrolase, 30 It is a step of heating at 120 ° C. for 5 to 6000 minutes, and the polyester resin polymerization step is preferably a step of heating at 70 to 180 ° C. for 60 to 6000 minutes in the presence of a hydrolase.

According to the present invention, a polyester resin can be synthesized in an environment in which the catalytic activity of a hydrolase is not impaired by a dicarboxylic acid component containing terephthalic acid or naphthalenedicarboxylic acid, or a derivative thereof, and a diol component. Select the type of monomer component to be used and the blending ratio thereof, and use a hydrolase exhibiting sufficient catalytic activity as a polymerization catalyst, adjust the temperature conditions during polycondensation, or pre-ester oligomer Is used for polycondensation to obtain a high molecular weight aromatic polyester resin having a low content of metal impurities and relatively excellent thermal properties and mechanical properties.

FIG. ₃ shows the results of ¹ H NMR spectrum analysis of an aromatic polyester resin (poly (hexamethylene terephthalate)) obtained in Test Example 3-1, (300 MHz, CDCl ₃ ). Effect of the ratio of diol (hexamethylene glycol) component and dicarboxylic acid (terephthalic acid) component contained in the mixture on the weight average molecular weight of aromatic polyester obtained by allowing immobilized enzyme to act on ester oligomer mixture FIG.

The aromatic polyester resin according to the present invention is obtained by polymerizing a dicarboxylic acid component containing terephthalic acid or naphthalenedicarboxylic acid, or a derivative thereof, and a diol component by the catalytic action of a hydrolase, and has a weight average molecular weight. Is 20,000 or more.

The dicarboxylic acid component used in the present invention contains terephthalic acid or naphthalenedicarboxylic acid, or a derivative thereof. The total amount of terephthalic acid or naphthalenedicarboxylic acid or derivatives thereof used in the present invention is preferably 40 mol% or more, more preferably 50 mol% or more, as a ratio to the total amount of the dicarboxylic acid component. When the ratio is 40 mol% or less, it is difficult to expect characteristics as an aromatic polyester resin. Further, the total amount of the dicarboxylic acid component may be terephthalic acid, naphthalenedicarboxylic acid, or a derivative thereof. Examples of terephthalic acid or naphthalenedicarboxylic acid derivatives include lower alkyl esters such as dimethyl terephthalate, diethyl terephthalate, dimethyl naphthalenecarboxylate, and diethyl naphthalenecarboxylate. Among these, it is particularly preferable to use a lower alkyl ester from the viewpoint of solubility and meltability in the reaction system. In addition, the dicarboxylic acid component other than terephthalic acid or naphthalenedicarboxylic acid or derivatives thereof is not particularly limited as long as an esterification reaction or a transesterification reaction can occur by an enzyme catalyst. Examples of other dicarboxylic acid components include aromatic dicarboxylic acids such as diphenyl dicarboxylic acid and diphenyl ether dicarboxylic acid, oxalic acid, succinic acid, maleic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, and itaconic acid. And aliphatic dicarboxylic acids such as polyvalent carboxylic acids such as pyromellitic acid. The dicarboxylic acid component may be derived from either a dicarboxylic acid or a lower alkyl ester of dicarboxylic acid. It is also possible to use hydroxy acids such as 6-hydroxyhexanoic acid derivatives, lactic acid derivatives, and glycolic acid derivatives instead of dicarboxylic acids. As the dicarboxylic acid component used in the present invention, a plurality of dicarboxylic acid components can be appropriately selected from the above-mentioned dicarboxylic acid components according to the desired physical properties and intended use of the resulting polyester resin.

The diol component used in the present invention is not particularly limited as long as an esterification reaction or a transesterification reaction can occur by an enzyme catalyst. Examples of the diol component include ethylene glycol, diethylene glycol, triethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, heptamethylene glycol, octamethylene glycol, decamethylene glycol, dodecamethylene glycol, polyethylene glycol. And aliphatic diols such as cyclohexanediol and cyclohexanedimethanol, and aromatic diols such as naphthalenediol, bisphenol A, and resorcin. As the diol component used in the present invention, an arbitrary number of components and blending ratio can be selected from the above diol components according to the purpose. Moreover, trihydric or more alcohols, such as glycerol and pentaerythritol, can also be used as needed.

The hydrolase used as a polymerization catalyst in the present invention is not particularly limited as long as it can promote the esterification reaction and transesterification reaction of the selected monomer or oligomer. For example, it can be selected from a hydrolase derived from a known strain, and among them, carboxylesterase (EC 3.1.1.1: carboxysterase) and lipase (EC 3.1.1.3: triacylglycolase lipase) are preferably used. be able to. In addition, from the viewpoint of heat resistance of the hydrolase and ease of separation from the resulting aromatic polyester resin, the hydrolase is preferably an immobilized hydrolase immobilized on a carrier. is there. The method for immobilizing the hydrolase is not particularly limited, and an immobilized hydrolase by a known immobilization method can be used. More specifically, Novozym 435 (manufactured by Novozyme; immobilized lipase immobilized on a porous acrylic resin), which is an immobilized enzyme in which lipase derived from Candida antarctica and carboxylesterase are immobilized, is particularly suitable hydrolyzate. It is mentioned as a degrading enzyme.

In addition, the aromatic polyester resin according to the present invention is obtained by allowing a hydrolase to act in the production stage in a state where a monomer used or an oligomer or polymer produced by a polymerization reaction is melted or dissolved. And For this reason, the aromatic polyester resin according to the present invention is adjusted in the type of monomer component used and the blending ratio thereof so that it can be synthesized in an environment where the catalytic activity of the hydrolase is not impaired. It will be necessary. More specifically, it is desirable to adjust the types of monomer components and the blending ratio thereof so that the resulting aromatic polyester resin has a melting point of less than 170 ° C. The combination of such monomer components is not particularly limited. For example, terephthalic acid / hexamethylene glycol, terephthalic acid / decamethylene glycol, 2,6-naphthalenedicarboxylic acid / decamethylene glycol, 2,6 A combination of naphthalenedicarboxylic acid / dodecamethylene glycol and the like. Moreover, as long as melting | fusing point of the obtained polyester resin is less than 170 degreeC, the other dicarboxylic acid component and diol which were enumerated above may be included appropriately. For example, when an aromatic polyester resin having a higher melting point such as polyethylene terephthalate or polybutylene terephthalate is selected, it is necessary to use severe reaction conditions such that the polymer produced by the reaction can be melted or dissolved. However, under such severe conditions, the catalytic activity of the hydrolase is remarkably reduced, so that it is difficult to obtain a high molecular weight product. The melting point can be measured by a known method. For example, the melting point can be measured by using a differential scanning calorimeter (DSC-60: manufactured by Shimadzu Corporation) at a temperature of 10 ° C./min in a nitrogen atmosphere. Can do. The melting point of the aromatic polyester resin according to the present invention is more preferably less than 165 ° C, still more preferably less than 160 ° C. The environment in which the catalytic activity of the hydrolase as described above is not impaired is largely governed by the resistance (heat resistance, chemical resistance, etc.) of the hydrolase used. If a hydrolase having high heat resistance is developed in the future (which does not exist at the time of filing), it is possible to obtain an aromatic polyester resin having a higher melting point by using the method of the present invention. .

The aromatic polyester resin according to the present invention has a weight average molecular weight of 20000 or more. When the molecular weight is less than 20000, for example, it is inferior in heat resistance and mechanical properties required when used as a structural material. In addition, a weight average molecular weight can be measured by a well-known method, for example, can be measured using a gel permeation chromatography (GPC). Examples of the weight average molecular weight measurement conditions by GPC include the following.
Column: Shodex K-804 (made by Showa Denko)
Detector: differential refractometer RI-980 (manufactured by JASCO)
Eluent: Chloroform: ethanol = 99: 1 (vol / vol)
Flow rate: 1.0 ml / min
Temperature: 37 ° C
Standard sample: TSK standard POLYSYRENE (manufactured by Tosoh Corporation)
The weight average molecular weight of the aromatic polyester resin according to the present invention is more preferably 25000 or more, and further preferably 30000 or more.

In addition, since the aromatic polyester resin according to the present invention is manufactured using a hydrolase instead of a heavy metal catalyst, for example, antimony, titanium, germanium, aluminum, zinc, tin, zirconium, magnesium, manganese Thus, it does not substantially contain metal impurities derived from metal catalysts that are conventionally used in the production of aromatic polyester resins. Therefore, the aromatic polyester resin according to the present invention can easily achieve less than 25 ppm in terms of metal elements with respect to the total content of these metal impurities. On the other hand, in a polyester resin produced using a conventionally used metal catalyst, it is extremely difficult to remove the residue of the used catalyst metal. In this case, there is a risk of causing environmental pollution and resin performance degradation. Although the amount of the residual catalyst metal can be reduced by an appropriate acid treatment or reprecipitation treatment, it is extremely difficult to completely remove it, which is not preferable from an economical viewpoint. The metal impurity content can be measured by a known method. For example, it can be measured by using an inductively coupled plasma emission analyzer (ICP emission analyzer P-4010: manufactured by Hitachi, Ltd.). . The total content of each metal impurity in the polyester resin according to the present invention is specifically less than 25 ppm, more preferably less than 20 ppm, and even more preferably less than 15 ppm in terms of metal element.

In the method for producing an aromatic polyester resin according to the present invention, a mixture of a chain or cyclic ester oligomer having a weight average molecular weight of less than 20,000 is preliminarily synthesized by intentionally operating synthesis conditions in the presence of a hydrolase. Then, a hydrolase is allowed to act on this ester oligomer mixture, and further polycondensation is performed to obtain a polyester having a weight average molecular weight of 20000 or more. By preparing an ester oligomer mixture having a weight average molecular weight of less than 20,000 in advance, the amount ratio (molar ratio) of the dicarboxylic acid component and the diol component in the reaction system at the end of the polycondensation reaction can be easily controlled (that is, in the reaction system). The ratio of the number of functional groups of the carboxylic acid and alcohol present tends to approach 1: 1). As a result, the aromatic polyester resin can have a higher molecular weight, and the molecular weight can be easily controlled. The ester oligomer production step and the subsequent polyester resin polymerization step can be carried out by changing the synthesis conditions in the same reaction vessel, or the ester oligomer mixture is produced in advance using a hydrolase. Separately, it is also possible to produce a polyester resin by allowing a hydrolase to act on this ester oligomer mixture.
As specific examples of the method for producing an aromatic polyester resin according to the present invention, for example, the following production method can be exemplified.

Manufacturing example 1
1) A dicarboxylic acid component containing terephthalic acid or naphthalenedicarboxylic acid or a derivative thereof, and a diol component are heated at 30 to 120 ° C. for 5 to 6000 minutes in the presence of a hydrolase immediately after the start of the reaction.
The lower limit of the reaction temperature in the first heating step is defined by the production efficiency of the ester oligomer. In other words, if the heating temperature is less than 30 ° C, at least one component of the monomer used cannot be melted or dissolved, or the catalytic efficiency by the hydrolase does not become sufficiently high. Alternatively, the reaction may take a long time. On the other hand, the upper limit of the temperature is defined by the sublimation or vaporization temperature of the dicarboxylic acid component or diol component used and the temperature range in which the catalytic activity of the hydrolase is maintained. That is, when the heating temperature exceeds 120 ° C., sublimation and vaporization of the dicarboxylic acid component and the diol component occur preferentially over the esterification reaction, and the abundance ratio of the dicarboxylic acid component and the diol component in the ester oligomer is efficiently increased. Therefore, it becomes difficult to obtain a high molecular weight polyester resin. The heating temperature in the first heating step is preferably 35 to 115 ° C, more preferably 40 to 110 ° C.

The heating time in the first heating step is 5 to 6000 minutes. If the heating time is less than 5 minutes, the reaction time is too short and the ester oligomer cannot be sufficiently formed. Therefore, in the subsequent polycondensation reaction, the amount ratio (molar ratio) of the dicarboxylic acid component and the diol component in the reaction system is set. It cannot be controlled, and as a result, a high molecular weight polyester resin cannot be obtained. On the other hand, heating exceeding 6000 minutes is not preferable from the viewpoint of production efficiency. The heating time in the first heating step is preferably 30 to 5000 minutes, and more preferably 60 to 4000 minutes.

2) After the heating step, the mixture is further heated at 70 to 180 ° C. for 60 to 6000 minutes in the presence of a hydrolase.
In the second heating step, the heating temperature is in the range of 70 to 180 ° C. When the heating temperature exceeds 180 ° C., the catalytic activity of the enzyme is significantly impaired, resulting in a decrease in yield or an increase in molecular weight. Also not preferable from the viewpoint of environmental burden, such as reduction or the like of the energy-saving and emission amount of CO _2. On the other hand, if it is less than 70 ° C., an aromatic polyester having a relatively high melting point cannot be melted, so that sufficient contact frequency with an enzyme cannot be provided, and a high molecular weight polyester is difficult to obtain. The heating temperature in the second heating step is preferably 75 to 175 ° C., more preferably 80 to 170 ° C. Here, for example, when an aromatic polyester resin having a melting point of about 140 to 170 ° C. is to be obtained, a sufficiently high molecular weight may not be obtained by heating at less than 80 ° C.
The heating time in the second heating step is 60 to 6000 minutes. When the heating time is less than 60 minutes, since the esterification reaction does not proceed sufficiently, a high molecular weight polyester resin may not be obtained. Moreover, heating exceeding 6000 minutes is not preferable from the viewpoint of production efficiency. The heating time in the second heating step is preferably 90 to 5000 minutes, more preferably 120 to 4000 minutes.

In the first heating step and the second heating step, the reaction may be continuously performed at the same heating temperature as long as it is within the specified temperature range. More specifically, when the temperature is in the range of 70 to 120 ° C., both heating steps can be performed continuously at the same heating temperature. In this case, the heating time only needs to be within the range of the sum of the prescribed times, and it is not necessary to clearly distinguish each heating step. On the other hand, when the temperature is changed between the first and second heating steps, the rate of temperature increase is not particularly limited, and the temperature may be gradually increased or rapidly increased. Further, in both the heating steps, the reaction may be carried out by constantly changing the temperature as long as it is within a specified temperature range.

Here, in the first heating step, since heating is performed in a relatively low temperature range of 30 to 120 ° C., the esterification reaction proceeds while sublimation and vaporization of the dicarboxylic acid component and the diol component are suppressed, A chain or cyclic ester oligomer mixture is formed. In this ester oligomer mixture, the dicarboxylic acid component and the diol component are present in an amount ratio (molar ratio) of about 1: 1. Moreover, the various ester oligomers in these ester oligomer mixtures are hardly damaged from the system by sublimation or vaporization by further heating. For this reason, when the ester oligomer mixture obtained in the ester oligomer production process is used, the polycondensation reaction of the polyester can proceed without the ratio of these amounts greatly deviating from 1: 1. As a result, it is possible to obtain a high molecular weight aromatic polyester resin that could not be obtained by the conventional enzyme-catalyzed polymerization method. On the other hand, for example, when heated to 120 ° C. or more immediately after the start of the reaction, the dicarboxylic acid component and the diol component are sublimated or vaporized, and the quantity ratio thereof deviates greatly. You will not be able to get.
Further, when using a highly sublimable monomer or the like, it is difficult to completely suppress sublimation only by the above production method. Therefore, in such a case, it is also possible to manufacture in a pressurized system or to prepare an excessively charged monomer that is easily sublimated.

Moreover, the said manufacturing method performs a 1st heating process and a 2nd heating process continuously in the same reaction container, However, An ester oligomer mixture is manufactured previously and it uses for the polymerization reaction of a polyester resin separately. Is also possible. This production method is particularly effective when a monomer that easily sublimes is selected, and a high molecular weight aromatic polyester resin is easily obtained. Hereinafter, such a manufacturing method will be described.

Manufacturing method example 2
1) A dicarboxylic acid component and a diol component containing terephthalic acid or naphthalenedicarboxylic acid or their derivatives are heated in an organic solvent for a predetermined time at a predetermined temperature in the presence of a hydrolase, and then the hydrolase is filtered off. Thereafter, the solvent is completely distilled off to produce a chain or cyclic ester oligomer mixture having a weight average molecular weight of less than 20,000.
In the ester oligomer production step, heating may be performed in an organic solvent at 30 to 120 ° C. for 5 to 6000 minutes in the presence of a hydrolase. More preferably, heating is performed at 35 to 120 ° C. for 30 to 5000 minutes, more preferably 40 to 115 ° C. for 60 to 4000 minutes.

In addition, the organic solvent used in the ester oligomer production step can sufficiently dissolve the intermediates produced in the process of obtaining the ester oligomer mixture having each monomer and the target composition, and in the reaction system to be selected. It can be freely selected as long as it does not vaporize remarkably quickly and the catalytic activity of the hydrolase used is not dramatically impaired. Although the kind of organic solvent which can be used changes also with the kind of monomer to be used, toluene, xylene, anisole, cumene etc. are mentioned, for example. Further, the amount of the organic solvent to be used is not particularly limited as long as it satisfies the above, but it is preferable to add it so that the concentration of the total amount of the dicarboxylic acid component is 1 to 10,000 mM. If it is less than 1 mM, not only the amount of the reaction solvent increases, but also ester oligomerization does not proceed sufficiently, so that sublimation and vaporization of dicarboxylic acid and diol cannot be suppressed in the following polyester resin production process. On the other hand, when the concentration is 10,000 mM or more, it becomes difficult to sufficiently dissolve the monomer and the ester oligomer.

In the ester oligomer production step, the monomer component is heated in an organic solvent for a predetermined time at a predetermined temperature in the presence of a hydrolase, whereby an esterification reaction or a transesterification reaction proceeds, and a target weight average molecular weight of 20000. A mixture of less than a chain or cyclic ester oligomer can be obtained. The weight average molecular weight and composition of the resulting ester oligomer mixture can also be adjusted as appropriate by changing the charging ratio of dicarboxylic acid component and diol component, heating temperature, heating time, substrate concentration, enzyme amount, etc. is there.

2) The ester oligomer mixture obtained in the above step is polycondensed by heating at a predetermined temperature for a predetermined time in the presence of a hydrolase to produce an aromatic polyester resin having a weight average molecular weight of 20000 or more.
In the polyester resin polymerization step, similarly to the second heating step in Production Example 1, specifically, heating may be performed at 70 to 180 ° C. for 60 to 6000 minutes. More preferably, heating is performed at 75 to 175 ° C. for 90 to 5000 minutes, more preferably 80 to 170 ° C. for 120 to 4000 minutes.

Here, the ester oligomer mixture obtained in the ester oligomer production step is a chain or cyclic ester oligomer having a weight average molecular weight of less than 20,000. In Production Method Example 2, since each monomer and oligomer to be produced are dissolved in an organic solvent, it is easier to prevent sublimation and vaporization than in Production Method Example 1, and the amount ratio (molar ratio) is about 1 : 1 is easily controlled, and as a result, a higher molecular weight polyester resin is easily obtained. For the same reason, it is suitable when using a monomer that is more easily sublimated or when using a plurality of dicarboxylic acid components or diol components having different sublimation properties. In addition, according to this production method in which an ester oligomer is prepared in advance, since the quantitative ratio (molar ratio) between the dicarboxylic acid component and the diol component is maintained at about 1: 1 from the start to the end of the polymerization reaction, As in the production method using a metal catalyst, for example, the heating temperature is set to a high temperature of 200 ° C. or higher, or an extreme pressure reduction operation is performed so that the quantitative ratio falls within a specific range in the polymerization reaction of the polyester. There is no need to go.

Further, in the cyclic ester oligomer, the quantitative ratio (molar ratio) of the dicarboxylic acid component and the diol component is completely 1: 1. Therefore, when a higher molecular weight aromatic polyester resin is desired, it is preferable that a larger amount of cyclic ester oligomer is contained in the ester oligomer mixture used in the polyester resin production process.
For this reason, it is also possible to separate and purify the cyclic oligomer from the ester oligomer mixture obtained as described above, and to use the obtained high-purity cyclic oligomer mixture for the polymerization reaction of the polyester resin. . Hereinafter, such a manufacturing method will be described.

Manufacturing method example 3
1) A linear or cyclic ester oligomer mixture having a weight average molecular weight of less than 20,000 is produced in the presence of hydrolase using a dicarboxylic acid component containing terephthalic acid or naphthalenedicarboxylic acid, or a derivative thereof, and a diol component. .
The ester oligomer production process is the same as in Production Method Example 2.

However, in the above ester oligomer production process, in order to more easily obtain a high-purity cyclic ester oligomer, the charge ratio (molar) of the dicarboxylic acid component containing terephthalic acid or naphthalenedicarboxylic acid or a derivative thereof and the diol component It is preferable that the ratio is slightly excessive. For example, when the lower alkyl ester is used as the dicarboxylic acid component, the diol component is preferably excessive, and the charging ratio (molar ratio) is dicarboxylic acid: diol = 1: 1.01 to 1: The range is preferably 1.70, more preferably 1: 1.05 to 1: 1.60. When a lower alkyl ester is used as a monomer, in the above ester oligomer mixture, in addition to the target cyclic ester oligomer, both ends thereof are (a) hydroxyl group-alkyl ester, (b) hydroxyl group-hydroxyl group, (c) alkyl group. Three types of ester-alkyl ester chain oligomers are included. Therefore, by slightly increasing the amount of the diol component, both ends of (c), which are relatively difficult to separate from the cyclic ester oligomer, suppress the formation of an alkyl ester-alkyl ester chain oligomer. Thereby, it becomes easy to separate and purify a high-purity cyclic oligomer. By adjusting the charged amount ratio (molar ratio) of the dicarboxylic acid component and diol component selected at this time, the amount of the chain (c) in the high purity cyclic ester oligomer mixture obtained after the cyclic oligomer purification step (that is, The amount ratio of the dicarboxylic acid component and the diol component) can be strictly and easily controlled, and as a result, an aromatic polyester resin having an arbitrary average molecular weight can be prepared after the polyester resin production process. Further, when a dicarboxylic acid is used as a monomer of the dicarboxylic acid component instead of the lower alkyl ester, the dicarboxylic acid component can be used in excess relative to the diol component.

2) A cyclic oligomer is separated and purified from the ester oligomer mixture obtained in the above step to obtain a high-purity cyclic oligomer mixture.
The cyclic oligomer separation step is not particularly limited, and known methods such as column chromatography and recrystallization can be used, and silica gel column chromatography is preferable. In addition, conventionally well-known things can be used suitably for a column filler, an eluent, etc. In addition, as described above, by appropriately selecting the charging amount ratio (molar ratio) of the dicarboxylic acid component and the diol component, it is easier to separate and purify the cyclic ester oligomer having the target composition, and the high purity. Cyclic ester oligomers can be obtained in a relatively high yield. As described above, the purity of the cyclic ester oligomer after separation and purification can be arbitrarily selected according to the molecular weight of the target aromatic polyester resin, and is not particularly limited. Usually, the amount of the dicarboxylic acid component and the diol component The ratio (molar ratio) is about 0.95 to 1.05, preferably about 0.99 to 1.01.

3) The cyclic ester oligomer obtained by the above step is further polycondensed in the presence of a hydrolase to produce an aromatic polyester resin having a weight average molecular weight of 20000 or more.
The polyester resin polymerization step is the same as in Production Method Example 2.

Here, in this manufacturing method using the high-purity cyclic ester oligomer mixture obtained by the cyclic ester oligomer separation step, the quantitative ratio (molar ratio) between the dicarboxylic acid component and the diol component is almost completely maintained at 1: 1. Therefore, it is possible to relatively easily obtain a high molecular weight aromatic polyester resin that could never be obtained by the conventional enzyme catalyst method. Further, as in the conventional method using a metal catalyst, for example, the heating temperature is set to a high temperature of 200 ° C. or higher so that the amount ratio falls within a specific range in the polyester polymerization reaction, or extreme pressure reduction is performed. There is no need to react underneath. Also, by using this production method, an aromatic polyester resin having an arbitrary average molecular weight can be easily obtained without finely adjusting the conditions such as the amount of raw materials supplied during the polymerization reaction and the heating temperature and heating time. .

In the process for producing the aromatic polyester resin described above, it is preferable to carry out the process without using any solvent because it is easier to obtain a high molecular weight product. However, a reaction system using a solvent can be arbitrarily selected according to physical properties expected of the obtained polyester resin. When a solvent is used, each monomer and oligomer, as well as the resulting polymer, can be sufficiently dissolved, it does not vaporize remarkably in the selected reaction system, and the catalytic activity of the enzyme used is dramatic. If it is not damaged, you can choose freely. Examples of such solvents include toluene, xylene, anisole, cumene and the like.

In addition, if there are many chemical species that can react with carbonyl groups such as water and alcohol in the reaction system, the target high molecular weight polyester resin cannot be obtained. Since the esterification reaction does not proceed, it is necessary to control these concentrations. In this control, a known method can be used without particular limitation as long as the target concentration can be achieved. For example, it is possible to perform a drying operation using a physical or chemical method on the raw material, enzyme, solvent, reaction vessel, etc. to be used, and specifically, an inert gas that is depressurized under heating and flowing. Examples thereof include a method of allowing an adsorbed substance having a molecular sieving effect such as synthetic zeolite to act on the reaction system in a contact or non-contact manner. Further, it is possible to control by adding water or the like according to the purpose.

The aromatic polyester resin of the present invention obtained as described above has a weight average molecular weight of 20000 or more despite the fact that it is produced using a hydrolase, and has excellent thermal properties and mechanical properties. Since it is relatively excellent, it can be particularly suitably used as a structural material. Moreover, since a metal catalyst is not used, it is possible to obtain a resin that does not substantially contain a catalytic metal element that has been conventionally used for polyester production. For this reason, it is possible to prevent environmental pollution due to metal outflow and the like, and further, it is difficult for the performance of the polyester resin to deteriorate due to metal impurities.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these Examples.
First, the present inventors use dimethyl terephthalate (dicarboxylic acid component) and hexamethylene glycol (diol component), and further use a hydrolase (immobilized hydrolase; Novozym 435) as a polymerization catalyst to produce a corresponding fragrance. The production of the aliphatic polyester resin was carried out according to Production Example 1 (Test Examples 1-1 to 1-5). The procedure for producing the aromatic polyester resin is as outlined below.

[Synthesis of aromatic polyester]
100 masses of immobilized lipase (Novozym 435, Candida-derived lipase and carboxylesterase: Novozyme) charged with a predetermined synthetic raw material (dicarboxylic acid component and diol component) at a predetermined ratio and previously dried. % Was added. A vessel containing dried molecular sieves was attached to the upper part of the reaction vessel, immediately sealed, heated to a predetermined temperature, and stirred for a predetermined time. Thereafter, the mixture was allowed to cool to room temperature, chloroform was added to dissolve the product, and the immobilized enzyme was filtered off. After concentrating the filtrate, this was added dropwise to toluene at room temperature, and the resulting precipitate was collected by filtration and dried to obtain the desired aromatic polyester resin.

In Test Examples 1-1 to 1-3, various charge ratios of dimethyl terephthalate and hexamethylene glycol were changed, heated at 90 ° C. for 5 hours, then heated to 140 ° C. over 1 hour, Stirring was performed for 42 hours. In Test Example 1-4, the same operation was performed without adding the immobilized enzyme. In Test Example 1-5, the mixture was heated to 140 ° C. immediately after the start of the reaction and stirred for 48 hours.
The product obtained by the above test ^{examples, 1 H NMR (VARIAN NMR300:} VARIAN Inc.) was used to confirm the structure, weight average molecular weight and molecular weight distribution of GPC (column: Shodex K-804 (manufactured by SHOWA DENKO Manufactured), detector: differential refractometer RI-980 (manufactured by JASCO), eluent: chloroform: ethanol = 99: 1 (vol / vol), flow rate: 1.0 ml / min, temperature: 37 ° C., standard sample : TSK standard POLYSYRENE (manufactured by Tosoh Corporation)). The results are shown in Table 1 below.

As shown in Table 1 above, Test Examples 1-1 to 1 in which dimethyl terephthalate and hexanemethylene glycol were preliminarily heated at 90 ° C. for 5 hours and further heated at 140 ° C. for 42 hours in the presence of a hydrolase. As for -3, it became clear that a high molecular weight aromatic polyester resin having a weight average molecular weight of 33,000 to 52,000 can be obtained in a high yield.
In contrast, in Test Example 1-4 in which no hydrolase was added, the polycondensation reaction did not proceed at all, and polyester could not be obtained. Furthermore, in Test Example 1-5, which was heated to 140 ° C. immediately after the start of the reaction, no polyester was obtained.

From the comparison between Test Example 1-1 and Test Example 1-4, it is understood that the production of the aromatic polyester of the present invention is due to the catalytic action of hydrolase. In Test Example 1-5, no polyester was obtained, but this was caused by the sublimation or vaporization of dimethyl terephthalate and hexamethylene glycol, and the reaction between the dicarboxylic acid component, the diol component, and the hydrolase as the catalyst. This is thought to be because they were unable to contact each other well in the system. On the other hand, in Test Examples 1-1 to 1-3, which were heated at a relatively low temperature of about 90 ° C. and then heated to a relatively high temperature of about 140 ° C., a high molecular weight aromatic polyester resin was obtained. The average molecular weight was the highest in Test Example 1-2 in which hexamethylene glycol, which was slightly vaporized slightly compared to dimethyl terephthalate, was used slightly in excess. From these results, it is understood that control of the amount ratio (molar ratio) of the carboxylic acid component and the diol component in the reaction system is extremely important for the production of a high molecular weight aromatic polyester. That is, in Test Examples 1-1 to 1-3, ester oligomerization sufficiently progressed in the first heating step, whereby sublimation could be sufficiently suppressed in the second heating step, and the ester oligomer mixture Since the amount ratio (molar ratio) between the dicarboxylic acid component and the diol component in the mixture was maintained at about 1: 1, the polycondensation reaction proceeded smoothly. As a result, a high molecular weight aromatic polyester was obtained. It is thought that it is obtained in a yield.

Furthermore, the present inventors conducted a similar test using a plurality of dicarboxylic acid components (dimethyl terephthalate and dimethyl 2,6-naphthalenedicarboxylate). The results are shown in Table 2 below.

As shown in Table 2, also in Test Example 1-6 using dimethyl terephthalate and dimethyl 2,6-naphthalenedicarboxylate as the dicarboxylic acid component, the weight average molecular weight was 35, A high molecular weight aromatic polyester resin having a molecular weight of 000 was obtained in a high yield.

Furthermore, the present inventors similarly attempted the synthesis of an aromatic polyester having 2,6-naphthalenedicarboxylic acid as a main dicarboxylic acid component as a dicarboxylic acid component. The results are shown in Table 3 below.

As shown in Table 3, in Example 1-7 using dimethyl 2,6-naphthalenedicarboxylate as the main dicarboxylic acid component, as in the above test example, a high molecular weight of 29,000 was obtained. Aromatic polyester was obtained in high yield.

Subsequently, the present inventors made a hydrolase to act on the dicarboxylic acid component and the diol component in an organic solvent in accordance with Production Example 2 to prepare an ester oligomer mixture in advance, and this was further added in the presence of the hydrolase. Then, production of the corresponding aromatic polyester resin was attempted by heating and polycondensation (Test Examples 2-1 to 2-4). The procedure for producing the ester oligomer mixture is as outlined below.

[Synthesis of ester oligomer mixture]
An immobilized lipase (Novozym 435, Candida-derived lipase: manufactured by Novozyme) charged with equimolar dimethyl terephthalate and various alkylene glycols and previously dried was added in an amount of 100% by mass based on the total amount of monomers. Further, toluene was added in an amount such that the concentration of dimethyl terephthalate was 25 mM, and a glass tube containing dried molecular sieves was attached to the top of the reaction vessel, immediately sealed, and stirred at 90 ° C. for 48 hours. Went. After completion of the reaction, the solution was allowed to cool to room temperature, the immobilized enzyme was filtered off, and the obtained filtrate was dried to obtain the target ester oligomer mixture.

In Test Example 2-1, the ester oligomer mixture obtained as described above was diluted in toluene to a concentration of 50 g / L, and heated and stirred at 100 ° C. for 48 hours in the presence of the immobilized enzyme. I did it. Thereafter, the mixture was allowed to cool to room temperature, chloroform was added to dissolve the product, and the immobilized enzyme was filtered off. After concentrating the filtrate, this was added dropwise to toluene at room temperature, and the resulting precipitate was collected by filtration and dried to obtain the desired aromatic polyester resin. In Test Examples 2-2 to 2-4, an ester oligomer mixture was prepared by variously changing the diol component, and then heated and stirred at 140 ° C. for 48 hours in the presence of the immobilized enzyme to carry out a polycondensation reaction. . The subsequent operation is the same as in Test Example 2-1.
For the products obtained by the above test examples, the structure was confirmed using ¹ H NMR (VARIAN NMR300: manufactured by VARIAN) and MALDI-TOF MASS (Ultraflex: manufactured by BRUKER), and the weight average molecular weight and The molecular weight distribution is GPC (column: Shodex K-804 (manufactured by Showa Denko KK), detector: differential refractometer RI-980 (manufactured by JASCO), eluent: chloroform: ethanol = 99: 1 (vol / vol), Flow rate: 1.0 ml / min, temperature: 37 ° C., standard sample: TSK standard POLYSTYRENE (manufactured by Tosoh Corporation)). The results are shown in Table 4 below.

As shown in Table 4 above, in Test Example 2-1, in which an ester oligomer mixture prepared in advance using a hydrolase was added to toluene and a heating / polycondensation reaction was performed, the weight average molecular weight was 21,000. It was confirmed that the present invention is sufficiently applicable even when a polycondensation reaction is carried out in an organic solvent. Also in Test Examples 2-2 to 2-4 using ester oligomer mixtures in which various diol components are changed, a high molecular weight aromatic polyester resin having a weight average molecular weight of 51,000 to 54,000 has a high yield. It became clear that it was obtained at a rate. In Test Example 2-4, an aromatic random copolyester resin having a composition ratio well matched with the charged amount ratio of the diol component was obtained.

Furthermore, the present inventors tried production of a corresponding aromatic polyester resin in the same manner as in the above test using a high-purity cyclic oligomer mixture obtained by purifying only a cyclic oligomer from an ester oligomer mixture according to Production Example 3. (Test Examples 3-1 and 3-2). The high-purity cyclic oligomer used here has a quantity ratio of the dicarboxylic acid component to the diol component of 1.000: 1.000 on ¹ H NMR. The procedure for producing the high-purity cyclic oligomer is as outlined below.

[Synthesis of high purity cyclic oligomer mixture]
An ester oligomer mixture was obtained in the same manner as in the synthesis of the ester oligomer mixture except that dimethyl terephthalate and 1.30 mole equivalent of alkylene glycol were added thereto and the reaction temperature was 105 ° C. Subsequently, this mixture was subjected to silica gel column chromatography, and the relevant fractions were collected and then concentrated and dried to obtain the intended high purity cyclic oligomer mixture.

In Test Example 3-1, the high-purity cyclic oligomer mixture was prepared using hexamethylene glycol as the diol component, and the mixture was heated and stirred at 140 ° C. for 48 hours in the presence of the immobilized enzyme to carry out a polycondensation reaction. In Test Example 3-2, the above-mentioned high-purity cyclic oligomer mixture was prepared using decamethylene glycol, and heated and stirred at 120 ° C. for 48 hours in the presence of the immobilized enzyme to carry out a polycondensation reaction. The subsequent operation is the same as in Test Examples 2-1 to 2-4.
For the products obtained by the above test examples, the structure was confirmed using ¹ H NMR (VARIAN NMR300: manufactured by VARIAN) and MALDI-TOF MASS (Ultraflex: manufactured by BRUKER), and the weight average molecular weight and The molecular weight distribution is GPC (column: Shodex K-804 (manufactured by Showa Denko KK), detector: differential refractometer RI-980 (manufactured by JASCO), eluent: chloroform: ethanol = 99: 1 (vol / vol), Flow rate: 1.0 ml / min, temperature: 37 ° C., standard sample: TSK standard POLYSTYRENE (manufactured by Tosoh Corporation)). The results are shown in Table 5 below. Further, FIG. 1 shows the ¹ H NMR measurement result of poly (hexamethylene terephthalate), which is an aromatic polyester resin obtained in Test Example 3-1.

As shown in Table 5 above, in Test Examples 3-1 and 3-2 in which a polycondensation reaction was performed using a cyclic oligomer mixture prepared with high purity, the weight average molecular weight was 130,000 to 140,000. It was revealed that an aromatic polyester resin having a high molecular weight was obtained. This is because in the cyclic oligomer used here, the amount ratio (molar ratio) of the dicarboxylic acid component and the diol component is almost completely 1: 1, and this ratio is maintained even during the polycondensation reaction. Conceivable.

In addition, the present inventors have produced high-purity cyclic oligomers by varying the charging amount ratio (molar ratio) of dimethyl terephthalate and hexamethylene glycol. Then, a polyester production process was performed in the same manner as in Test Example 3-1 on the ester oligomer mixture containing the chain oligomers of the both-end alkyl ester-alkyl ester in various ratios. Thus, the influence of the ratio of the dicarboxylic acid component / diol component in the high-purity cyclic ester oligomer used in the polyester production process on the molecular weight of the aromatic polyester obtained after the polyester production process was investigated. A summary of the results is shown in FIG. In the figure, [H] / [T] (mol / mol) represents the quantitative ratio (molar ratio) of the hexamethylene glycol component / terephthalic acid component in the high-purity cyclic oligomer mixture.

As shown in FIG. 2, it was confirmed that the amount ratio (molar ratio) of the dicarboxylic acid component / diol component in the high purity cyclic ester oligomer mixture greatly affects the molecular weight of the resulting aromatic polyester resin. It was. For example, it can be seen that the weight average molecular weight of the obtained resin is only about 60,000 even when the above-mentioned ratio is only 1 mol%. From this, it can be said that in order to obtain a high molecular weight aromatic polyester resin, it is necessary to control the dicarboxylic acid component / diol component in the polycondensation reaction to 1: 1 with considerably high accuracy. Moreover, by making the preparation amount ratio (molar ratio) of the dicarboxylic acid component and the diol component in the ester oligomer production process arbitrary, for the purpose of the quantitative ratio of the dicarboxylic acid component and the diol component in the obtained cyclic ester oligomer Accordingly, the molecular weight of the aromatic polyester can be strictly controlled without changing other conditions. From these it is understood that the use of a high purity cyclic ester oligomer mixture is extremely useful.

Subsequently, physical properties tests (thermal properties and mechanical properties) for actual use were performed on the high molecular weight aromatic polyester resin of the present invention obtained as described above. The results are shown in Tables 6 and 7 below.
Among the evaluation of thermal characteristics, the glass transition point, melting point, and temperature drop crystallization temperature are measured using a differential scanning calorimeter (DSC-60: manufactured by Shimadzu Corporation). (DTG-60H: manufactured by Shimadzu Corporation) was used. The measurement was performed by changing the temperature at 10 ° C./min in a nitrogen atmosphere. Evaluation of mechanical properties (tensile test) was performed by punching a dumbbell with a width of the test part of 5.0 mm and a length of 30.0 mm for a sheet of about 100 μm thickness prepared by hot pressing each resin. A test piece was used and a precision universal testing machine (Autograph AGS-J: manufactured by Shimadzu Corporation) was used. The distance between the grips was 10 mm, the test temperature was 25 ° C., and the test speed was 10 mm / min.

As shown in Tables 6 and 7 above, the aromatic polyester resin of the present invention produced using a hydrolase has heat comparable to that of high density polyethylene used as a conventional structural material. The characteristics and mechanical properties are shown. From this, it was confirmed that the aromatic polyester resin of the present invention can be sufficiently used as a structural material.

The high molecular weight aromatic polyester resin of the present invention obtained as described above was subjected to a quantitative test of the metal ion content. The results are shown in Table 8 below.
The metal ion quantitative test was conducted using an inductively coupled plasma optical emission spectrometer (ICP optical emission spectrometer P-4010 manufactured by Hitachi, Ltd.). For a resin sample immersed in concentrated sulfuric acid (Test Example 3-1; polyhexamethylene terephthalate), an operation of allowing concentrated nitric acid to act while refluxing at about 320 ° C. was repeated until the solution became transparent. Concentrated nitric acid was distilled off by heating. The obtained solution was diluted with pure water at 20 ° C., and this was used as a sample solution for ICP emission analysis.

As shown in Table 8 above, the heavy metal content contained in the aromatic polyester resin of the present invention produced using a hydrolase was less than the detection limit for all measured metals. From this, it is understood that the aromatic polyester resin obtained by the present invention has very few metal impurities. For this reason, it is considered that environmental pollution due to metal outflow or the like can be prevented, and further, the performance deterioration of the polyester resin due to metal impurities is hardly caused.

Claims

A fragrance obtained by polymerizing a dicarboxylic acid component containing terephthalic acid or naphthalenedicarboxylic acid, or a derivative thereof, and a diol component by the catalytic action of a hydrolase, and having a weight average molecular weight of 20000 or more Family polyester resin.
The aromatic polyester resin according to claim 1, wherein the aromatic polyester resin has a melting point of less than 170 ° C.
3. The aromatic polyester resin according to claim 1, wherein the hydrolase is a lipase.
4. The aromatic polyester resin according to claim 3, wherein the lipase is an immobilized lipase immobilized on a carrier.
The aromatic polyester resin according to any one of claims 1 to 4, which is substantially free of antimony, titanium, germanium, aluminum, zinc, tin, zirconium, magnesium and manganese. resin.
Ester oligomer for producing a chain or cyclic ester oligomer mixture having a weight average molecular weight of less than 20,000 in the presence of hydrolase, using a dicarboxylic acid component containing terephthalic acid or naphthalenedicarboxylic acid, or a derivative thereof, and a diol component Manufacturing process,
A polyester resin polymerization step of producing an aromatic polyester resin having a weight average molecular weight of 20000 or more by further polycondensing the ester oligomer mixture obtained in the above step in the presence of a hydrolase. A method for producing an aromatic polyester resin.
7. The method for producing an aromatic polyester resin according to claim 6, wherein the ester oligomer production step comprises diteric acid component containing terephthalic acid or naphthalenedicarboxylic acid, or a derivative thereof, and a diol component in the presence of hydrolase. The first heating step is to heat at 30 to 120 ° C. for 5 to 6000 minutes immediately after the start of the reaction, and the polyester resin polymerization step is further performed in the presence of a hydrolase after the first heating step. A method for producing an aromatic polyester resin, which is a second heating step of heating at 60 ° C. for 60 to 6000 minutes.
Ester oligomer for producing a chain or cyclic ester oligomer mixture having a weight average molecular weight of less than 20,000 in the presence of hydrolase, using a dicarboxylic acid component containing terephthalic acid or naphthalenedicarboxylic acid, or a derivative thereof, and a diol component Manufacturing process,
A cyclic ester oligomer purification step for separating and purifying a cyclic ester oligomer from the ester oligomer mixture obtained by the above step to obtain a high purity cyclic ester oligomer mixture;
A polyester resin polymerization step of producing an aromatic polyester resin having a weight average molecular weight of 20000 or more by further polycondensing the high-purity cyclic ester oligomer mixture obtained in the above step in the presence of a hydrolase. A process for producing an aromatic polyester resin characterized by
9. The method for producing an aromatic polyester resin according to claim 8, wherein the ester oligomer production step comprises a dicarboxylic acid component containing terephthalic acid or naphthalenedicarboxylic acid, or a derivative thereof, and a diol component in the presence of a hydrolase. The polyester resin polymerization step is a step of heating at 70 to 180 ° C. for 60 to 6000 minutes in the presence of a hydrolase, and a step of heating at 30 to 120 ° C. for 5 to 6000 minutes. A method for producing an aromatic polyester resin.