JP5351612B2 - Polyester, production method thereof, and molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new polyester resin usable for producing a molded article excellent in quality stabilization by virtue of a higher polymerization degree, and a method for producing the same. <P>SOLUTION: The polyester resin includes a structural unit represented by formula (1) and has a number-average molecular weight of 110,000-190,000, wherein R denotes an aromatic hydrocarbon group which may be substituted or an aliphatic hydrocarbon group which may be substituted. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

The present invention, various resin materials useful polyester Le, its manufacturing method, and a molded article.

Polyester is excellent in physical properties such as mechanical strength and chemical properties, and has excellent processing properties such as injection molding and extrusion molding. Therefore, it can be used in various fields and is being developed as various engineering plastics. .
As a method for producing polyester, a method in which a glycol ester is obtained by esterification reaction of dicarboxylic acid and glycol or ester exchange reaction of alkyl ester of dicarboxylic acid and glycol, and polycondensation thereof is widely used industrially. It has been adopted. To be used as an engineering plastic, it is necessary to have excellent mechanical properties such as strength. When a polyester is produced through a transesterification reaction, the glycol ester polycondensation is heated and stirred under a high vacuum. Therefore, to obtain a highly polymerized polyester, it is necessary to keep the high vacuum for a long period of time, which is simpler. New manufacturing methods are required.
Improvement of the method for manufacturing a high polymerization degree polyesters, in particular the degree of polymerization has been reported high polymerization degree polyester Le of 185-600 (Patent Document 1).

JP 2007-146153 A

In Patent Document 1, a polymer compound having a skeleton structure containing a furan ring and having excellent moldability and mechanical strength is obtained by regulating the degree of polymerization (number of repeating units). However, the polyester Le disclosed in Patent Document 1, a high polymerization degree improvement of quality stabilization by reduction is not always sufficient, in order to expand the variety of applications is further improvement of the high degree of polymerization Is required.
The present invention has been made in view of such background art, it can be used to produce a molded article having excellent quality stabilized by high polymerization degree, the production of novel polyester Le及 benefactor A method is provided. Further, the present invention is to provide a simple manufacturing process than can be produced the polyester Le.

式中、Ｒはエチレン基を示す。
Polyester which solves said subject consists of a structural unit (repeating unit) represented by following formula (1), and has a number average molecular weight of 110,000 to 190,000.

In the formula, R represents an ethylene group .

Further, the molded article to solve the above problem is characterized by being obtained by molding the composition for a molded article comprising the above polyester Le.
A method of manufacturing a polyester Le solving the aforementioned problem, a flange carboxylic acid or its ester, ethylene glycol, 1,3-propanediol, at least one esterification selected from the group consisting of 1,4-butanediol Or it has the process of transesterification, and the process of superposition | polymerization, and is characterized by the presence of dimethyl sulfoxide (DMSO) in the case of esterification or transesterification, and in the case of superposition | polymerization.

The present invention is excellent in quality stabilization has high polymerization degree can provide polyester Le及 originator manufacturing method is suitable for various molded articles produced material.
The present invention, by using the above polyester Le, can provide excellent various molded articles in stable quality.

Is a diagram showing a spectrum due polyester Le proton nuclear magnetic resonance spectroscopy (1H-NMR) measurements of Example 1 of the present invention. It is a diagram showing a spectrum obtained by IH-NMR measurement of the polyester Le Example 2 of the present invention.

（式中、Ｒは置換されていてもよい芳香族炭化水素基又は置換されていてもよい脂肪族炭化水素基を示す。）
フラン環を有するポリエステルの数平均分子量を１１万〜１９万に高重合度化させた時、品質安定化できる。
式（１）中のＲはエチレン基であることが好ましい。
また、上記ポリエステルを成形品用組成物として用いると品質安定性に優れた成形品となることを見出した。 Hereinafter, the present invention will be described in detail.
The present inventors have made intensive studies, as a result, has a structural unit represented by the following formula (1), depending on the number-average molecular weight of from 110,000 to 190,000 polyester Le, found that the object can be achieved, the present The invention has been completed.

(In the formula, R represents an optionally substituted aromatic hydrocarbon group or an optionally substituted aliphatic hydrocarbon group.)
When the number average molecular weight of polyester Le having a furan ring were highly polymerized into 110000-190000 be stable quality.
R in the formula (1) is preferably an ethylene group.
Also found that the use the molded article having excellent quality stability the polyester Le as composition for a molded article.

Method for producing a polyester Le according to the present invention, a flange carboxylic acid or its ester, ethylene glycol, 1,3-propanediol, with at least one esterification or transesterification is selected from the group consisting of 1,4-butanediol Characterized in that DMSO is present during esterification or transesterification and during polymerization.
Further, at the time of polymerization of the polyester Le, by adding DMSO, and dispersed polyester Le is in DMSO, and it found that the high polymerization degree is readily proceeds. Further, high viscosity during polymerization of the resin is suppressed, high polymerization degree was polyester Le was obtained a finding that can be manufactured easily.
DMSO is preferably added simultaneously with furandicarboxylic acid, dihydric alcohol and catalyst, since furancarboxylic acid dissolves in DMSO and the reaction proceeds uniformly.

  As the dicarboxylic acid having a furan ring, 2,5-furandicarboxylic acid can be used as a raw material. As the 2,5-furandicarboxylic acid, those obtained by conversion from biomass such as cellulose, glucose, fructose, and mucic acid by a known method can be used. Therefore, when a furan ring is used, a plant-derived material can be used as an aromatic ring that contributes to heat resistance.

  R in the formula (1) represents an aromatic hydrocarbon group or a linear or cyclic aliphatic hydrocarbon group, which may have a substituent. Examples of the aromatic hydrocarbon group include a benzene ring, a biphenyl ring and a bis (phenyl) alkane, a condensed ring such as a naphthalene ring, an indene ring, an anthracene ring and a phenanthrene ring, and a divalent group of a heterocyclic ring. Can do. Examples of the bis (phenyl) alkane include bis (2-hydroxyphenyl) methane and 2,2'-bis (hydroxyphenyl) propane. On the other hand, examples of the heterocyclic ring include five-membered rings such as furan, thiophene, pyrrole, oxazole, thiazole, and imidazole. Six-membered rings such as pyran, pyridine, pyridazine, pyrimidine, pyrazine. Examples thereof include condensed rings such as indole, carbazole, coumarin, quinoline, isoquinoline, acridine, benzothiazole, quinoloxane, and purine.

Examples of the linear aliphatic hydrocarbon group include an ethylene group, a propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, and an n-heptylene group. Among these, a linear alkylene group having 2 to 4 carbon atoms of an ethylene group, a propylene group, and an n-butylene group is preferable, and an ethylene group and an n-butylene group can be particularly preferable.
The molecular weight of the polyester Le of the present invention, in 1,1,1,3,3,3-hexafluoro-2-propanol molecular weight determined by gel permeation chromatography (GPC) dissolved in (HFIP), number average The molecular weight is 100,000 to 500,000, preferably 110,000 to 190,000. This molecular weight range is preferable because it exhibits excellent quality stability and is easy to mold.

Polyester Le having a structural unit represented by the formula (1) of the present invention is a polyhydric alcohol excess under ethylene glycol, 1,3-propanediol, at least one selected from the group consisting of 1,4-butanediol The furandicarboxylic acid or its ester can be obtained by polycondensation in the presence of DMSO.
Specific examples of the dicarboxylic acid having a furan ring include 2,5-furandicarboxylic acid, 2,4-furandicarboxylic acid, and 3,4-furandicarboxylic acid. In particular, it is preferable to use 2,5-furandicarboxylic acid. As the 2,5-furandicarboxylic acid, those obtained by conversion from biomass such as cellulose, glucose, fructose, and mucic acid by a known method can be used. Therefore, the ratio of plant-derived raw materials can be increased by using 2,5-furandicarboxylic acid synthesized by converting plant-derived raw materials as dicarboxylic acids. These can also be used 1 type or in combination of 2 or more types.

Examples of the ester of furandicarboxylic acid include methyl ester and ethyl ester of dicarboxylic acid having the furan ring mentioned above. Specifically, dimethyl 2,5-furandicarboxylate, diethyl 2,5-furandicarboxylate, ethyl methyl 2,5-furandicarboxylate, dipropyl 2,5-furandicarboxylate, dibutyl 2,5-furandicarboxylate, Examples include dimethyl 2,4-furandicarboxylate, diethyl 2,4-furandicarboxylate, dimethyl 3,4-furandicarboxylate, diethyl 3,4-furandicarboxylate, and the like. Moreover, said mixture etc. can also be mentioned.
Moreover, as a polyhydric alcohol, what is shown by following formula (2) can be mentioned.

式（２）のａは２以上の整数であればよいが、式（１）で表される構造単位を有するポリエステルを得るためには２が好ましい。式（２）のＲ’は、置換されていてもよい芳香族炭化水素基又は置換されていてもよい脂肪族炭化水素基を示す。具体的には、式（１）中のＲに関して例示した基を挙げることができる。
式（２）で示される２価のアルコールとしては、具体的には、以下のものを例示することができる。鎖状又は環状脂肪族ジオールとしてエチレングリコール、１，３−プロパンジオール、１，４−ブタンジオール、１，４−シクロヘキサンジメタノール。ジヒドロキシベンゼンとして１，３−ジヒドロキシベンゼン、１，４−ジヒドロキシベンゼン。ビスフェノールとしてビス（２−ヒドロキシフェニル）メタン、２，２’−ビス（ヒドロキシフェニル）プロパン、２，２’−ビス（４−ヒドロキシフェニル）−スルホン。グリセリン、トリメチロールプロパン、ペンタエリスリトール、ソルビトール、糖類。ヒドロキシ安息香酸。１，２−シクロヘキサンジオール、１，４−シクロヘキサンジオール、１，１−シクロヘキサンジメチロール、１，４−シクロヘキサンジメチロール等の脂環式ジオール類など。これらは適宜組み合わせて使用してもよい。
これらのうち、エチレングリコール、１，３−プロパンジオール、１，４−ブタンジオールが好ましい。ポリエステル樹脂を合成する際の重縮合反応においては、過剰な２価アルコールや重縮合が進行するにつれて生成する2価アルコールを減圧した時に留去させて反応を進行させる必要がある。エチレングリコール、１，３−プロパンジオール、１，４−ブタンジオールは他の２価のアルコールと比較して沸点が低い。そのためエチレングリコール、１，３−プロパンジオール、１，４−ブタンジオールを用いた時には過剰な２価アルコールや重縮合が進行するにつれて生成する2価アルコールを減圧した時に留去させやすく、重縮合反応を進行させて高分子量化させることが出来る。

A may be any integer of 2 or more of the formula (2), in order to obtain a polyester Le having a structural unit represented by the formula (1) is 2 is preferred. R ′ in the formula (2) represents an optionally substituted aromatic hydrocarbon group or an optionally substituted aliphatic hydrocarbon group. Specifically, the group illustrated regarding R in Formula (1) can be mentioned.
Specific examples of the divalent alcohol represented by the formula (2) include the following. As the chain or cyclic aliphatic diol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol. 1,3-dihydroxybenzene and 1,4-dihydroxybenzene as dihydroxybenzene. Bis (2-hydroxyphenyl) methane, 2,2'-bis (hydroxyphenyl) propane, 2,2'-bis (4-hydroxyphenyl) -sulfone as bisphenol. Glycerin, trimethylolpropane, pentaerythritol, sorbitol, sugars. Hydroxybenzoic acid. Alicyclic diols such as 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethylol, 1,4-cyclohexanedimethylol, and the like. You may use these in combination suitably.
Of these, ethylene glycol, 1,3-propanediol, and 1,4-butanediol are preferable. In the polycondensation reaction when synthesizing a polyester resin, it is necessary to proceed by distilling off excess dihydric alcohol or dihydric alcohol produced as polycondensation proceeds when the pressure is reduced. Ethylene glycol, 1,3-propanediol, and 1,4-butanediol have lower boiling points than other divalent alcohols. Therefore, when ethylene glycol, 1,3-propanediol, or 1,4-butanediol is used, it is easy to distill off excess dihydric alcohol or dihydric alcohol produced as the polycondensation proceeds, reducing the polycondensation reaction. To increase the molecular weight.

Examples of the method of polycondensing the dihydric alcohol and furandicarboxylic acid in the presence of DMSO include a method of directly polycondensing these (a method of polycondensation after esterification). In addition, a method of synthesizing an ester of the dihydric alcohol and furandicarboxylic acid in the presence of DMSO and then polycondensing it (a method of polycondensation after esterification and transesterification) can be used.
Examples of the polycondensation method include solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization and the like, and can be appropriately selected depending on the molded product to be molded. A polymerization temperature, a polymerization catalyst, a medium such as a solvent, and the like can be appropriately selected depending on each polymerization method.
As a method for polycondensation of the dihydric alcohol and furandicarboxylic acid in the presence of DMSO, a transesterification method comprising an esterification step and a subsequent polycondensation step of an ester compound is preferred. In direct polycondensation, the feed ratio must be strictly controlled in order to increase the molecular weight. In contrast, in the transesterification method, dihydric alcohol charged excessively can be distilled off when the pressure is reduced to allow the reaction to proceed. Therefore, when the transesterification method is used, the molecular weight can be increased more easily than direct polycondensation.

In the esterification step, in the presence of DMSO, the dihydric alcohol, furandicarboxylic acid, and catalyst are gradually heated to 80 ° C. to 190 ° C., preferably 90 ° C. to 185 ° C. with stirring to obtain an ester compound. In order to obtain an ester by dehydrating dihydric alcohol and furandicarboxylic acid in the presence of DMSO, it is preferable to raise the temperature stepwise in the range of 80 ° C to 190 ° C. Specifically, after holding for about 1 to 2 hours, it is preferable to raise the temperature and hold it for about 1 to 2 hours, and then raise the temperature stepwise to advance the reaction.
The amount of DMSO used is preferably 50 to 82 parts by weight with respect to 100 parts by weight of the total amount of furandicarboxylic acid, dihydric alcohol, DMSO and catalyst. If it is less than 50 parts by weight, the degree of polymerization will not be sufficiently increased. If it exceeds 82 parts by weight, the concentration of alcohol and furan carboxylic acid with respect to the total amount of furandicarboxylic acid, dihydric alcohol and DMSO will be low, and the reaction will take a long time. Since it requires, it is not preferable. More preferably, it is 55 parts by weight or more and 82 parts by weight or less.

  Moreover, it is preferable that the usage-amount of a bihydric alcohol is 1 to 3 times the mole number of a bihydric alcohol with respect to the mole number of furandicarboxylic acid or its ester. Excess dihydric alcohol and dihydric alcohol produced as the polycondensation reaction proceeds are distilled off by heating the reaction system or under reduced pressure, or azeotropically distilled with another solvent, Alternatively, it can be removed out of the reaction system by other methods.

In polyester Le production method of the present invention, the flange carboxylic acid or its ester, may be used DMSO, and other monomer other than polyhydric alcohols.
Other monomers include dicarboxylic acid components such as terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid, 4,4'-biphenyldicarboxylic acid and other aromatic dicarboxylic acids, 1,4-cyclohexane Alicyclic dicarboxylic acids such as dicarboxylic acids, aliphatic dicarboxylic acids having aromatic rings such as 1,3-phenylenedioxydiacetic acid, aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, diglycolic acid, etc. The above-mentioned esters of dicarboxylic acids can also be mentioned. Examples of the hydroxycarboxylic acid component include p-hydroxybenzoic acid, 4- (2-hydroxyethoxy) benzoic acid, glycolic acid, and lactic acid. Examples of lactones include caprolactone, butyrolactone, and valerolactone. Moreover, alicyclic diols, such as 1, 2- cyclohexane diol, 1, 4- cyclohexane diol, 1, 1- cyclohexane dimethylol, 1, 4- cyclohexane dimethylol, can be mentioned.

Vinyl compounds such as styrene, vinyl toluene, α-methyl styrene, chlorostyrene, dichlorostyrene, vinyl naphthalene, ethyl vinyl ether, methyl vinyl ketone, methyl acrylate, ethyl acrylate, methyl methacrylate, acrylonitrile, methacrylonitrile, and diallyl phthalate, diallyl There can also be mentioned allyl compounds such as fumarate, diallyl succinate, triallyl cyanurate and the like.
These may be used alone or in combination. The amount of other monomers added is 50 parts by weight or less, preferably 5 parts by weight or less, based on 100 parts by weight of the total amount of raw materials.

The reaction proceeds even if the catalyst is not added due to the autocatalytic action of the dicarboxylic acid, but is preferably added because the concentration of the dicarboxylic acid decreases as the reaction proceeds. As the catalyst used, organometallic compounds such as metal oxides and salts, tin, lead, and titanium are preferable. The amount of the catalyst used is preferably 0.05 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the total amount of furandicarboxylic acid, dihydric alcohol and DMSO. If the amount of the catalyst used is less than 0.05 parts by weight, the effect of the catalyst is small and the reaction does not proceed easily. If the amount exceeds 5 parts by weight, the catalyst is used in a large amount, so the stability of the material such as heat resistance decreases Therefore, it is not preferable.
The end point of this esterification step can be confirmed by the reaction mixture becoming transparent.

  In the subsequent polycondensation step, the temperature of the reaction system is heated to a range of 80 ° C. to 190 ° C., preferably 90 ° C. to 185 ° C., to start the polycondensation reaction. The polycondensation reaction can be carried out under vacuum or atmospheric pressure. However, it is preferably carried out under atmospheric pressure because the polycondensation reaction proceeds in the presence of DMSO. In a general polycondensation step, it is necessary to maintain a vacuum of 1 to 2 torr for a long time to increase the degree of polymerization, but in the present invention, the degree of polymerization can be easily increased at atmospheric pressure.

Specific examples of the optimum catalyst for this polycondensation include the following. Acetates and carbonates such as lead, zinc, manganese, calcium, cobalt, and magnesium, or metal oxides such as magnesium, zinc, lead, and antimony, and organometallic compounds such as tin, lead, and titanium.
Moreover, titanium alkoxide can also be used as an effective catalyst in each process of esterification, transesterification, and polycondensation. The catalyst may be added separately in the esterification step and the polycondensation step, or the catalyst in the polycondensation step may be added from the beginning. In the addition of the catalyst, furan carboxylic acid and dihydric alcohol may be heated as necessary, or may be added in multiple portions.

  In the polycondensation reaction, it is possible to promote the polycondensation reaction by removing from the reaction system excess dihydric alcohol that has not been consumed in the esterification or transesterification step or dihydric alcohol produced as a by-product. it can. The dihydric alcohol can be removed by heating or removing the reaction system under reduced pressure, or by removing it from the reaction system by azeotropic distillation with another solvent. Moreover, after obtaining a polymer by polycondensation reaction, solid phase polymerization can also be performed by a known method.

The number-average degree of polymerization of polyester Le of the present invention obtained in such polycondensation step is 610 or more 1040 or less.
The molecular weight of the polyester Le of the present invention, the molecular weight determination by 1,1,1,3,3,3 hexafluoro-2-propanol (HFIP) to dissolved gel permeation chromatography (GPC), The number average molecular weight is 110,000 to 190,000, preferably 120,000 to 190,000. When the number average molecular weight is 110,000 or more, the quality is stabilized by increasing the degree of polymerization. If it exceeds 190,000, polycondensation takes a long time, and problems such as excessive coloration of the polyester occur.

The polyester Le of the present invention may contain other structural unit other than the structural unit represented by the above formula (1).
Other structural units include dicarboxylic acid components such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 4,4′-diphenylsulfone dicarboxylic acid, aromatic dicarboxylic acid such as 4,4′-biphenyldicarboxylic acid, 1,4 -Aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, aliphatic dicarboxylic acids having an aromatic ring such as 1,3-phenylenedioxydiacetic acid, aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and diglycolic acid Mention may also be made of the esters of the above dicarboxylic acids, such as acids. Examples of the hydroxycarboxylic acid component include p-hydroxybenzoic acid, 4- (2-hydroxyethoxy) benzoic acid, glycolic acid, and lactic acid. Examples of lactones include caprolactone, butyrolactone, and valerolactone.
The other structural unit may be introduced after copolymerization with furandicarboxylic acid or its ester in the presence of a polyhydric alcohol.
The content of other structural units contained in the polyester Le 50 parts by weight or less relative to 100 parts by weight of the total amount of the polyester Le, preferably from 5 parts by weight or less.

Composition for a molded article of the present invention, including the polyester Le. The content of polyester Le contained in composition for a molded article of the present invention, preferably at least 50 wt% 100 wt% or less.
Furthermore, the molded product composition of the present invention within a range that does not inhibit the function of the polyester Le, optionally, may contain an additive. Specific examples include flame retardants, colorants, internal mold release agents, antioxidants, ultraviolet absorbers, and various fillers. The content of the additive contained in the molded article composition of the present invention is preferably 0.5% by weight or more and 50% by weight or less.

Examples of molded products that can be molded using the molded product composition include excellent molded products in a wide range of fields such as fibers, films, sheets, and various molded products. For example, a container such as a bottle, a pipe, a tube, a sheet, a plate, or a film. Particularly preferable molded articles include constituent materials such as an ink tank of an ink jet printer, an electrophotographic toner container, a packaging resin, a copying machine, a business machine such as a printer, or a camera casing.
As a molding method of a molded product using the above-described molded product composition, the same method as the thermoplastic resin molding method can be used. For example, compression molding, extrusion molding, injection molding, or the like can be used. it can.

The polyester Le of the present invention will be described specifically in detail, the technical scope of the present invention is not limited thereto. The evaluation of the polyester Le of the following examples and comparative examples were performed using the following measurement methods.
[Molecular weight measurement]
Analytical instrument: high performance liquid chromatograph Waters Alliance 2695
Detector: Differential refraction detector Eluent: Hexafluoroisopropanol solution having a concentration of 5 mM sodium trifluoroacetate Flow rate: 1.0 ml / min
Column temperature: 40 ° C
Molecular weight: The number average molecular weight (Mn), the weight average molecular weight (Mw), and the polydispersity (Mw / Mn) were determined using a standard of polymethyl methacrylate resin (PMMA).
[NMR measurement]
Device name: JEM-ECA-400 nuclear magnetic resonance apparatus manufactured by JEOL Ltd.
Measurement conditions: 1H-NMR
Solvent: CF ₃ COOD
In the following examples and comparative examples, PEF represents polyethylene-2,5-furandicarboxylate. Moreover,% of PEF shows mol%.
As an evaluation of quality stabilization, a hydrolysis resistance test of the polyester resin was conducted.
In the test, 0.1 g of a sample was placed in 10 g of a 1 mol / l NaOH aqueous solution and hydrolyzed by heating in an oven at 100 ° C. for 24 hours.
The hydrolyzed sample solution was filtered, and the filtrate was vacuum dried at 60 ° C. for 3 days.
Hydrolysis resistance was evaluated by the following formula.
Filter weight / 0.1 * 100 (%)

Example 1
[In the presence of DMSO, the preparation of ethylene glycol, polyester Le consisting furandicarboxylic acid (PEF)]
A 100 mL three-necked flask equipped with a thermometer and a stainless steel (SUS) stirring blade was prepared. In this three-necked flask, DMSO was charged at 82 mol% with respect to the total of 2,5-furandicarboxylic acid, ethylene glycol and DMSO. That is, 2,5-furandicarboxylic acid (3.9 g), ethylene glycol (3.5 g), DMSO (39 g), monobutyltin oxide catalyst (0.50 g), titanium-n-butoxide catalyst (0.50 g) added.
While nitrogen was introduced into the three-necked flask, stirring was started and the contents were heated by an oil bath. After the internal temperature reached 100 ° C., it was kept for 1 hour, and further kept at 185 ° C. for 9 hours to prepare PEF.

Example 2
[In the presence of DMSO, the preparation of ethylene glycol, polyester Le consisting furandicarboxylic acid (PEF)]
A 100 mL three-necked flask equipped with a thermometer and a SUS stirring blade was prepared. In this three-necked flask, DMSO was charged at 82 mol% with respect to the total of 2,5-furandicarboxylic acid, ethylene glycol and DMSO. That is, 2,5-furandicarboxylic acid (3.9 g), ethylene glycol (3.5 g), DMSO (39 g), monobutyltin oxide catalyst (0.50 g), titanium-n-butoxide catalyst (0.50 g) added.
While nitrogen was introduced into the three-necked flask, stirring was started and the contents were heated by an oil bath. After the internal temperature reached 100 ° C., it was held for 1 hour, further held at 175 ° C. for 1 hour, held at 180 ° C. for 1 hour, and then held at 185 ° C. for 2 hours to prepare PEF under atmospheric pressure.

Comparative Example 1
[With no DMSO addition, the preparation of ethylene glycol, polyester Le consisting furandicarboxylic acid (PEF)]
A 100 mL three-necked flask equipped with a thermometer and a SUS stirring blade was prepared. 2,5-furandicarboxylic acid (7.81 g), ethylene glycol (8.07 g), monobutyltin oxide catalyst (0.014 g), and titanium-n-butoxide catalyst (0.014 g) were added to the three-necked flask. .
While nitrogen was introduced into the three-necked flask, stirring was started and the contents were heated by an oil bath. After the internal temperature reached 160 ° C., it was held for 1 hour, and further held at 165 ° C. for 1 hour and at 185 ° C. for 2 hours.
Depressurization was started at 185 ° C., and the pressure was increased to about 133 Pa over about one hour, and further increased to 230 ° C. The reaction was continued at about 133 Pa and 230 ° C. for 4.5 hours.

Comparative Example 2
[N- methylpyrrolidone (NMP) in the presence of the preparation of ethylene glycol, polyester Le consisting furandicarboxylic acid (PEF)]
The raw material was charged so that the amount of NMP was 82 mol% with respect to the total of 2,5-furandicarboxylic acid, ethylene glycol and NMP. That is, 2,5-furandicarboxylic acid (3.9 g), ethylene glycol (3.5 g), NMP (38 g), monobutyltin oxide catalyst (0.5), titanium-n-butoxide catalyst (0.5 g) The same procedure as in Example 1 was followed except that.

Comparative Example 3
[N, N-dimethylformamide (DMF) in the presence of the preparation of ethylene glycol, polyester Le consisting furandicarboxylic acid (PEF)]
The raw material was charged so that DMF was 82 mol% with respect to the total of 2,5-furandicarboxylic acid, ethylene glycol and DMF. That is, 2,5-furandicarboxylic acid (3.9 g), ethylene glycol (3.5 g), DMF (40 g), monobutyltin oxide catalyst (0.5 g), titanium-n-butoxide catalyst (0.5 g) The same procedure as in Example 1 was followed except that.

The 1H-NMR spectrum of the PEF of Example 1 is shown in FIG.
The 1H-NMR spectrum of PEF of Example 2 is shown in FIG.
Next, Table 1 shows the molecular weight measurement results of Examples 1 and 2 and Comparative Examples 1, 2, and 3.

実施例のポリエステルは比較例にくらべ数平均分子量の値が大きく、重合度が改善されていることが分かる。
品質安定化評価としての耐加水分解性測定結果を表２に示す。

Polyester Le examples large values of the number average molecular weight compared to the comparative example, it can be seen that the degree of polymerization is improved.
Table 2 shows the results of measurement of hydrolysis resistance as a quality stabilization evaluation.

実施例1,2のポリエステルは耐加水分解性が高く、品質安定化されていることがわかる。

Polyester Le of Examples 1 and 2 have high hydrolysis resistance, it is found that they are stable quality.

Polyester Le of the present invention, highly polymerization degree, can be utilized to produce a molded article having excellent quality stabilization.

Claims (7)

Made of a structural unit represented by the following formula (1), a polyester, wherein the number-average molecular weight of from 110,000 to 190,000.

(In the formula, R represents an ethylene group .) A molded product obtained by molding the polyester according to claim 1 . Further, a molded product having an additive,
The molded article according to claim 2 , wherein the additive is at least one selected from the group consisting of a flame retardant, a colorant, an internal mold release agent, an antioxidant, an ultraviolet absorber, and a filler. An ink tank which is a molded article according to claim 2 or 3. The housing of the printer, which is a molded article according to claim 2 or 3. Camera housing of which is a molded article according to claim 2 or 3. A film characterized by being a molded product according to claim 2 or 3 .

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