JP2012111789A - Method for producing aromatic polyester ether - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a polyester having an ether bond in the main chain in a usual method for producing a polyester, without requiring any complicated operation and without using a monomer having an ether bond.SOLUTION: In the method for producing an aromatic polyester ether, a diol component of a phenylene group, a naphthalenediyl group, a biphenylene group, or a bisphenylene group, protected with an acetoxy group, is used in a situation in which a glycol component exists more than 2.5 times in terms of molar ratio, as a copolymerization component, when the aromatic polyester is produced from an aromatic dicarboxylic acid and an alkylene glycol.

Description

  The present invention relates to a method for producing a novel aromatic polyester ether.

  Aromatic polyesters typified by polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), etc., today, due to their excellent physical and chemical properties, fibers, films or molded products Widely used in applications.

  Although it is an excellent aromatic polyester as described above, there is a problem in durability in that the intrinsic viscosity tends to decrease due to hydrolysis. One of the causes is a structural problem that the ester bond portion easily reacts with water. As a solution, there is a method of copolymerizing units such as an ether bond that does not easily react with water, For example, a method in which a long glycol is used to expand the ester bond is used. When the modification by copolymerization of these third components is performed, it is relatively easy to introduce a long-chain glycol component or the like into the main chain through an ester bond. However, in order to introduce an ether bond into the main chain, it is necessary to prepare a monomer body having an ether bond, etc., and it is easy to produce in a transesterification reaction / polycondensation reaction in a normal polyester production method. It's hard to say.

  In fact, as a method for producing polyester ether, there are reports that a glycol component having an ether bond such as polypropylene glycol (Patent Document 1) and poly (tetramethylene oxide) glycol (Patent Document 2) is used as a raw material in advance. No examples have been reported starting from the missing raw materials.

  Patent Document 3 reports a method for synthesizing a biphenol derivative to which ethylene glycol is added. If this product is used as a raw material, it is possible to introduce an ether-linked polymer main chain, but if you want to change the hydrocarbon length or the type of aromatic ring, you must start by synthesizing the original structure, making it difficult to use. There is.

Japanese translation of PCT publication No. 8-511578 JP 2010-24328 A JP-A-10-330306

An object of the present invention is to provide an aromatic polyester ether by an ordinary polyester polymerization method without using a structure having an ether bond as a raw material. Another object of the present invention is to change the alkyl chain length, the number / shape of the aromatic ring, and the copolymerization rate by an ether bond by a simple method that does not require resynthesis of raw materials but only changes the charged components. It is to change the combination of connected molecules.
Furthermore, another object of the present invention is to impart crystallinity to the aromatic polyester ether obtained.

  As a result of diligent research to solve the above-mentioned problems, the inventors of the present invention copolymerized an acetoxy-protected aromatic diol in the presence of a specific amount or more of a glycol component, thereby obtaining an ether in a normal polyester polymerization method. The inventors have found that an aromatic polyester ether resin having a bond can be provided, and have reached the present invention.

Thus, according to the present invention, an acetoxy-protected aromatic diol component represented by the following formula (I) is converted into an aromatic dicarboxylic acid component represented by the following formula (II) and a glycol component represented by the following formula (III): A process for producing an aromatic polyester ether to be reacted,
Aromatic polyester having a molar ratio of 2.5 or more in terms of the proportion of glycol represented by the following formula (III) with respect to the ratio of the acetoxy-protected aromatic diol component represented by the following formula (I) A method for producing ethers is provided.

（ここで、Ｒ^１は、炭素数１〜４のアルキル基、Ｒ^２は、水素または炭素数１〜４のアルキル基Ｒ^３は炭素数１〜２のアルキレン基、Ｘは単結合、シクロアルキレン基、フェニレン基、ナフタレンジイル基、Ｐｈ^１およびＰｈ^２は、以下の式（ＩＶ）〜（ＶＩＩ）のいずれかを表す。）

(Where R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² is hydrogen or an alkyl group having 1 to 4 carbon atoms R ³ is an alkylene group having 1 to 2 carbon atoms, X is a single bond, cycloalkylene Group, phenylene group, naphthalenediyl group, Ph ¹ and Ph ² represent any of the following formulas (IV) to (VII).)

（ここで、上記構造式〔ＩＶ〕〜〔ＶＩＩ〕中のＲ^４は炭素数１〜１２のアルキル基またはアルケニル基を示し、ｍは０〜２の整数を示し、Ｒ^５は炭素数１〜１２のアルキレン基、スルホニル基、チオール基、オキソ基、ホスホニル基、シクロアルキレン基、フルオレン基、ジオキシインダン基を示す。）

(Here, R ⁴ in the structural formulas [IV] to [VII] represents an alkyl group or alkenyl group having 1 to 12 carbon atoms, m represents an integer of 0 to 2, and R ⁵ represents 1 to C carbon atoms. 12 represents an alkylene group, a sulfonyl group, a thiol group, an oxo group, a phosphonyl group, a cycloalkylene group, a fluorene group, and a dioxyindane group.)

Further, according to the present invention, as a preferred embodiment of the present invention, the ratio of the acetoxy-protected aromatic diol component represented by the above formula (I) is the mole of the aromatic dicarboxylic acid component represented by the above formula (II). The aromatic dicarboxylic acid component represented by the above formula (II) is in the range of 1 to 99 mol% based on the number, and the ratio of the acetoxy-protected aromatic diol component represented by the above formula (I) Of the aromatic polyester ether in which Ph ¹ in the above formula (I) is at least one selected from the group consisting of the above formulas (IV) to (VI), based on the number of moles of A manufacturing method is also provided.

  According to the present invention, by using an acetoxy-protected aromatic diol, an aromatic polyester ether is provided by a normal polyester polymerization method without using a structure having an ether bond as a raw material. Can do. In addition, according to the present invention, when it is desired to change the alkyl chain length, the number / shape of the aromatic ring, and the copolymerization rate, it is not necessary to re-synthesize the raw material, and by an easy method of changing the charged components, an ether bond can be obtained. It is also possible to easily change the combination of connected molecules.

  Moreover, the obtained aromatic polyester ether has improved hydrolysis resistance by introducing an ether bond into the polymer main chain. Furthermore, the aromatic polyester ether obtained can be provided with crystallinity by adjusting the kind and copolymerization amount of the aromatic diol protected with acetoxy.

  The method for producing an aromatic polyester ether of the present invention comprises an acetoxy-protected aromatic diol component represented by the following formula (I), an aromatic dicarboxylic acid component represented by the following formula (II), and the following formula (III). It is a manufacturing method of the aromatic polyester ether made to react with the glycol component shown, Comprising: It is a manufacturing method which makes the ratio of this glycol component 2.5 times or more with respect to the ratio of this aromatic diol.

（ここで、Ｒ^１は、炭素数１〜４のアルキル基、Ｒ^２は、水素または炭素数１〜４のアルキル基Ｒ^３は炭素数１〜２のアルキレン基、Ｘは単結合、シクロアルキレン基、フェニレン基、ナフタレンジイル基、Ｐｈ^１およびＰｈ^２は、以下の式（ＩＶ）〜（ＶＩＩ）をいずれかを表す。）

(Where R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² is hydrogen or an alkyl group having 1 to 4 carbon atoms R ³ is an alkylene group having 1 to 2 carbon atoms, X is a single bond, cycloalkylene Group, phenylene group, naphthalenediyl group, Ph ¹ and Ph ² represent any of the following formulas (IV) to (VII).)

（ここで、上記構造式〔ＩＶ〕〜〔ＶＩＩ〕中のＲ^４は炭素数１〜１２のアルキル基またはアルケニル基を示し、ｍは０〜２の整数を示し、Ｒ^５は炭素数１〜１２のアルキレン基を示す。）

(Here, R ⁴ in the structural formulas [IV] to [VII] represents an alkyl group or alkenyl group having 1 to 12 carbon atoms, m represents an integer of 0 to 2, and R ⁵ represents 1 to C carbon atoms. 12 alkylene groups are shown.)

One of the characteristics of the present invention is that an ether bond is copolymerized in the main chain in a normal polyester synthesis reaction using a raw material having no ether bond represented by the above formula (I). .
Examples of the preferred acetoxy-protected aromatic diol component represented by the above formula (I) in the present invention include biphenol, dihydroxyphenyl (hydroquinone), dihydroxynaphthyl, and bisphenol whose ends are protected with an acetoxy group. Among these, since the aromatic polyester ether obtained has crystallinity, it is easy to improve hydrolysis resistance and the like, so that 4,4′-diacetoxybiphenyl, 1,4-diacetoxyphenyl, 2,6 -Diacetoxynaphthyl is preferably mentioned.

  When biphenol, dihydroxyphenyl (hydroquinone), or dihydroxynaphthyl that is not protected by an acetoxy group is used, the hydroxyl group directly bonded to the aromatic ring is poorly reactive and is difficult to enter the main chain. Also, glycols such as ethylene glycol The reaction of forming an ether bond between the component and the glycol component hardly occurs. Incidentally, even if an ether bond is formed, its formation probability is much lower than the formation probability of by-products such as diethylene glycol, and it cannot be said to be a copolymer.

  The ether conjugate produced in the reaction system of the present invention can be obtained by reacting, for example, diacetoxybiphenyl / diacetoxyphenyl / diacetoxynaphthyl and ethylene glycol under the same temperature, atmosphere, and reaction time conditions as those in normal polyester polymerization conditions. It is not produced, and the coexistence of the dicarboxylic acid represented by the above formula (II) or its ester derivative is necessary.

  Preferred aromatic dicarboxylic acids represented by the above formula (II) or ester derivatives thereof in the present invention include terephthalic acid, dimethyl terephthalate, 2,6-naphthalenedicarboxylic acid, methyl 2,6-naphthalenedicarboxylate, 4,4 '-Biphenylenedicarboxylic acid, dimethyl 4,4'-biphenylenedicarboxylate and the like can be mentioned, and dimethyl terephthalate and methyl 2,6-naphthalenedicarboxylate are particularly preferable.

  In the present invention, the ratio of the acetoxy-protected diol component represented by the above formula (I) is in the range of 1 to 99 mol% based on the number of moles of the aromatic dicarboxylic acid component represented by the above formula (II). It is preferable. In particular, the aromatic polyester ether obtained is preferably 60 mol% or less because it is likely to have a sufficiently high intrinsic viscosity by melt polymerization, and from the viewpoint of providing crystallinity, it is preferably 50 mol% or less. On the other hand, the lower limit is not particularly limited, but is preferably 1 mol% or more, more preferably 10 mol% or more, even more preferably 20 mol% or more, and particularly preferably 30 mol% or more because hydrolysis resistance is easily improved. .

  In the production method of the present invention, a glycol component represented by the above formula (III) is further required. Preferred glycol components represented by the above formula (III) include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol, bisphenoxyethanol, and xylene glycol. Among these, it is preferable because the resin from which ethylene glycol is obtained has crystallinity and is easily provided with a film forming property.

  By the way, in the production method of the present invention, an ether bond is formed between the acetoxy-protected aromatic diol component represented by the formula (I) and the glycol component represented by the formula (III). As for the ratio of both (the above formula (I) and the above formula (III)), the higher the ratio of the glycol component represented by the above formula (III), the higher the ether bond introduction rate. Theoretically, the ratio of the ether bond is the highest when the ratio of the formula (I) to the formula (III) is 1: 2. If the ratio of the aromatic diol component represented by the above formula (I) is excessive, the excess forms an ester bond with the acid component of (II) by an acidolysis reaction and efficiently introduces an ether bond. I can't. From such a viewpoint, the lower limit of the proportion of the glycol component represented by the formula (III) is 2.5 times or more with respect to the acetoxy-protected aromatic diol component represented by the formula (I). It is necessary to be 3 times or more, more preferably 3.5 times or more. On the other hand, the upper limit is not particularly limited, but is preferably 200 times from the viewpoint of productivity.

  It is preferable to add the acetoxy-protected aromatic diol component represented by the above formula (I) together with other raw materials / catalysts at the start of the esterification reaction or transesterification reaction in order to improve the copolymerization rate. .

  Although the acetoxy-protected aromatic diol component represented by the above formula (I), which is an important component for forming an ether bond in the present invention, can be purchased, it is relatively simple with an inexpensive material. It can be synthesized. For example, acetic anhydride is added dropwise at room temperature under basic conditions to biphenol, hydroquinone or binaphthol, and the white crystals obtained after stirring for about 30 minutes may be filtered and washed with water.

  Incidentally, Patent Document 3 reports a method for synthesizing a structure in which ethylene glycol is added to both ends of biphenol. Even when this structure is used as a part of the glycol component, a polyester ether having the same unit as in the present study can be obtained. However, this structure manufacturing method is described in Comparative Examples 1 and 5. However, as the reaction progresses, the phenomenon that the product precipitates and solidifies occurs, and when the reaction proceeds about 90%, it is taken out and crushed. A process for cleaning is required, and productivity is difficult.

  Further, the structure in which ethylene glycol is added to both ends of the hydroquinone of Reference Example 5 is less efficient than the method of the present invention because the yield is as low as 76% and it takes time to remove by-products. From another viewpoint, in the structure of Patent Document 3, both ends of the aromatic glycol are ethylene glycol. If you want something with trimethylene glycol or tetramethylene glycol at both ends, you must start by synthesizing the raw materials. In that case, it is compoundable by the method of the reference examples 6 and 7, for example. However, since the process of synthesizing raw materials increases, it takes time to obtain the target polymer, and the yield of raw material synthesis is poor, which is not economically preferable.

In the production method of the present invention, raw materials of the above formulas (I), (II) and (III) are prepared, and a reaction product obtained by esterifying and / or transesterifying them is further polycondensed. Can be manufactured. In that case, a known catalyst can be suitably used for each of those reactions. For example, the catalyst for transesterification includes alkaline earth metal compounds such as magnesium acetate, alkali metal compounds, titanium compounds and manganese acetate, and the polycondensation reaction catalysts include titanium compounds, antimony dioxide, germanium dioxide and the like. Is mentioned. Moreover, in order to improve the heat resistance of the aromatic polyester ether obtained, a phosphorus compound known per se may be added as a stabilizer, and among the phosphorus compounds, it is particularly preferable to use a phosphonate compound.
According to the present invention, an ether bond can be introduced into the resulting polymer in a normal polyester production method, while using a raw material having no ether bond.

Next, the aromatic polyester ether obtained by the production method of the present invention will be described.
The aromatic polyester ether obtained by the production method of the present invention comprises a repeating unit of an aromatic dicarboxylic acid and a diol component obtained by adding an alkylene glycol component to an aromatic diol, and a repeating unit of an aromatic dicarboxylic acid and an alkylene glycol. The main repeating unit. The aromatic polyester ether of the present invention has an intrinsic viscosity of 0.3 dl / g or more when measured at 40 ° C. using a mixture of phenol and 2,4,6-trichlorophenol at a weight ratio of 3: 2 as a solvent. In particular, it is preferably 0.4 dl / g or more. Moreover, the upper limit of the intrinsic viscosity is not particularly limited, but it is desirable not to exceed 1.0 dl / g so as not to impair the uniformity of thickness during extrusion. If the aromatic polyester ether has a high melt viscosity and it is difficult to reach the target intrinsic viscosity only by melt polymerization, solid phase polymerization may be carried out after the melt polymerization.

  Of course, the aromatic polyester ether obtained by the production method of the present invention is copolymerized with components known per se or inactive particles within the range that does not impair the effects of the present invention in consideration of the handleability of the molded product. (Inorganic particles, organic particles, etc.) and various functional agents (for example, plasticizers, weathering agents, antioxidants, heat stabilizers, lubricants, antistatic agents, whitening agents, colorants, conductive agents), etc. Other polymers may be used as a composition in which a small amount, for example, 20% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less is mixed.

  Hereinafter, the present invention will be described more specifically based on examples which are examples of the present invention. In addition, the measurement and evaluation of each characteristic in an Example are as follows.

(1) Intrinsic viscosity The polymer obtained was dissolved in a solution in which phenol and 2,4,6-trichlorophenol were mixed at a weight ratio of 3: 2, and measured at 40 ° C. The unit is dl / g.

(2) Quantification of introduction rate of ether bond into polymer main chain The obtained polymer was dissolved in deuterated trifluoroacetic acid / deuterated chloroform = 1/1 mixed solvent and esterified using NMR JEOL A-600 manufactured by JEOL. The copolymerization rate was calculated from the integration of each peak of the bond and the ether bond. That is, the ether bond / (ester bond and ether bond) was defined as the ether bond introduction rate.

(3) Melting point (Tm)
Using a thermal differential analyzer DSC2920 manufactured by TA Instruments, the chip 10 mg was heated to 300 ° C. at 20 ° C./min, and the melting peak temperature (Tm) was determined.

(4) Moisture and heat resistance test In this test, a test film was prepared and evaluated by the following method as a simple evaluation.
30 g of polymer chips are dried in a dryer at 140 ° C. for 4 hours. The chip was placed on a hot plate set at a melting point + 20 ° C., melted, and pressed to form a square test piece having a length and width of 100 mm square to obtain a film-like molded body.
This was processed for 30 hours in an autoclave under a saturated vapor pressure of 140 ° C., and the intrinsic viscosity after the treatment was divided by the intrinsic viscosity before the treatment to obtain the intrinsic viscosity retention after the treatment. If this value was 70% or more, the water resistance under wet heat was considered good.

[Reference Example 1] Synthesis method of biphenol (diacetoxybiphenyl) whose both ends are acetoxy-protected Synthesis was performed with reference to SYNTHETIC COMMUNICATIONS 22 (18), 2703-2710, 1992.
Specifically, a reactor equipped with a stirrer was charged with 50 g of biphenol, 1.3 liters of isopropyl alcohol, and a sodium hydroxide solution (a solution obtained by adding 29.4 g of sodium hydroxide to 250 ml of water) 75.1 g of acetic anhydride was added dropwise thereto and then reacted at 30 ° C. for 30 minutes.
After completion of the reaction, isopropyl alcohol was distilled off with an evaporator. Acetic acid was added to the resulting reaction solution, acidified, washed and dried to obtain the desired compound. The yield of the obtained diacetoxybiphenyl was 90% by mass. The results are shown in Table 1.

[Reference Example 2] Synthesis method of hydroquinone (diacetoxyphenyl) in which both ends are acetoxy-protected In Reference Example 1, the same operation was repeated except that 30 g of hydroquinone was used instead of 50 g of biphenol. The results are shown in Table 1.

[Reference Example 3] Method for synthesizing 2,6-naphthalenediol (diacetoxynaphthyl) having both ends protected with acetoxy In Reference Example 1, 43 g of 2,6-naphthalenediol was used instead of 50 g of biphenol. Similar operations were repeated. The results are shown in Table 1.

[Reference Example 4]
(1) Synthesis method of ether structure (BP-2EG) in which ethylene glycol is added to both ends of biphenol Synthesis was performed with reference to Example 1 of Patent Document 3. Specifically, 18.6 g (0.1 mol) of biphenol and 100 g of ethylene glycol were charged into a four-necked flask, and after substitution with N ₂ , 9.0 g of 30% sodium methylate (0 .05 mol) was added dropwise. Thereafter, the temperature was raised to 100 ° C., and 36.6 g (0.4 mol) of dimethyl carbonate was added dropwise over 20 minutes to react. Stirring was carried out for 6 hours while distilling the produced methanol in order to keep the temperature at 100 ° C. Crystals precipitated gradually during stirring. Water was added to the obtained crystals and washed with water, and the pH was adjusted to 7, followed by filtration to synthesize 4,4′-di (2-hydroxy-ethoxy) biphenyl. The results are shown in Table 1.

[Reference Example 5] Synthesis method of ether structure (HQ-2EG) in which ethylene glycol was added to both ends of hydroquinone In Reference Example 4, instead of 18.6 g (0.1 mol) of biphenol, hydroquinone 11. The same operation was repeated except that 0 g (0.1 mol) was used. The results are shown in Table 1.

[Reference Example 6] Synthesis method of ether structure (BP-2 (C3G)) in which trimethylene glycol is added to both ends of biphenol. In a reactor equipped with a stirrer, a rectifying column and a condenser, 50 g of biphenol, carbonic acid 3.7 g of potassium, 26.7 g of 1-chloropropanol and 0.5 L of N, N-dimethylformamide (DMF) are charged and reacted for 10 hours under reflux. Extraction, washing, and drying gave the desired product. The results are shown in Table 1.

[Reference Example 7] Synthesis method of ether structure (HQ-2 (C3G)) in which trimethylene glycol was added to both ends of hydroquinone The same operation was repeated except that hydroquinone was used instead of biphenol in Reference Example 6. . The results are shown in Table 1.

The reaction conditions and yield of each monomer synthesis were shown.
In Table 1, AcBP is 4,4'-diacetoxybiphenyl, AcHQ is 1,4-diacetoxyphenyl, AcNP is 2,6-diacetoxynaphthyl, and BP-2EG is ethylene glycol at both ends of biphenol. Added ether structure, HQ-2EG is an ether structure in which ethylene glycol is added to both ends of hydroquinone, BP-2 (C3G) is an ether structure in which trimethylene glycol is added to both ends of biphenol, HQ-2 ( C3G) means an ether structure in which trimethylene glycol is added to both ends of hydroquinone. The reaction time and reaction temperature in Table 1 are the time required for the reaction and the temperature maintained, respectively. t means room temperature.

[Example 1]
In a transesterification reactor equipped with a stirrer, a rectifying column and a condenser, with respect to 100 mol of methyl 2,6-naphthalenedicarboxylate, 180 mol of ethylene glycol, 30 mol of diacetoxybiphenyl prepared in Reference Example 1, titanium After feeding 30 mmol of tetrabutyrate, transesterification was carried out at 210 ° C. while continuously distilling the produced methanol and acetic acid out of the reaction system. To the reaction product thus obtained, 60 mmol of antimony dioxide was added, and then the polycondensation reaction was carried out by reducing the pressure to 0.2 mmHg while raising the temperature to 280 ° C. while continuously distilling ethylene glycol. An aromatic polyester ether of 0.50 dl / g was obtained.
The obtained aromatic polyester ether was extruded as a strand having an elliptical cross section of 2 mm in length and 4 mm in width, cooled with water, then cut into a length of 4 mm, and an aromatic polyester having an average mass of 30 to 35 mg per grain. Ether chips were used.
The obtained aromatic polyester ether chips were dried at 190 ° C. for 2 hours, then supplied to a melt-kneading extruder, heated to 260 ° C. to be in a molten state, on a cooling drum rotating in a die-shaped sheet shape To obtain an unstretched sheet.
The unstretched sheet thus obtained was stretched 3.5 times in the film forming direction at 140 ° C., and then stretched 3.0 times in the width direction at 140 ° C. In this stretching step, it was confirmed that the film was not broken and had good stretchability. Thereafter, the obtained stretched film was heat treated at 200 ° C. for 5 seconds to obtain a biaxially stretched film having a thickness of 200 μm.
Table 2 shows the characteristics of the obtained aromatic polyester ether and the biaxially oriented film.

[Examples 2 to 7]
Aromatic polyester ether, aromatic polyester ether chip and the same as in Example 1 except that the types and amounts of the acetoxy-protected aromatic diol component and acid component and other glycol components are changed as shown in Table 1. A biaxially oriented film was obtained.
Table 2 shows the characteristics of the obtained aromatic polyester ether and the biaxially oriented film.

[Comparative Example 1]
In a transesterification reactor equipped with a stirrer, a rectifying column and a condenser, with respect to 100 mol of methyl 2,6-naphthalenedicarboxylate, 180 mol of ethylene glycol, the ether structure prepared in Reference Example 4 (BP- 2EG) After supplying 30 mol and 20 mmol of titanium tetrabutyrate, an ester exchange reaction was carried out at 210 ° C. while continuously distilling the produced methanol out of the reaction system. To the reaction product thus obtained, 60 mmol of antimony dioxide was added, and then the polycondensation reaction was carried out by reducing the pressure to 0.2 mmHg while raising the temperature to 280 ° C. while continuously distilling ethylene glycol. An aromatic polyester ether of 0.50 dl / g was obtained.
The obtained aromatic polyester ether was extruded as a strand having an elliptical cross section of 2 mm in length and 4 mm in width, cooled with water, then cut into a length of 4 mm, and an aromatic polyester having an average mass of 30 to 35 mg per grain. It was a chip. The obtained aromatic polyester ether was a crystalline polymer. And it carried out similarly to Example 1, and obtained the biaxially oriented film.
Table 2 shows the characteristics of the obtained aromatic polyester ether and the biaxially oriented film.

[Comparative Example 2]
In Comparative Example 1, aromatic polyester ether and aromatic polyester ether chips were obtained in the same manner except that the ratio was changed as shown in Table 1. And the operation similar to Example 1 was repeated and the biaxially oriented film was obtained.
Table 2 shows the characteristics of the obtained aromatic polyester ether and the biaxially oriented film.

[Comparative Example 3]
In Example 1, the charging ratio of diacetoxybiphenyl and ethylene glycol was changed as shown in Table 1. However, the unreacted portion of diacetoxybiphenyl was decomposed and the viscosity did not increase. Therefore, subsequent evaluation was not performed.
The properties of the obtained aromatic polyester ether are shown in Table 2.

[Comparative Example 4]
In Example 1, the charge ratio of diacetoxybiphenyl was changed as shown in Table 1. However, methyl 2,6-naphthalenedicarboxylate and diacetoxybiphenyl caused an acidolysis reaction, resulting in a liquid crystalline high melting point product, and film formation was impossible.
The properties of the obtained aromatic polyester ether are shown in Table 2.

  In Table 2, AcBP is 4,4'-diacetoxybiphenyl, AcP is 1,4-diacetoxyphenyl, AcNP is 2,6-diacetoxynaphthyl, and BP-2EG is 4,4'-di (2-hydroxy). -Ethoxy) biphenyl, NDC means dimethyl naphthalenedicarboxylate, DMT means dimethyl terephthalate.

  Since the aromatic polyester ether resin composition of the present invention can introduce an ether bond into the main chain by an ordinary polyester production method without complicated operations and the use of molecules having an ether bond, it is one of the effective polyester modifying means. It can be used as one.

Claims (3)

An aromatic polyester ether obtained by reacting an acetoxy-protected aromatic diol component represented by the following formula (I) with an aromatic dicarboxylic acid component represented by the following formula (II) and a glycol component represented by the following formula (III): A manufacturing method comprising:
The glycol composition ratio represented by the following formula (III) is 2.5 times or more in molar ratio with respect to the ratio of the acetoxy-protected aromatic diol component represented by the following formula (I). A method for producing an aromatic polyester ether.

Wherein R ¹ and R ² are alkyl groups having 1 to 4 carbon atoms, R ³ is an alkylene group having 1 to 2 carbon atoms, X is a single bond, a cycloalkylene group, a phenylene group or a naphthalenediyl group, Ph ¹ And Ph ² represents any of the following formulas (IV) to (VII).)

(Here, R ⁴ in the structural formulas [IV] to [VII] represents an alkyl group or alkenyl group having 1 to 12 carbon atoms, m represents an integer of 0 to 2, and R ⁵ represents 1 to C carbon atoms. 12 alkylene groups are shown.)   The ratio of the acetoxy-protected aromatic diol component represented by the formula (I) is in the range of 1 to 99 mol% based on the number of moles of the aromatic dicarboxylic acid component represented by the formula (II). Item 2. A process for producing an aromatic polyester ether according to Item 1. The ratio of the acetoxy-protected aromatic diol component represented by the formula (I) is in the range of 1 to 50 mol% based on the number of moles of the aromatic dicarboxylic acid component represented by the formula (II), and The method for producing an aromatic polyester ether according to claim 1, wherein Ph ¹ in the formula (I) is at least one selected from the group consisting of the formulas (IV) to (VI).