CN101454374A - Method for producing polyester block copolymer - Google Patents

Abstract

In the production method of the present invention, the molten crystalline aromatic polyester (A) and (B1) or the lactone composition (B2) are continuously supplied to the static mixer at a constant speed by a constant speed pump, The reaction is carried out and a polyester block copolymer is obtained. In this production method, it is preferable to supply the crystalline aromatic polyester (A) at a gear pump input side pressure of 0.0098 MPa (gauge pressure) or higher. In addition, the feed pressure of the lactone (B1) or the lactone composition (B2) is preferably adjusted to 1.96 MPa (gauge pressure) or higher. According to this production method, a crystalline aromatic polyester and lactones react to industrially efficiently produce a polyester block copolymer of constant quality.

Description

Method for producing polyester block copolymer

technical field

The present invention relates to a method for producing a polyester block copolymer, and more particularly to a method for continuously producing a polyester block copolymer, which can continuously obtain a polyester block copolymer of generally constant quality. Polyester block copolymers are generally used as materials such as fibers, shaped articles, and films.

Background technique

In JP-A-61-281124 and JP-A-61-283619, it is described that melted crystalline aromatic polyester and lactones are continuously fed into a reaction tank for addition polymerization to produce elastic polyester. method. However, these methods take a long time to react, and the aromatic polyester constituting the hard segment and the polylactone constituting the soft segment are partially randomized due to the transesterification reaction, and only elastic polyesters with large fluctuations in melting point and mechanical strength can be obtained. .

Japanese Unexamined Patent Publication No. 5-93050 discloses a so-called CSTR continuous production method in which a plurality of stirring tanks are arranged in series, and lactides are continuously supplied therein to polymerize them. A reaction apparatus with a dynamic stirrer is used in this method. However, when lactides are polymerized by this method, the viscosity of the polymer rises to a very high viscosity range of 10,000 poise or more along with the increase in the average molecular weight of the polymer produced, making it difficult to stir with a normal mixer. , it is difficult to remove the reaction content. In addition, even if a powerful stirrer is used and the stirring blades are designed to stir the reaction system, the reaction content will form a motion close to laminar flow with the rotation of the stirring blades, making it difficult to uniformly mix the entire system. In addition, the ring-opening polymerization of cyclic esters is accompanied by heat generation, and the high viscosity makes it difficult to uniformly stir, which easily causes difficulty in temperature control in the reaction tank, and the reaction is out of control. deteriorating. In this document, when continuously producing high-molecular-weight polyester-based polymers from lactides or lactones, neither the difficulty of uniform stirring nor the difficulty of slow heating due to the high viscosity of the reactants is disclosed or suggested to be solved. Method.

JP-A-7-26001 discloses that in a continuous reaction device with a static mixer, a cyclic ester formed between two molecules of a hydroxycarboxylic acid and one or more lactones are continuously supplied, and ring-opening polymerization is performed continuously. A method of producing a biodegradable polyester polymer. In addition, JP-A-7-149878 discloses a method of producing a lactone-based copolymer by reacting a lactone (A) and a polyester (B) in the presence of a ring-opening polymerization catalyst (C). The ester (B) has a repeating unit of an aromatic dicarboxylic acid component and a diol component, and a repeating unit of an aliphatic dicarboxylic acid component and a diol component as essential constituents. However, these methods are only effective for the polymerization of low-viscosity liquid monomers. In the copolymerization of high-viscosity polymer melts and low-viscosity liquid monomers, it is difficult to continuously supply two or more raw materials in the correct ratio. The physical properties of the obtained polyester block copolymers vary widely.

Patent Document 1: JP-A-61-281124

Patent Document 2: JP-A-61-283619

Patent Document 3: Japanese Unexamined Patent Publication No. 5-93050

Patent Document 4: Japanese Unexamined Patent Publication No. 7-26001

Patent Document 5: JP-A-7-149878

Contents of the invention

The problem the invention solves

An object of the present invention is to provide a method capable of industrially and efficiently producing a polyester block copolymer of constant quality when a crystalline aromatic polyester and lactones are reacted to obtain a polyester block copolymer.

Solution to the problem

In order to achieve the above object, the inventors of the present invention made repeated studies, and found that the molten crystalline aromatic polyester and the lactones were continuously supplied to the static mixer at a constant speed by a gear pump and a constant rate pump respectively. Even when two kinds of compounds having a large difference are used as raw materials, the homogeneity of the reaction can be maintained, and a polyester block copolymer of constant quality can be efficiently produced, thereby completing the present invention.

That is, the present invention provides a method for producing a polyester block copolymer, the method comprising: feeding molten crystalline aromatic polyester (A) through a gear pump and feeding lactone (B1) or a lactone composition ( B2), respectively, were continuously supplied to a static mixer at a constant speed, and reacted to obtain a polyester block copolymer.

In this production method, a crystalline aromatic polyester (A1) with an acid value greater than 2 mg-KOH/g can be reacted with a lactone (B1), or a crystalline aromatic polyester with an acid value below 2 mg-KOH/g can be reacted. The polyester (A2) and the lactone composition (B2) are reacted.

As the lactone composition (B2), a composition containing a lactone (B1) and a phosphite compound (C) can be used. In this case, the lactone composition (B2) may further optionally contain at least one compound selected from acidic phosphoric acid ester (D) and tin compound (E).

In this production method, it is preferable to supply the crystalline aromatic polyester (A) at a gear pump input side pressure of 0.0098 MPa (gauge pressure) or higher. Furthermore, it is preferable to adjust the feeding pressure of the lactone (B1) or the lactone composition (B2) to 1.96 MPa (gauge pressure) or more.

Invention effect

According to the production method of the present invention, since the molten crystalline aromatic polyester (A) and the lactone (B1) or lactone composition (B2) are continuously supplied at a constant speed to the static The reaction is carried out in a mixer, and the copolymerization ratio and conversion rate are generally constant. Therefore, it is possible to continuously and efficiently obtain a polyester block copolymer of constant quality industrially without performing a mixing treatment for quality leveling. Therefore, the method of the present invention is particularly useful for continuous production of polyester block copolymers whose physical properties vary greatly depending on the copolymerization ratio or conversion rate.

Detailed ways

[Crystalline aromatic polyester (A)]

The crystalline aromatic polyester (A) used in the present invention is a polyester of an acid component (a) (dicarboxylic acid component) and a diol component (b), which is a polymer mainly having an ester bond, and has a molecular The terminal has a hydroxyl group. As the acid component (a), an aromatic dicarboxylic acid is used as an essential component, and an aliphatic dicarboxylic acid and/or an alicyclic dicarboxylic acid is added as needed; as a diol component (b), an aliphatic diol, an aromatic diols and/or cycloaliphatic diols.

The aforementioned crystalline aromatic polyester (A) is preferably a polyester having a high degree of polymerization and a melting point of 160°C or higher (for example, about 160°C to 285°C). Furthermore, as a molding material, it is preferable that the number average molecular weight (in terms of polymethyl methacrylate) is 5,000 or more (for example, about 5,000 to 100,000).

Specific examples of the acid component (a) constituting the crystalline aromatic polyester (A) are as follows. Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, biphenyl dicarboxylic acid, etc. As the aliphatic dicarboxylic acid, a dicarboxylic acid having 2 to 20 carbon atoms is suitable, for example, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, lauric acid, Polyacid etc. Examples of the alicyclic dicarboxylic acid include 1,4-cyclohexanedicarboxylic acid and the like. When these dicarboxylic acids are used as raw materials, they may be esters, acid salts, or cyclic acid anhydrides. The acid component (a) can be used individually or in combination of 2 or more types.

Among them, it is preferable to use at least terephthalic acid as the acid component (a). The amount of terephthalic acid is preferably 60 mol% or more, more preferably 80 mol% or more, of the entire acid component (a).

Specific examples of the diol component (b) of the crystalline aromatic polyester (A) are as follows. Examples of aliphatic diols include 1,4-butanediol, 1,3-butanediol, 1, 2-butanediol, ethylene glycol, propylene glycol, 1,3-propanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9 - Nonanediol, neopentyl glycol, polymethylene glycol and the like. Examples of aromatic diols include additions of resorcinol, naphthalenediol, 2,2-bis(4-hydroxyphenyl)propane, bisphenol A, and alkylene oxides such as ethylene oxide or propylene oxide. products, such as 2,2-bis(4-hydroxyethoxyphenyl)propane, 2,2-bis(4-hydroxydiethoxyphenyl)propane, 2,2-bis(4-hydroxytriethyl oxyphenyl)propane, 2,2-bis(4-hydroxypolyethoxyphenyl)propane, etc. Examples of alicyclic diols include 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2,2-bis(4-hydroxyethoxycyclohexyl)propane, or hydrogenated bis Adducts of phenol A and alkylene oxides such as ethylene oxide or propylene oxide, etc. The diol component (b) can be used individually or in combination of 2 or more types.

Among them, as the diol component (b), at least one component selected from 1,4-butanediol and ethylene glycol is preferably used. The total amount of 1,4-butanediol and ethylene glycol accounts for preferably 60 mol% or more of the entire diol component (b), more preferably 80 mol% or more.

The crystalline aromatic polyester (A) can be used alone or in combination of two or more.

In the crystalline aromatic polyester (A), it is preferable to contain at least one selected from a butylene terephthalate unit and an ethylene terephthalate unit in consideration of crystallinity, heat resistance, or raw material cost. Aromatic polyesters containing such units are particularly preferably aromatic polyesters containing 60 mol% or more of these units in total.

In the present invention, the crystalline aromatic polyester (A) and the lactone (B1) or the lactone composition (B2) are continuously supplied to a static mixer at a constant speed and reacted to produce a polyester block copolymer . When the crystalline aromatic polyester (A) is a crystalline aromatic polyester (A1) having an acid value of more than 2 mg-KOH/g in the continuous production of a polyester block copolymer with excellent hue (hue) and heat resistance , preferably react with lactone (B1); when the crystalline aromatic polyester (A) is a crystalline aromatic polyester (A2) with an acid value of 2 mg-KOH/g or less, preferably react with the lactone composition (B2) reaction. As the lactone composition (B2), any composition may be used as long as it contains the lactone (B1), but a composition containing the lactone (B1) and a phosphite compound (C) is preferred, and it is particularly preferred that the lactone (B1) ) and phosphite compound (C), also contain at least one selected from acidic phosphoric acid ester (D) and tin compound (E) (especially at least one of acidic phosphoric acid ester (D) and tin compound (E ) at least one) composition. When using a crystalline aromatic polyester (A2) with an acid value of 2 mg-KOH/g or less, a polyester block copolymer obtained by performing a transesterification reaction between a crystalline aromatic polyester component and a lactone-derived polyester component There are cases where the melting point, hue, and heat resistance are lowered, or the polymerization rate is lowered. At this time, if the phosphite compound (C), or the phosphite compound (C) and the acidic phosphoric acid ester (D) are supplied to the reaction system, the above-mentioned transesterification reaction can be suppressed, and the crystallization of the crystalline aromatic polyester can be maintained. Therefore, it is possible to obtain a polyester block copolymer with a high melting point, excellent hue and heat resistance. In addition, when the tin compound (E) is supplied to the reaction system, the desired polymerization reaction can proceed smoothly, and a polyester block copolymer excellent in heat resistance and the like can be obtained.

[Lactone (B1) or lactone composition (B2)]

Examples of the lactone (B1) include ε-caprolactone; 2-methyl-ε-caprolactone, 4-methyl-ε-caprolactone, 4,4-dimethyl ε-caprolactone Equal methylation (ε-caprolactone); δ-valerolactone; methylation (δ-valerolactone); β-propiolactone, etc. Lactone (B1) can be used individually or in combination of 2 or more types.

Among them, as the lactone (B1), ε-caprolactone is most preferable in consideration of cost, physical properties of the obtained polyester block copolymer, and the like. The amount of ε-caprolactone is preferably 60 mol% or more, more preferably 80 mol% or more of the whole lactone (B1).

The supply ratio [(A)/(B1) or (B2)] of the crystalline aromatic polyester (A) and the lactone (B1) or the lactone composition (B2) is not particularly limited, but a weight ratio of 90/ 10-35/65, especially 85/15-40/60.

A ring-opening polymerization catalyst is optionally used in the polymerization reaction. As the ring-opening polymerization catalyst, an esterification catalyst generally used in polyester synthesis can be used. Examples of these catalysts include metals such as tin, zinc, lead, titanium, bismuth, zirconium, and germanium, or compounds (organometallic compounds, carbonates, oxides, halides, etc.) containing the metals. Among them, tin compounds are most preferable in consideration of the physical properties of the obtained polyester block copolymer and the like.

[Phosphite compound (C)]

The phosphite compound (C) is not particularly limited as long as it is a phosphite compound having one or more phosphorus in the same molecule. Preferable examples of phosphite compounds (C) include bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol-diphosphite (jiphosfeit), bis(2,4-di tert-butylphenyl) pentaerythritol-diphosphite, three (2,4-di-tert-butylphenyl) phosphite (Hosfeit), three (single, dinonylphenyl) phosphite, three ( Monononylphenyl)phosphite, triisodecylphosphite, etc.

The supply amount of the phosphite compound (C) is, for example, 0.0001 to 0.3 parts by weight, preferably 0.001 to 0.05 parts by weight, based on 100 parts by weight of the total of the crystalline aromatic polyester (A) and the lactone composition (B1). range of servings. If the supply amount of the phosphite compound (C) is less than 0.0001 parts by weight, the transesterification inhibitory effect tends to become insufficient, so a crystalline aromatic polyester (A2) with an acid value of 2 mg-KOH/g or less is used as the crystal. When the aromatic polyester (A) is used, the obtained polyester block copolymer has a low melting point, and tends to decrease in hue and heat resistance. On the other hand, when the supplied amount of the phosphite compound (C) exceeds 0.3 parts by weight, the hydrolysis resistance of the polyester block copolymer may decrease.

[Acid Phosphate (D)]

The acidic phosphoric acid ester (D) is not particularly limited as long as it is an acidic phosphoric acid ester compound having one or more phosphorus in the same molecule. Preferable examples of acidic phosphoric acid ester (D) include methyl acidic phosphoric acid ester (Hosfet), butyl acidic phosphoric acid ester, dibutyl phosphoric acid ester, monobutyl phosphoric acid ester, 2-ethylhexyl acidic phosphoric acid ester ester, bis(2-ethylhexyl) phosphate, isodecyl acid phosphate, monoisodecyl phosphate, etc.

The supply amount of the acidic phosphoric acid ester (D) is, for example, 0.0001 to 0.03 parts by weight, preferably 0.001 to 0.01 parts by weight, based on 100 parts by weight of the total of the crystalline aromatic polyester (A) and the lactone composition (B1). scope. If the supply amount of the acidic phosphoric acid ester (D) is less than 0.0001 parts by weight, the effect of inhibiting the transesterification may be insufficient, so a crystalline aromatic polyester (A2) having an acid value of 2 mg-KOH/g or less is used as the crystalline aromatic polyester (A2). In the case of polyester (A), the obtained polyester block copolymer has a low melting point, and tends to decrease in hue and heat resistance. On the other hand, when the supply amount of acidic phosphoric acid ester (D) exceeds 0.01 weight part, there exists a possibility that the hydrolysis resistance of a polyester block copolymer may fall.

[Tin compound (E)]

The tin compound (E) is not particularly limited as long as it has one or more tin compounds in the same molecule. Preferable examples of the tin compound (E) include inorganic tin compounds such as tin halides such as stannous chloride, stannous bromide, and stannous iodide; tin carboxylates such as tin 2-ethylhexanoate or organic tin compounds such as dibutyltin oxide; wait.

The supply amount of the tin compound (E) is, for example, 0.0001 to 0.6 parts by weight, preferably 0.002 to 0.1 parts by weight relative to 100 parts by weight of the total amount of the crystalline aromatic polyester (A) and the lactone composition (B1). scope. In addition, when the tin compound (E) and the acidic phosphoric acid ester (D) are used together, the supply amount of the tin compound (E) is, for example, 1 to 20 parts by weight relative to 1 part by weight of the acidic phosphoric acid ester (D), preferably 2 to 10 parts by weight. If the supply amount of the tin compound (E) is too small, when the crystalline aromatic polyester (A2) having an acid value of 2 mg-KOH/g or less is used as the crystalline aromatic polyester (A), the polymerization rate becomes slow. It takes a long time to obtain the polyester block copolymer, and if it is too much, the hydrolysis resistance of the polyester block copolymer may decrease. In addition, the lactone composition (B2) forms a polymer before injecting it into the static mixer. , it is difficult to obtain the target polyester block copolymer.

In addition, in addition to the crystalline aromatic polyester (A) and the lactone (B1) or the lactone composition (B2), lactides may be supplied to the polymerization reaction. The amount of lactide used is, for example, 0 to 50 parts by weight, preferably 0 to 20 parts by weight relative to 100 parts by weight of the total of the crystalline aromatic polyester (A) and lactone (B1) or lactone composition (B2). parts by weight, more preferably 0 to 5 parts by weight.

In the present invention, a solvent may be used in the polymerization reaction, but even if no solvent is used, the homogeneity of the reaction can be ensured, the copolymerization ratio or conversion rate can be kept constant, and polyester block copolymers of constant quality can be continuously produced.

The polymerization temperature can be appropriately selected according to the type of crystalline aromatic polyester (A) or lactone (B1) or lactone composition (B2), the feed ratio, etc., but it is generally 200°C to 300°C, preferably 210°C ~270°C or so. Also, the residence time in the static mixer can also be appropriately selected according to the type of crystalline aromatic polyester (A) or lactone (B1) or lactone composition (B2), feed ratio, etc., and is usually 10 minutes ~180 minutes, preferably around 60 minutes to 120 minutes.

Next, the devices used in the present invention will be described in detail, but are not limited thereto. The static mixer used in the present invention refers to a static mixer without a driving part, and blades called mixing elements are arranged in a line in a pipe or a flow path. The shapes of the mixing elements can be the same shape, or different shapes. In addition, elements having the same shape but different inner diameters can also be arranged. In addition, adjacent elements are arranged only in a state of being rotated by a constant angle (for example, 90°). The shape of the mixing element includes a spiral shape, a state type (sta-tastaip) and the like. Through this mixing element, fluids can be divided, reversed, switched, allowing fluids (reactants) to mix.

The static mixer is not particularly limited, but for example, Kenics (ケニックス) type static mixer, "SMX" and "SMXL" of Sulzer Corporation, Toray type static mixer (Toray type スタテイックミキサ-, static mixers of Toray style) and so on. In the present invention, two or more types of static mixers may be used in combination.

In the present invention, the molten crystalline aromatic polyester (A) is continuously supplied to the static mixer at a constant speed by a gear pump, but the pressure on the input side of the gear pump is maintained for quantitative properties. As a method of applying pressure, there may be mentioned a method of connecting the extruder and the gear pump with piping provided with a pressure gauge, and controlling the rotation speed of the extruder so that the piping pressure is constant. At this time, the pressure on the input side of the gear pump is preferably 0.0098 MPa (gauge pressure) or more [for example, 0.0098 MPa (gauge pressure) to 0.98 MPa (gauge pressure), especially 0.098 MPa (gauge pressure) to 0.49 MPa (gauge pressure)] . If the pressure is less than 0.0098 MPa (gauge pressure), the supply of the crystalline aromatic polyester may not be stable, and it is difficult to continuously obtain a polyester block copolymer of constant quality.

In the present invention, the lactone (B1) or the lactone composition (B2) is continuously supplied to the static mixer at a constant speed by a metered pump, and in order to achieve mixing with the molten crystalline aromatic polyester (A) Keep up the pressure. As a method of maintaining the pressure, a method of providing an injection valve between a metering pump (for example, a plunger pump (plunger pump)) and a static mixer, etc. are mentioned. At this time, the set pressure of the injection valve [feed pressure of lactone (B1) or lactone composition (B2)] is preferably above 1.96MPa (gauge pressure) [for example, 1.96MPa (gauge pressure) to 25.48MPa (gauge pressure) Pressure), especially 7.84MPa (gauge pressure) ~ 21.56MPa (gauge pressure)]. If it is less than 1.96 MPa (gauge pressure), the mixing of crystalline aromatic polyester and lactone [lactone (B1) or lactone composition (B2)] is unstable, and it is difficult to continuously obtain polyester blocks of constant quality copolymer.

The polyester block copolymer thus obtained can be used as materials for fibers, shaped articles, films and the like.

Example

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, in an Example, MI (melt index) value and a melting point were measured by the following method.

(1) MI value

Measured at 230° C. using a load of 2.160 kg (unit: g/10 minutes).

(2) Melting point

Using a differential scanning calorimeter (DSC), it was measured in accordance with JIS K7121, and the melting peak temperature was defined as the melting point (in °C).

(3) acid value

After the sample was dried at 120° C. for 5 hours, about 1.0 g was weighed, and dissolved by heating at 160° C. for 1 hour in 50 g of benzyl alcohol. After water cooling, add 50g of chloroform, mix, use phenolphthalein as indicator, and titrate with 1/10 equivalent KOH ethanol solution. Then subtract the acid value of the benzyl alcohol and chloroform mixture measured separately to obtain the acid value.

Manufacturing example 1

Mix 1000 parts by weight of ε-caprolactone (CLM), 1.25 parts by weight of phosphite (manufactured by Asahi Denka Industry Co., Ltd., trade name "adekastab (アデカスタブ) PEP-30"), 0.13 parts by weight of acid phosphate (Dahachi Chemical Industry Co., Ltd. Company manufacture, trade name "AP-4"), 0.25 parts by weight of a tin compound (Nitto Chemicals Co. ).

Embodiment 1-5

Polybutylene terephthalate (PBT, melting point 228° C., number average molecular weight 30,000, acid value 2.6 mg-KOH/g) melted in a single-screw extruder was fed to the static mixer at a constant speed with a gear pump A device (manufactured by Sulzer (スル—ザ—) company, trade name "SMXL", inner diameter 3.8cm, length 798cm, 72 mixing elements are arranged in it), supplies ε-hexyl in the above-mentioned static mixer with a plunger pump at a constant speed Lactones (CLM), continuously obtained polyester block copolymers. The reaction temperature is 235° C., the pressure on the input side of the gear pump is 0.196 MPa (gauge pressure), and the feed pressure of ε-caprolactone is 15.68 MPa (gauge pressure). The pelletized polyester block copolymer was discharged from the static mixer and sampled every 15 minutes to measure its physical properties. The results are shown in Table 1. According to Table 1, it can be seen that the deviation of MI value and melting point is very small.

Comparative example 1

Use a quantitative feeder to supply polybutylene terephthalate (PBT, melting point 228°C, number average molecular weight 30000, acid value 2.6mg-KOH/g) to the twin-screw extruder at 3kg/hour, and use a plunger pump ε-caprolactone (CLM) was supplied to the twin-screw extruder at 2 kg/hour, mixed (at a temperature of 260° C.), and supplied to a static mixer (manufactured by Sulzer Corporation, trade name ) through a gear pump set at a constant speed. "SMXL", inner diameter 3.8 cm, length 798 cm, containing 72 mixing elements), whereby a polyester block copolymer is continuously obtained. The reaction temperature was 235°C. The pelletized polyester block copolymer was discharged from the static mixer and sampled every 15 minutes to measure its physical properties. The results are shown in Table 1. According to Table 1, it can be seen that the deviation of MI value and melting point is large.

Comparative example 2

To the complete mixing tank, 60 parts by weight of polybutylene terephthalate (PBT, 228° C. of fusing point, number average molecular weight 30000, acid value 2.6 mg-KOH/g), 40 parts by weight of ε-caprolactone ( CLM), mixed (temperature 235° C.), supplied to a static mixer (manufactured by Sulzer Company, trade name “SMXL”, inner diameter 3.8 cm, length 798 cm, 72 mixing elements inside) by a gear pump set at a constant speed , thereby continuously obtaining polyester block copolymers. The reaction temperature was 235°C. The pelletized polyester block copolymer was discharged from the static mixer and sampled every 15 minutes to measure its physical properties. The results are shown in Table 1. According to Table 1, it can be seen that the deviation of MI value and melting point is large.

Embodiment 6-10

Polybutylene terephthalate (PBT, melting point 228° C., number average molecular weight 35,000, acid value 0.8 mg-KOH/g) melted in a single-screw extruder was fed to the static mixer at a constant speed with a gear pump (manufactured by Sulzer Company, trade name "SMXL", inner diameter 3.8 cm, length 798 cm, 72 mixing elements inside), supply the lactone combination obtained in Production Example 1 to the above static mixer at a constant speed by a plunger pump product (a mixed liquid containing ε-caprolactone (CLM) as the main component), thereby continuously obtaining a polyester block copolymer. The reaction temperature is 235° C., the pressure on the input side of the gear pump is 0.196 MPa (gauge pressure), and the feed pressure of the above-mentioned lactone composition is 15.68 MPa (gauge pressure). The pelletized polyester block copolymer was discharged from the static mixer and sampled every 15 minutes to measure its physical properties. The results are shown in Table 2. According to Table 2, it can be seen that the deviation of MI value and melting point is very small.

Example 11

Polybutylene terephthalate (PBT, melting point 228° C., number average molecular weight 35,000, acid value 0.8 mg-KOH/g) melted in a single-screw extruder was fed to the static mixer at a constant speed with a gear pump A device (manufactured by Sulzer Company, trade name "SMXL", inner diameter 3.8 cm, length 798 cm, 72 mixing elements inside), feeds ε-caprolactone (CLM) into the above-mentioned static mixer at a constant speed through a plunger pump, Thereby the polyester block copolymer is continuously obtained. The reaction temperature is 235° C., the pressure on the input side of the gear pump is 0.196 MPa (gauge pressure), and the feed pressure of ε-caprolactone is 15.68 MPa (gauge pressure). The pelletized polyester block copolymer was discharged from the static mixer and sampled every 15 minutes to measure its physical properties. The results are shown in Table 2. According to Table 2, it can be seen that the deviation of MI value and melting point is very small. In addition, compared with Example 6, the melting point of the polyester block copolymer obtained in Example 11 is lower. In Example 6, the lactone composition obtained in Production Example 1 was used instead of ε-caprolactone (CLM). , implemented under the same conditions as in Example 11.

[Table 1]

[Table 2]

Industrial Applicability

According to the production method of the present invention, a polyester block copolymer of constant quality can be efficiently produced industrially by reacting a crystalline aromatic polyester with a lactone.

Claims (7)

1, the manufacture method of polyester block copolymer, this method comprises: by toothed gear pump with fused crystalline aromatic polyester (A) and by pump of constant delivery type with lactone (B1) or lactone composition (B2), be supplied in static mixer continuously with constant speed respectively, react and obtain polyester block copolymer.

2, as the manufacture method of the polyester block copolymer of record in the claim 1, wherein crystalline aromatic polyester (A1) and the lactone (B1) of acid number greater than 2mg-KOH/g reacted.

3, as the manufacture method of the polyester block copolymer of record in the claim 1, wherein crystalline aromatic polyester (A2) and the lactone composition (B2) of acid number below 2mg-KOH/g reacted.

4, as the manufacture method of the polyester block copolymer of record in the claim 3, wherein lactone composition (B2) contains lactone (B1) and bi-ester of phosphite (C).

5, as the manufacture method of the polyester block copolymer of record in the claim 4, wherein lactone composition (B2) also contains at least a compound that is selected from acid phosphoric acid ester (D) and the tin compound (E).

6, as the manufacture method of the polyester block copolymer of any one record in the claim 1～5, wherein toothed gear pump input side pressure be 0.0098MPa (gauge pressure) with on supply with crystalline aromatic polyester (A).

7, as the manufacture method of the polyester block copolymer of any one record in the claim 1～6, wherein the feed pressure of lactone (B1) or lactone composition (B2) is adjusted into more than the 1.96MPa (gauge pressure).