KR20120067523A - Furan type polyester and method for preparing the same - Google Patents

Abstract

PURPOSE: A furan-based polyester is provided to be manufactured from carboxylic acid and/or alcohol capable of obtaining from biomass, and to provide a container, a film, and fiber. CONSTITUTION: A furan-based polyester is in chemical formula 1 or 2. In chemical formula 1, R^1 and R^2 is respectively C1-9 alkylene group, i and j is respectively 0 or 1, p is an integer from 0-3, R^3 is C2-9 alkylene group, and n is as an integer, a repeat number of a repeating unit. The weight average molecular weight of the furan-based polyester is 5,000-1,000,000. In chemical formula, R^4 is respectively C1-9 alkylene group, w, x, y, and z is respectively as an integer, a repeat number of a repeating unit. The weight average molecular weight of the furan-based polyester is 5,000-1,000,000.

Description

Furan polyester and manufacturing method thereof {FURAN TYPE POLYESTER AND METHOD FOR PREPARING THE SAME}

The present invention relates to a polyester, and more particularly, to an furan polyester and a method for producing the same.

It is the current human production and consumption pattern that fossil fuels are collected and used in production and consumption activities and finally decomposed into carbon dioxide (CO ₂ ) and water. Solids are also left as waste, incinerated and broken down into CO ₂ and water. As a result, the global environment has been deteriorated by a one-way street that emits and accumulates CO ₂ and waste in the surrounding environment. On the other hand, the use of biomass uses the products of life on earth as fuel and raw material instead of fossil fuel. The CO ₂ emitted as a result of decomposition and incineration after use is absorbed by the plant again, and the biomass discharged in the form of waste is reused as energy. In other words, as the material is circulated, CO ₂ or waste is not accumulated in the global environment by 'carbon cycle' or 'material cycle'. The use of biomass is the concept of returning the 'one-way' of fossil fuel consumption, CO ₂ and waste emission and accumulation since the Industrial Revolution back to the natural mechanism of circulation.

Currently, bioplastics are mostly used as biodegradable packaging. The properties of bioplastics (strength, durability, etc.) are significantly lower than those of conventional plastics, making them difficult to use with other materials. It is also economically inferior to plastics obtained from fossil raw materials in demanding processes and prices. Therefore, it is necessary to develop bioplastic materials with new characteristics, high functionalization technology of bioplastics, and research and development of new bioplastics with price competitiveness.

Accordingly, the first technical problem to be achieved by the present invention is to provide a furan-based polyester having excellent physical properties that can be prepared from carboxylic acids and / or alcohols in order to solve the problems of the prior art.

The second technical problem to be achieved by the present invention is to provide a method for producing the furan-based polyester from carboxylic acid and / or alcohol.

The third technical problem to be achieved by the present invention is to provide a film, fiber and a container obtained from the furan-based polyester.

According to one aspect of the present invention, the present invention provides a furan-based polyester represented by the following formula (1).

[Formula 1]

In Formula 1,

R ¹ and R ² are each independently a C _{1 -9} alkylene group, more preferably C _{1 -6} alkylene group, still more preferably a C _{1 -3} alkylene group,

i and j are each independently 0 or 1,

p is an integer from 0 to 3,

And R ³ is C _{2 -9} alkylene group, more preferably C _{2 -6} alkylene group, still more preferably C _{3 -5} alkylene group,

n is an integer that is the number of repetitions of the repeating unit,

The weight average molecular weight of the furan-based polyester is 5,000 to 1,000,000.

According to another aspect of the present invention, the present invention provides a furan-based polyester represented by the following formula (2).

[Formula 2]

In Formula 2,

R ⁴ are each independently C _{1 -9} alkylene group, more preferably C _{1 -6} alkylene group, still more preferably C _{3 -5} alkylene group,

w, x, y and z are each independently an integer number of repetitions of the repeating unit,

R ⁵ are each independently a C _{1 -9} alkyl, more preferably C _{1 -6} alkyl group, still more preferably C _{1 -3} alkyl,

The weight average molecular weight of the furan-based polyester is 5,000 to 1,000,000.

According to another aspect of the present invention, the method for producing a furan-based polyester of the present invention

(A) preparing 2,5-dihydroxymethylfuran;

(B) preparing the 2,5-dihydroxymethylfuran into furan-2,5-dicarboxylic acid using an oxidation reaction; And

(C) preparing a furan-based polyester by reacting the furan-2,5-dicarboxylic acid with at least one selected from a compound represented by the following Formula 3 and a compound represented by the following Formulas 4 and 5

.

(3)

And R ⁶ is C _{1 -9} alkylene group, more preferably C _{1 -6} alkylene group, still more preferably C _{3 -5} alkylene group in the formula (3),

[Formula 4]

In formula 4 R ⁷ are each independently C _{1 -9} alkylene group, more preferably C _{1 -6} alkylene group, still more preferably a C _{1 -3} alkylene group, q is each independently 0 or 1,

[Chemical Formula 5]

In formula 5 R ⁸ are each independently C _{1 -9} alkyl, more preferably C _{1 -6} alkyl group, and still more preferably a C _{1 -3} alkyl group, r and s are repeated in the repeating unit as a constant, each independently The weight average molecular weight of the compound represented by the formula (5) is 1,000 to 200,000.

Another aspect of the present invention can provide a fiber (fiber) made of the furan-based polyester.

Another aspect of the present invention may provide a film or a bottle made of the furan-based polyester.

As described above, the present invention can provide a furan-based polyester having excellent physical properties that can be prepared from carboxylic acids and / or alcohols obtainable from biomass, and carboxylic acids obtainable from biomass and It is possible to provide a method for producing the furan-based polyester from the alcohol, and also to provide a container, a film and a fiber which can be obtained from the furan-based polyester.

1 is a process diagram schematically showing a process of a furan-based polyester manufacturing method according to an embodiment of the present invention.
Figure 2 is a view showing the infrared spectrum of the furan-based polyester prepared according to the comparative example and the embodiment of the present invention.
3 is a view showing a 4000 ~ 2600 cm ^-1 infrared spectrum of the furan-based polyester prepared according to the comparative example and the embodiment of the present invention.
4 is a view showing a 2000 ~ 400 cm ^-1 infrared spectrum of the furan-based polyester prepared according to the comparative example and the embodiment of the present invention.
5 is a diagram illustrating a thermal analysis spectrum of a differential thermal analyzer (DSC) of a furan-based polyester prepared according to a comparative example and an embodiment of the present invention.

Hereinafter, with reference to the accompanying drawings, preferred embodiments of the furan-based polyester, a method for producing the same and a film and a fiber product produced therefrom will be described in detail with reference to the accompanying drawings, the same or corresponding configuration Elements are given the same reference numerals and redundant description thereof will be omitted.

Also, the term and / or as used below includes any combination of a plurality of related items or any of a plurality of related items.

According to one aspect of the present invention, the present invention provides a furan-based polyester represented by the following formula (1).

[Formula 1]

In Formula 1,

R ¹ and R ² are each independently a C _{1 -9} alkylene group, more preferably C _{1 -6} alkylene group, still more preferably a C _{1 -3} alkylene group,

i and j are each independently 0 or 1,

p is an integer from 0 to 3,

And R ³ is C _{2 -9} alkylene group, more preferably C _{2 -6} alkylene group, still more preferably C _{3 -5} alkylene group,

n is an integer that is the number of repetitions of the repeating unit,

The weight average molecular weight of the furan-based polyester is 5,000 to 1,000,000.

According to another aspect of the present invention, the present invention provides a furan-based polyester represented by the following formula (2).

[Formula 2]

In Formula 2,

R ⁴ are each independently C _{1 -9} alkylene group, more preferably C _{1 -6} alkylene group, still more preferably C _{3 -5} alkylene group,

w, x, y and z are each independently an integer number of repetitions of the repeating unit,

R ⁵ are each independently a C _{1 -9} alkyl, more preferably C _{1 -6} alkyl group, still more preferably C _{1 -3} alkyl,

The weight average molecular weight of the furan polyester of the formula (2) is 5,000 to 1,000,000.

1 is a view schematically showing a process of a furan-based polyester manufacturing method according to an embodiment of the present invention.

Referring to Figure 1, according to another aspect of the present invention manufacturing method of furan polyester (S100) is

Preparing a 2,5-dihydroxymethylfuran (S101);

Preparing 2,5-dihydroxymethylfuran to furan-2,5-dicarboxylic acid using an oxidation reaction (S103); And

And reacting the furan-2,5-dicarboxylic acid with at least one selected from a compound represented by the following Chemical Formula 3 and a compound represented by the following Chemical Formulas 4 and 5 to prepare a furan-based polyester (S105). .

(3)

And R ⁶ is C _{1 -9} alkylene group, more preferably C _{1 -6} alkylene group, still more preferably C _{3 -5} alkylene group in the formula (3),

[Formula 4]

In formula 4 R ⁷ are each independently C _{1 -9} alkylene group, more preferably C _{1 -6} alkylene group, still more preferably a C _{1 -3} alkylene group, q is each independently 0 or 1,

[Chemical Formula 5]

In formula 5 R ⁸ are each independently C _{1 -9} alkyl, more preferably C _{1 -6} alkyl group, and still more preferably a C _{1 -3} alkyl group, r and s are repeated in the repeating unit as a constant, each independently The weight average molecular weight of the compound represented by the formula (5) is 1,000 to 200,000.

Where step S105 is

Reacting the furan-2,5-dicarboxylic acid with a compound represented by Formula 3 (S107); And

It may include a step (S109) of producing a furan-based polyester by reacting the reaction product of the step (S107) with one or more selected from the compounds represented by Formulas 4 and 5.

Here step (S107) is reacted for 1 to 10 hours at 160 to 200 ℃, step (S109) is reacted for 1 to 20 hours at 160 to 200 ℃, 0.1 to 5 hours at 160 to 200 ℃ reaction under reduced pressure and 200 to It is preferable to make it react at 230 degreeC for 0.1 to 5 hours.

According to another embodiment of the present invention, the 2,5-dihydroxymethylfuran is characterized in that it is prepared from monosaccharides or polysaccharide carbohydrates. 2,5-dihydroxymethylfuran can be obtained from monosaccharide or polysaccharide carbohydrate, which is a kind of biomass, and the method of using such biomass is environmentally friendly.

According to another embodiment of the present invention at least one compound selected from compounds represented by Formulas 4 and 5 is 0.001 to 0.5 mole parts, more preferably 0.003 to about 100 mole parts of the furan-2,5-dicarboxylic acid 0.2 mole parts.

According to another embodiment of the present invention, step (S105) is characterized in that the step of producing a furan-based polyester by melting condensation reaction (melting condensation reaction).

According to another embodiment of the present invention, the step (S107) and (S109) is characterized in that the step performed by the melting condensation reaction (melting condensation reaction).

Another aspect of the present invention can provide a fiber (fiber) made of the furan-based polyester.

Another aspect of the present invention may provide a film made of the furan-based polyester.

Another aspect of the present invention can provide a container made of the furan-based polyester.

[Example]

Furan-based polyester to be implemented in the present invention, a method for producing the same and a preferred embodiment of the film and fiber products produced therefrom are described below, but the present invention is not limited thereto.

<Reagents and Materials>

2,5-Dihydroxymethylfuran (DHMF, 97%) was purchased from PennAKem, manufactured by Biomass, and used KMnO ₄ (99%), NaOH (98%), HCl (35-36%), celite, butane- 1,4-diol (BDO, 99%) was purchased from Samjeon Chem. Pentaerythritol (99%), pentaerythritol ethoxylate (3/4 EO / OH), PVA (hydrolyzed 80%; M _w 9,500, 87-89%; M _w 18,000) was purchased from Aldrich. Tyzor catalyst used as a catalyst was titanium (IV) (triethanolaminato) -isopropoxide from Aldrich. All samples used in this experiment were used without further purification.

<Synthesis>

Manufacturing example  One. Furan -2,5- dicarboxlic acid Synthesis of

750 ml of 10% -NaOH (24eq) aqueous solution and 10 g (0.078 mol) of DHMF were added to a 1L beaker, and the mixture was sufficiently stirred at room temperature. Then, 60 g (4.8eq) of KMnO4 was added thereto and stirred for 15 minutes. A bright yellow transparent solution was obtained by using the prepared celite vacuum filtration. The filtrate was transferred to a beaker and HCl was added dropwise until the pH was 1 or less at room temperature. The solution was filtered under reduced pressure to separate the precipitate, and the precipitate was washed with distilled water and dried in a vacuum oven. In this experiment a light yellow solid was obtained with a yield of 52% (Scheme 1). The synthesized furan-2,5-dicarboxylic acid (FDCA) was used in the next polymerization without any purification.

[Reaction Scheme 1]

Comparative Example 1. Poly (butylene polymerization of furandicarboxylate ) ( PBF )

5.7 ml (2 eq) of BDO was added together to 5 g (0.032 mol) of monomer FDCA, and the mixture was stirred for 4 hours at 180 ° C. under a nitrogen atmosphere. The stirring speed was 50 rpm. Catalyst was injected and stirred for 9 hours. The temperature was maintained at 180 ° C. and the nitrogen injection was stopped, followed by stirring for 1 hour under reduced pressure. The temperature was raised to 210 ° C. and stirred for 1 hour. After slowly converting to room temperature and atmospheric pressure, phenol and TCE were dissolved in a solvent mixed with 6: 4 and precipitated in excess methanol to remove the remaining FDCA and filtered to recover the polymer. This was dried in a vacuum oven to obtain a light brown polymer fiber (Scheme 2).

Scheme 2

Example  One. Poly ( butylene furandicarboxylate - co - pentaerythritol ) ( PBFP Polymerization of

5.7 ml of BDO was added together to 5 g of monomer FDCA and stirred at 50 rpm for 4 hours under a nitrogen atmosphere at 180 ° C. Catalyst and pentaerythritol were injected and stirred for 9 hours. The temperature was maintained at 180 ° C., and the nitrogen injection was stopped. Then, the pressure was raised to 210 ° C. for 1 hour, the mixture was stirred for 1 hour, and slowly converted to room temperature and atmospheric pressure. Phenol and TCE were dissolved in a solvent of 6: 4, precipitated in excess methanol to remove residual FDCA, and then filtered to recover the polymer. This was dried in a vacuum oven to obtain a light brown polymer fiber (Scheme 3).

Scheme 3

Example  2. Poly ( butylene furandicarboxylate - co - pentaerythritol ethoxylate ) ( PBFPE Polymerization of

5.7 ml of BDO was added to the flask with respect to 5 g of monomer FDCA, and stirred at 50 rpm for 4 hours under a nitrogen atmosphere at 180 ° C. Catalyst and pentaerythritol ethoxylate were injected and stirred for 9 hours. After the nitrogen injection was stopped while maintaining the temperature at 180 ° C, the mixture was stirred under reduced pressure and stirred for 1 hour at 210 ° C. After slowly switching to normal temperature and pressure, the mixture was dissolved in a solvent mixed with phenol and TCE 6: 4 and precipitated in excess methanol to remove residual FDCA, and then filtered to recover the polymer. This was dried in a vacuum oven to obtain a light brown polymer fiber (Scheme 4).

Scheme 4

Example  3. Poly [ butylene furandicarboxylate - co -poly ( vinyl alcohol )] ( PBFPVA  80, polymerization of PBFPVA 88)

5.7 ml of BDO was added to the flask with respect to 5 g of monomer FDCA, and stirred at 50 rpm for 4 hours under a nitrogen atmosphere at 180 ° C. 80% of the catalyst and PVA were injected and stirred for 9 hours. After the nitrogen injection was stopped while maintaining the temperature at 180 ° C, the mixture was stirred under reduced pressure for 1 hour and stirred at 210 ° C for 1 hour. After slowly switching to normal temperature and normal pressure, phenol and TCE were dissolved in a solvent mixed with 6: 4 and precipitated in excess methanol to remove residual FDCA and filtered to recover the polymer. This was dried in a vacuum oven to obtain a light brown polymer fiber (Scheme 5). In this way, the experiments were also performed on PVA 87-89%.

Scheme 5

<Analysis>

Check structure

In order to analyze the structure of the synthesized monomer, an infrared spectrometer and ¹ H-NMR (Bruker, 600MHz) were used, and dimethylsulfoxide-d (99.9 atom% D) containing TMS was used. In addition, an infrared spectrometer, ¹ H-NMR and ¹³ C-NMR (Bruker, 600MHz) were used to identify the polymer, and trifluoroacetic acid-d (99.5 atom% D) containing TMS was used as a solvent.

Intrinsic viscosity

Intrinsic viscosity is Brookfield after dissolving the sample to be measured in PTCE, a mixed solvent prepared in 6: 4 by volume ratio of phenol and 1,1,2,2-tetrachloroethane, and making five samples at the concentration of 0.1-0.5 d / dl. Absolute viscosity was measured with a viscometer and calculated through a formula.

Thermal Characteristic Investigation

Differential Scanning Calorimeter (DSC, PerkinElmer) was used to investigate the melting point (T _m ) and glass transition temperature (T _g ) of the synthesized polymer. The melting point was measured using DSC using a heating rate of 10 ° C./min from 0 ° C. to 250 ° C. under a nitrogen atmosphere. Thermogravimetric analyzer (TGA, PerkinElmer) was used to measure the thermal stability, and the temperature was raised at 10 ℃ / min according to the sample from room temperature to 800 ℃ under nitrogen atmosphere using TGA.

The tensile strength  Measure

Tensile strength and elongation at break of the polymerized polyester were measured using Z005 of Zwick / Roell. The polymer of each sample was heated at a temperature higher than the melting point of the sample by using a heating hydraulic press, and pressed at 2000 psi for 1 minute to prepare a uniform film having a thickness of 0.16-0.18 mm, and in the form of a dog-bone specimen. Was made and measured.

Results and Discussion

One. Furan -2,5- dicarboxlic acid ( FDCA ) Synthesis

In this study, monomers were synthesized to polymerize furan polyester. 2,5-furandimethnaol was oxidized with KMnO ₄ to synthesize FDCA as dicarboxylic acid (see Scheme 1).

In the ¹ H-NMR spectrum of the synthesized FDCA, solvent was used as DMSO, and the characteristic peaks of FDCA which were found at 13.58 (s, Hb, 2H) and 7.25 (s, Ha, 2H) ppm were also identified. By disappearing the peak of ₂ , it turned out that the desired monomer was synthesize | combined. From the FT-IR spectrum of the FDCA monomer, the (-COO-) peak of 1710-1725cm ^-1 , which was not present in the initial material, was confirmed, indicating that the synthesis was performed. Thermal characterization by DSC of the monomer synthesized as DSC Thermogram shows that the melting point of FDCA is 350.2 ° C.

2. Furan Of polyester type (Furan type Polyester)  polymerization

NMR  analysis

In this study, to the furan-based monomer of FDCA and BDO under a small amount of the linker present melting condensation was tested using a ¹ H-NMR and ¹³ C-NMR to analyze the branched polymer composition was prepared. Trifluoroacetic acid-d was used as a solvent. The peak of the solvent is found at 11.50 (s, OH, 1H) ppm.

The polymer of polyesters was analyzed by 1H-NMR by calculating the hydrogen composition ratio of each structure by integrating the area at the peak based on the hydrogen of the furan ring.

PBF had 7.33 (m, furan, 2H) ppm peaks at ¹ H-NMR, 1.1 (m, OCH ₂ , 4H) and 1.99 (m, CH ₂ ) peaks at 1,4-butandiol. , 4H) ppm.

In 13C-NMR, solvent peaks were found at 122.03 and 163.30 ppm, and peaks attributable to furan ring were 113.83 to 119.46 (m, furan, 2C), 163.77 to 164.64 (m, furan, 2C), and 148.09 (s, furan, At 2C) ppm, peaks attributable to 1,4-butandiol were found at 26.71 (s, CH ₂ , 2C), 69.00 (s, OCH ₂ , 2C) ppm.

The structures of PBFP, PBFPE, PBFPVA80, and PBFPVA88 in addition to PBF were confirmed by NMR test methods.

IR  analysis

The structure of the polymerized polyesters was analyzed by IR. As a result of the ester coupling in the IR spectrum, C = O stretching at 1738 cm ^-1 and CO stretching at 1270 cm ^-1 . C = C binding of the furan ring was confirmed through 3110 cm ⁻¹ and 1580 cm ⁻¹ (FIGS. 2 to 4).

Intrinsic viscosity

In order to measure the intrinsic viscosity of the synthesized polyester, absolute viscosity was obtained using a Brookfield viscometer, and the intrinsic viscosity (I.V.) was calculated according to Equation 1, which is shown in Table 1 below. PBF had a value of 0.54, PBFP had 0.48, PBFPE had 0.69, PBFPVA80 had 0.82, and PBFPVA88 had 0.64. It was found that the I.V. value of the polymer containing most linkers except PBFP had a higher value than PBF.

[Formula 1]

In Equation 1, [η] is the intrinsic viscosity (IV), η _sp is the specific viscosity, and c is the concentration of the polymer to be measured.

sample Intrinsic Viscosity (I.V.) Comparative Example 1 (PBF) 0.54 Example 1 (PBFP) 0.48 Example 2 (PBFPE) 0.69 Example 3 (PBFPVA 80) 0.82 Example 3 (PBFPVA 88) 0.64

Thermal properties

5 shows the DSC thermogram of the polyester polymer. The Tg of PBF was 38.5 ° C, PBFP was 38.0 ° C, PBFPE was 36.5 ° C, PBFPVA80 was 37.5 ° C, and PBFPVA88 was 38.0 ° C. The Tc of PBF was 109.8 ° C, PBFP was 110.5 ° C, PBFPE was 107.5 ° C, PBFPVA80 was 104.6 ° C and PBFPVA88 was 104.9 ° C. Most of the polymers containing linker showed lower Tg than PBF. The Tm of PBF was 161.5 ° C, PBFP was 160.5 ° C, PBFPE was 161.5 ° C, PVAPBF80 was 164.1 ° C, and PBFPVA88 was 166.8 ° C.

Tensile Properties Measurement

The mechanical properties of polymers polymerized with FDCA, BDO and various linkers were measured. Tensile properties were measured after the film was molded in dog-bone form.

Claims (13)

Furan-based polyester represented by the following formula (1).
[Formula 1]

In Formula 1,
R ¹ and R ² are each independently a C _{1 -9} alkylene group,
i and j are each independently 0 or 1,
p is an integer from 0 to 3,
And R ³ is C _{2 -9} alkylene group,
n is an integer that is the number of repetitions of the repeating unit,
The weight average molecular weight of the furan-based polyester is 5,000 to 1,000,000. The method of claim 1,
R ¹ and R ² are each independently a C _{1 -6} alkyl group,
R ³ is a furan-based polyester, characterized in that C _{2 -6} alkylene group. The method of claim 2,
R ¹ and R ² are each independently a C _{1 -3} alkylene group,
R ³ is a furan-based polyester, characterized in that C _{3 -5} alkylene group. Furan-based polyester represented by the following formula (2).
(2)

In Formula 2,
R ⁴ are each independently C _{1 -9} alkylene group,
w, x, y and z are each independently an integer number of repetitions of the repeating unit,
R ⁵ are each independently a C _{1 -9} alkyl,
The weight average molecular weight of the furan-based polyester is 5,000 to 1,000,000. The method of claim 4, wherein
And R ⁴ is C _{1 -6} alkyl group,
R ⁵ is a furan-based polyester, characterized in that C _{1 -6} alkyl group; The method of claim 5,
And R ⁴ is C _{3 -5} alkylene group,
R ⁵ is a furan-based polyester, characterized in that C _{1 -3} alkyl. (A) preparing 2,5-dihydroxymethylfuran;
(B) preparing the 2,5-dihydroxymethylfuran into furan-2,5-dicarboxylic acid using an oxidation reaction; And
(C) preparing a furan-based polyester by reacting the furan-2,5-dicarboxylic acid with at least one selected from a compound represented by the following Formula 3 and a compound represented by the following Formulas 4 and 5
Method for producing a furan-based polyester comprising.
(3)

And R ⁶ is C _{1 -9} alkylene group in the formula (3),
[Chemical Formula 4]

In formula 4 R ⁷ are each independently C _{1 -9} alkylene group, q is each independently 0 or 1,
[Chemical Formula 5]

In formula 5 R ⁸ are each independently C _{1 -9} alkyl group, r and s are each independently an integer number of repetitions of the repeating unit, the weight average molecular weight of the compound represented by the formula (5) is 1,000 to 200,000. 8. The method of claim 7, wherein step (c)
(D) reacting the furan-2,5-dicarboxylic acid with a compound represented by Formula 3; And
(E) preparing a furan polyester by reacting the reaction product of step (d) with at least one selected from compounds represented by Formulas 4 and 5
Method for producing a furan-based polyester comprising a. The method of claim 8,
Step (d) is reacted for 1 to 10 hours at 160 to 200 ℃,
Step (e) of the furan-based polyester, characterized in that the reaction for 1 to 20 hours at 160 to 200 ℃, 0.1 to 5 hours at 160 to 200 ℃ and 0.1 to 5 hours at 200 to 230 ℃ while reducing the pressure Manufacturing method. The method of claim 7, wherein
At least one compound selected from the compounds represented by Formulas 4 and 5 is a method for producing a furan-based polyester, characterized in that 0.001 to 0.5 mole parts relative to 100 mole parts of the furan-2,5-dicarboxylic acid. A fiber made of the furan polyester of claim 1. A film made of the furan polyester according to claim 1. A container made of furan polyester according to claim 1.

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