WO2022065690A1 - Polyester including component derived from biomass and method for preparing same - Google Patents

Abstract

The present invention provides a polyester and a method for preparing same, wherein the polyester comprises a tetrahydrofuran derivative-derived repeating unit obtained from biomass and a trihydric or higher polyhydric alcohol-derived repeating unit and thus has a carbon reduction effect, and can be utilized for food containers and toys due to an excellent Young's modulus compared with existing polyethyleneterephthalate (PET).

Description

Polyester containing biomass-derived component and method for preparing same

The present invention relates to a polyester including a biomass-derived component and a manufacturing method thereof, and more particularly, to a polyester that can be used as a novel biomass PET for packaging and a manufacturing method thereof.

In modern society, plastics can be mass-produced in various ways and have excellent light weight, durability, price competitiveness, chemical resistance and mechanical properties. has been used extensively.

However, when these plastic materials are buried after use, they remain in the ground without being decomposed, and when incinerated, harmful gases such as dioxins are generated.

Environmental pollution caused by plastics has reached a level of concern around the world at present, and the development and application of biodegradable resins for disposable products as a means for solving this problem is being actively carried out.

Biodegradable resins are resins that are finally decomposed into water and carbon dioxide by microorganisms in soil or water. Biodegradable resins developed so far are polylactic acid synthesized by ring-opening reaction of lactic acid or lactide in the presence of a chemical catalyst or enzyme. (PLA), polycaprolactone chemically synthesized starting from epsilon caprolactone monomer, and diol-dicarboxylic acid-based aliphatic polyester, and polyhydroxybutyrate (PHB) produced by synthesis of other microorganisms in the body. , the most representative material among them is aliphatic (or aliphatic/aromatic) polyester obtained by polymerization of polylactic acid (PLA) and diol and dicarboxylic acid, which is bisecting the world market.

Among them, polylactic acid is the most eco-friendly product derived from biomass resources, but its use is limited due to physical limitations such as low heat resistance temperature and strong brittleness and slow biodegradation rate.

On the other hand, in the case of aliphatic (or aliphatic/aromatic) polyester prepared from diol and dicarboxylic acid, it has characteristics similar to polyethylene and polypropylene, but it is difficult to control the decomposition rate, and most commercialized products are derived from fossil raw materials. being synthesized However, the aliphatic-aromatic copolyester resins cannot help solve the problem of depletion of petroleum resources, which are finite resources, and the problem of global warming, and are not environmentally friendly.

In order to solve the above problems, due to the background of problems such as environmental pollution due to carbon dioxide emission and depletion of fossil raw materials, research on converting these raw materials to biomass resources is being actively conducted.

However, the biodegradable polyester resins using the biomass-derived raw materials have a lower degree of completion of the reaction due to impurities contained in the biomass-derived raw materials, and thus hydrolysis occurs more easily compared to polyesters using fossil raw materials, resulting in lower durability. There is a problem in that it lacks mechanical properties compared to the existing polyethylene terephthalate (PET).

One embodiment has a carbon reduction effect including a bio-derivative monomer, and has excellent transparency, impact resistance, flexibility, and elasticity compared to conventional polyethyleneterephthalate (PET), so that packaging ( Polyester that can be used as a new biomass PET for packaging) is provided.

Another embodiment provides a method for producing the polyester.

According to one embodiment, there is provided a polyester including a repeating unit represented by the following formula (1).

[Formula 1]

In Formula 1, A ¹¹ and A ¹² are each independently a linear or branched divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms, a ketone group (C(=O)), or a combination thereof, and the A ¹³ is a divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms including a hydroxyl group or an alkoxy group, R ¹¹ is a halogen group, a hydroxyl group, an alkoxy group, or an alkyl group, and n ¹¹ is the number of repetitions of the repeating unit; , n ¹² is an integer of 0 to 6.

A ¹³ may be a divalent aliphatic hydrocarbon group having 2 to 15 carbon atoms that further includes a hydroxy group or an alkoxy group and a branched chain having 1 to 5 carbon atoms.

The A ¹³ is -CH ₂ CH(OH)CH ₂ -, -CHR'CH(OH)CH ₂ -, -CH ₂ C(OH)R'CH ₂ -, -CH ₂ CH(OH)CH ₂ CH ₂ -, -CHR'CH(OH)CH ₂ CH ₂ -, -CH ₂ C(OH)R'CH ₂ CH ₂ -, -CH ₂ CH(OH)CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH(OH)CH ₂ CH ₂ -, -CHR'CH(OH)CH ₂ CH ₂ CH ₂ -, -CH ₂ C(OH)R'CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(OH)CHR 'CH ₂ CH ₂ -, -CHR'CH ₂ CH(OH)CH ₂ CH ₂ -, -CH ₂ CHR'CH(OH)CH ₂ CH ₂ -, -CH ₂ CH ₂ C(OH)R'CH ₂ CH ₂ -, -CH ₂ CH(OR')CH ₂ -, -CH(OR')CH ₂ CH ₂ -, -CH(OR')CHR"CH ₂ -, -CH ₂ C(OR')R" CH ₂ -, -C(OR')R"CH ₂ CH ₂ -, -CHR"CH(OR')CH ₂ -, or -CH ₂ C(OR')(OR")CH ₂ - (wherein R' and R" is each independently an alkyl group).

The repeating unit represented by Formula 1 may be represented by Formula 2 below.

[Formula 2]

In Formula 2, A ¹¹ and A ¹² are each independently a linear or branched divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms, a ketone group (C(=O)), or a combination thereof, and R ¹¹ is a halogen group, a hydroxyl group, an alkoxy group, or an alkyl group, wherein R ²¹ to R ²⁶ are each independently a hydrogen group, a halogen group, a hydroxyl group, an alkoxy group, or an alkyl group, at least one of which is a hydroxy group. time, n ¹¹ is the number of repetitions of the repeating unit, and n ¹² is an integer of 0 to 6.

The polyester may include 60 mol% or more of the repeating unit represented by Chemical Formula 1 based on the entire polyester.

The polyester may further include repeating units derived from an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, an aromatic diol, an aliphatic diol, or a mixture thereof.

The polyester may have a glass transition temperature (Tg) of 40 °C to 100 °C, and a weight average molecular weight of 6000 g/mol to 50000 g/mol.

According to another embodiment, a polyester comprising a repeating unit represented by the following formula (1) by reacting a mixture containing a tetrahydrofuran derivative represented by the following formula (3) with a trihydric or higher polyhydric alcohol represented by the following formula (4) It provides a method for producing a polyester, comprising the step of producing a.

[Formula 3]

[Formula 4]

[Formula 1]

In Formulas 1, 3 and 4, A ¹¹ and A ¹² are each independently a linear or branched divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms, a ketone group (C(=O)), or their combination, wherein A ¹³ is a hydroxy group or a branched-chain divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms including an alkoxy group, wherein R ¹¹ is a halogen group, a hydroxyl group, an alkoxy group, or an alkyl group, wherein n ¹¹ is the number of repetitions of the repeating unit, and n ¹² is an integer of 0 to 6.

The trihydric or higher polyhydric alcohol may be a trihydric or higher polyhydric alcohol substituted with at least one or more C1 to C5 alkyl groups.

The trihydric or higher polyhydric alcohol is propanetriol, alkylpropanetriol, butanetriol, alkylbutanetriol, pentanetriol, alkylpentanetriol, (hydroxyalkyl)propanediol, (hydroxyalkyl)alkylpropanediol , or pentaerythritol.

The trihydric or higher polyhydric alcohol is propane-1,2,3-triol (propane-1,2,3-triol), 1-methyl-propane-1,2,3-triol (1-methyl-propane- 1,2,3-triol), 2-methyl-propane-1,2,3-triol (2-methyl-propane-1,2,3-triol), butane-1,2,4-triol ( butane-1,2,4-triol), 1-methyl-butane-1,2,4-triol (1-methyl-butane-1,2,4-triol), 2-methyl-butane-1,2 ,4-triol (2-methyl-butane-1,2,4-triol), pentane-1,2,5-triol (pentane-1,2,5-triol), pentane-1,3,5 -triol (pentane-1,3,5-triol), 1-methyl-pentane-1,2,5-triol (1-methyl-pentane-1,2,5-triol), 2-methyl-pentane -1,2,5-triol (2-methyl-pentane-1,2,5-triol), 3-methyl-pentane-1,2,5-triol (3-methyl-pentane-1,2, 5-triol), 1-methyl-pentane-1,3,5-triol (1-methyl-pentane-1,3,5-triol), 2-methyl-pentane-1,3,5-triol ( 2-methyl-pentane-1,3,5-triol), 3-methyl-pentane-1,3,5-triol (3-methyl-pentane-1,3,5-triol), 1- (hydroxy Methyl) propane-1,3-diol (1- (hydroxymethyl) propane-1,3-diol), 2- (hydroxymethyl) propane-1,3-diol (2- (hydroxymethyl) propane-1,3- diol), 1-(hydroxymethyl)-2-methylpropane-1,3-diol (1-(hydroxymethyl)-2-methylpropane-1,3-diol), 2-(hydroxymethyl)-2-methyl Propane-1,3-diol (2-(hydroxymethyl)-2-methylpropane-1,3-diol), 1-(hydroxymethyl)-1-methylpropane-1,3-diol (1-(hydroxymethyl)- 1-methylpropane-1,3-diol), 2-(hydroxymethyl)-1-methylpropane-1,3-diol Ol (2-(hydroxymethyl)-1-methylpropane-1,3-diol), 1-(hydroxymethyl)-2-ethylpropane-1,3-diol (1-(hydroxymethyl)-2-ethylpropane-1, 3-diol), 2-(hydroxymethyl)-2-ethylpropane-1,3-diol (2-(hydroxymethyl)-2-ethylpropane-1,3-diol), 1-(hydroxymethyl)-1 -Ethylpropane-1,3-diol (1-(hydroxymethyl)-1-ethylpropane-1,3-diol), 2-(hydroxymethyl)-1-ethylpropane-1,3-diol (2-(hydroxymethyl) )-1-ethylpropane-1,3-diol), or pentaerythritol.

The mixture may further include an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, an aromatic diol, an aliphatic diol, or a mixture thereof.

The reaction includes esterifying a mixture comprising the tetrahydrofuran derivative represented by Formula 3 and a trihydric or higher polyhydric alcohol represented by Formula 4, and polycondensing the esterification reaction product in the presence of a polycondensation catalyst. It may include a step of merging.

The esterification reaction may be performed at a pressure of 0 kg/cm ² to 10.0 kg/cm ² and a temperature of 150° C. to 270° C.

The polycondensation may be performed at a pressure of 600 mmHg to 0.01 mmHg and a temperature of 150° C. to 290° C. for 0.5 hours to 2.75 hours.

The polycondensation catalyst may include a titanium-based compound, a germanium-based compound, an antimony-based compound, an aluminum-based compound, a tin-based compound, or a mixture thereof.

Polyester according to one embodiment has a carbon reduction effect including a bio-derived monomer, and has an excellent Young's modulus compared to existing polyethylene terephthalate, so it can be used for food containers or toys.

1 is a HOMO electron cloud distribution diagram of the three-dimensional structural formula of Chemical Formula 5.

2 is a LUMO electron cloud distribution diagram of the three-dimensional structural formula of Chemical Formula 5;

3 is a HOMO electron cloud distribution diagram of the three-dimensional structural formula of Chemical Formula 7.

4 is a LUMO electron cloud distribution diagram of the three-dimensional structural formula of Chemical Formula 7.

Advantages and features of the techniques described hereinafter, and methods of achieving them, will become apparent with reference to the embodiments described below in detail in conjunction with the accompanying drawings. However, the implemented form may not be limited to the embodiments disclosed below. Unless otherwise defined, all terms (including technical and scientific terms) used herein may be used with meanings commonly understood by those of ordinary skill in the art. In addition, terms defined in a commonly used dictionary are not to be interpreted ideally or excessively unless clearly defined in particular.

In the present specification, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated. The singular also includes the plural, unless the phrase specifically dictates otherwise.

The term “alkyl,” as used herein, unless otherwise specified, refers to saturated monovalent aliphatic hydrocarbon radicals, including straight and branched chains, having the specified number of carbon atoms. Alkyl groups typically have 1 to 20 carbon atoms ("C ₁ -C ₂₀ alkyl"), preferably 1 to 12 carbon atoms ("C ₁ -C ₁₂ alkyl"), more preferably 1 to 8 carbon atoms (“C ₁ -C ₈ alkyl”), or 1 to 6 carbon atoms (“C ₁ -C ₆ alkyl”), or 1 to 4 carbon atoms (“C ₁ -C ₄ alkyl”) ) contains Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, n-octyl and the like. include Alkyl groups may be substituted or unsubstituted. In particular, unless otherwise specified, an alkyl group may be substituted with one or more halogens, up to the total number of hydrogen atoms present on the alkyl moiety. Thus, C ₁ -C ₄ alkyl is a halogenated alkyl group, for example a fluorinated alkyl group having 1 to 4 carbon atoms, such as trifluoromethyl (—CF ₃ ) or difluoroethyl (—CH ₂ ). CHF ₂ ).

Alkyl groups described herein as being optionally substituted may be substituted with one or more substituents, which substituents are independently selected unless otherwise stated. The total number of substituents is equal to the total number of hydrogen atoms on the alkyl moiety to the extent that such substitutions satisfy the chemical sense. Optionally substituted alkyl groups typically have 1 to 6 optional substituents, often 1 to 5 optional substituents, preferably 1 to 4 optional substituents, more preferably 1 to 3 optional substituents It may contain substituents.

Optional substituents suitable for the above alkyl groups include, but are not limited to, C ₁ -C ₈ alkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, C ₃ -C ₈ cycloalkyl, 3 to 12 membered heterocycle. reyl, C ₆ -C ₁₂ aryl and 5 to 12 membered heteroaryl, halo, =O(oxo), =S(thiono), =N-CN, =N-OR ^x , =NR ^x , -CN, -C(O)R ^x , -CO ₂ R ^x , -C(O)NR ^x R ^y , -SR ^x , -SOR ^x , -SO ₂ R ^x , -SO ₂ NR ^x R ^y , -NO ₂ , -NR ^x R ^y , -NR ^x C(O)R ^y , -NR ^x C(O)NR ^x R ^y , -NR ^x C(O)OR ^x , -NR ^x SO ₂ R ^y , -NR ^x SO ₂ NR ^x R ^y , -OR ^x , -OC(O)R ^x and -OC(O)NR ^x R ^y , wherein each R ^x and R ^y is independently hydrogen (H), C ₁ -C ₈ alkyl, C ₁ -C ₈ acyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, C ₃ -C ₈ cycloalkyl, 3 to 12 membered heterocyclyl, C ₆ -C ₁₂ aryl or 5 to 12 membered heteroaryl, or R ^x and R ^y together with the N atom to which they are attached may form a 3 to 12 membered heterocyclyl or 5 to 12 membered heteroaryl ring, each optionally being O , N and S(O) _q , wherein q is 0 to 2; may contain 1, 2 or 3 additional heteroatoms; each of R ^x and R ^y is halo, =O, =S, =N-CN, =N-OR', =NR', -CN, -C(O)R', -CO ₂ R', -C (O)NR' ₂ , -SOR', -SO ₂ R', -SO ₂ NR' ₂ , -NO ₂ , -NR' ₂ , -NR'C(O)R', -NR'C(O) NR' ₂ , -NR'C(O)OR', -NR'SO ₂ R', -NR'SO ₂ NR' ₂ , -OR', -OC(O)R' and -OC(O)NR' optionally substituted with 1 to 3 substituents independently selected from the group consisting of ₂ , wherein each R' is independently hydrogen (H), C ₁ -C ₈ alkyl, C ₁ -C ₈ acyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, C ₃ -C ₈ cycloalkyl, 3-12 membered heterocyclyl, C ₆ -C ₁₂ aryl or C ₅ -C ₁₂ heteroaryl; each of the above C ₁ -C ₈ alkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, C ₃ -C ₈ cycloalkyl, 3-12 membered heterocyclyl, C ₆ -C ₁₂ aryl and A 5-12 membered heteroaryl may be optionally substituted as further defined herein.

The term “divalent aliphatic hydrocarbon (ie, alkylene),” as used herein, unless otherwise specified, refers to a divalent hydrocarbyl group having the specified number of carbon atoms, which may link two other groups together. Often alkylene refers to -(CH ₂ ) _n -, wherein n is 1 to 8, preferably n is 1 to 4. Where specified, alkylene may also be substituted with other groups and may contain at least one degree of unsubstitution (ie, an alkenylene or alkynylene moiety) or ring. The open valence of the alkylene need not be at the opposite end of the chain. Accordingly, branched alkylene groups such as -CH(Me)-, -CH ₂ CH(Me)- and -C(Me) ₂ - are also included within the scope of the term “alkylene” and include cyclic groups such as cyclopropane The same is true for -1,1-diyl and unsaturated groups, such as ethylene (-CH=CH-) or propylene (-CH ₂ -CH=CH-). Alkylene groups are unsubstituted or substituted by the same groups as described herein as suitable for alkyl.

As used herein, the term “halo” or “halogen” refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I), unless otherwise specified.

The term “hydroxy,” as used herein, unless otherwise specified, refers to the group —OH.

The term "alkoxy," as used herein, unless otherwise specified, refers to a monovalent -O-alkyl group in which the alkyl moiety has the specified number of carbon atoms. An alkoxy group typically has 1 to 8 carbon atoms (“C ₁ -C ₈ alkoxy”), or 1 to 6 carbon atoms (“C ₁ -C ₆ alkoxy”), or 1 to 4 carbon atoms ( "C ₁ -C ₄ alkoxy"). For example, C ₁ -C ₄ alkoxy is methoxy (-OCH ₃ ), ethoxy (-OCH ₂ CH ₃ ), isopropoxy (-OCH(CH ₃ ) ₂ ), tert-butyloxy (-OC( CH ₃ ) ₃ ) and the like. Alkoxy groups are unsubstituted or substituted on the alkyl moiety by the same groups as described herein as suitable for alkyl. In particular, the alkoxy group may be optionally substituted with one or more halo atoms, in particular one or more fluoro atoms, up to the total number of hydrogen atoms present on the alkyl moiety. Such groups have the specified number of carbon atoms and are referred to as “haloalkoxy” groups substituted with one or more halo substituents, eg, more specifically “fluoroalkoxy” when fluorinated, and typically such groups contain from 1 to 6 carbon atoms. contains atoms, preferably 1 to 4 carbon atoms, often 1 or 2 carbon atoms, and 1, 2 or 3 halo atoms (ie "C ₁ -C ₆ haloalkoxy", " C ₁ -C ₄ haloalkoxy” or “C ₁ -C ₂ haloalkoxy”). More specifically, a fluorinated alkyl group is a fluoroalkoxy group, typically substituted with 1, 2 or 3 fluoro atoms, such as C ₁ -C ₆ , C ₁ -C ₄ or C ₁ -C ₂ fluoroalkoxy may be specifically referred to as a group. Thus, C ₁ -C ₄ fluoroalkoxy is trifluoromethyloxy (-OCF ₃ ), difluoromethyloxy (-OCF ₂ H), fluoromethyloxy (-OCFH ₂ ), difluoroethyloxy ( -OCH ₂ CF ₂ H) and the like.

As used herein, the terms “optionally substituted” and “substituted or unsubstituted” mean that the particular group being described may have no non-hydrogen substituents (ie, unsubstituted), or that the group may have one or more non- Used interchangeably to indicate that it may have a hydrogen substituent (ie, substituted). Unless otherwise specified, the total number of substituents that may be present is equal to the number of H atoms present on the unsubstituted form of the group being described. When an optional substituent is attached via a double bond (eg, an oxo (=O) substituent), the group occupies the available valence, reducing the total number of other substituents included by two. When optional substituents are independently selected from a list of substitutes, the selected groups are the same or different. Throughout this specification, it will be understood that the number and nature of optional substituents will be limited to the extent that such substitutions satisfy chemistry.

In the present specification, * indicated at both ends of a chemical formula indicates that it is connected to another adjacent chemical formula.

According to one embodiment, there is provided a polyester including a repeating unit represented by the following formula (1).

[Formula 1]

In Formula 1, A ¹¹ and A ¹² may each independently represent a linear or branched divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms, a ketone group (C(=O)), or a combination thereof. For example, the divalent aliphatic hydrocarbon group may be a methylene group, an ethylene group, a propylene group, or an isopropylene group.

The combination of the divalent aliphatic hydrocarbon group and the ketone group means that one of the ketone groups is connected to one of the divalent aliphatic hydrocarbon groups, and the other of the ketone group and the other of the divalent aliphatic hydrocarbon group are in the formula 1 means that it is connected to tetrahydrofuran and oxygen, respectively.

A ¹³ may be a divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms including a hydroxyl group or an alkoxy group. For example, A ¹³ is -CH ₂ CH(OH)CH ₂ -, -CH ₂ CH(OH)CH ₂ CH ₂ -, -CH ₂ CH(OH)CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH(OH)CH ₂ CH ₂ -, -CH ₂ CH(OR')CH ₂ -, -CH(OR')CH ₂ CH ₂ -, or -CH ₂ C(OR')(OR")CH ₂ -. Each of R' and R" may independently be an alkyl group (eg, a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group).

In addition, A ¹³ may be a divalent aliphatic hydrocarbon group having 2 to 15 carbon atoms, which further includes a hydroxy group or an alkoxy group and a branched chain having 1 to 5 carbon atoms. For example, A ¹³ is -CHR'CH(OH)CH ₂ -, -CH ₂ C(OH)R'CH ₂ -, -CHR'CH(OH)CH ₂ CH ₂ -, -CH ₂ C( OH)R'CH ₂ CH ₂ -, -CHR'CH(OH)CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(OH)CHR'CH ₂ CH ₂ -, -CHR'CH ₂ CH(OH)CH ₂ CH ₂ -, -CH ₂ CHR'CH(OH)CH ₂ CH ₂ -, -CH ₂ CH ₂ C(OH)R'CH ₂ CH ₂ -, -CH ₂ C(OR')R"CH ₂ - , -C(OR')R"CH ₂ CH ₂ -, or -CHR"CH(OR')CH ₂ -. R' and R" are each independently an alkyl group (eg, a methyl group, an ethyl group, a propyl group). group, butyl group, or pentyl group).

That is, A ¹³ and the oxygen groups positioned on both sides of A ¹³ may be derived from trihydric or higher polyhydric alcohols. For example, the trihydric or higher polyhydric alcohol is propanetriol, alkylpropanetriol, butanetriol, alkylbutanetriol, pentanetriol, alkylpentanetriol, (hydroxyalkyl)propanediol, (hydroxyalkyl ) alkylpropanediol, or pentaerythritol.

In Formula 1, R ¹¹ represents a substituent of the tetrahydrofuran group, and may be, for example, a halogen group, a hydroxyl group, an alkoxy group, or an alkyl group, and n ¹² may be an integer of 0 to 6. When n ¹² is 0, the tetrahydrofuran is substituted with only hydrogen.

In Chemical Formula 1, n ¹¹ represents the number of repetitions of the repeating unit, and n ¹¹ may be appropriately adjusted according to the weight average molecular weight of the polyester, for example, 1 or more, 100 to 200, or 30 to 80, but the present invention is not limited thereto.

The repeating unit represented by Formula 1 may be represented by Formula 2 below.

[Formula 2]

In Formula 2, A ¹¹ , A ¹² , R ¹¹ , n ¹¹ , and n ¹² are the same as described in Formula 1, and thus a repetitive description will be omitted.

In Formula 2, R ²¹ to R ²⁶ are each independently a hydrogen group, a halogen group, a hydroxyl group, an alkoxy group, or an alkyl group, at least one of which may be a hydroxyl group.

The polyester may include 60 mol% or more of the repeating unit represented by Formula 1 based on the entire polyester, for example, 70 mol% or more, 80 mol% or more, 90 mol% or more, or even 100 It may be included in mole %.

Accordingly, the polyester may further include a repeating unit derived from an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, an aromatic diol, an aliphatic diol, or a mixture thereof. These will be described later in the method for producing the polyester.

The polyester may have a glass transition temperature (Tg) of 40 °C to 100 °C, for example, 40 °C to 60 °C, or 60 °C to 80 °C.

If the glass transition temperature is less than 40 ℃ may not have physical properties or thermal stability at room temperature, there may be a limit to the polyester film processing process for use as a packaging material. In addition, in order for the glass transition temperature to exceed 100° C., the molecular structure must have a high density.

The polyester may have a weight average molecular weight of 6000 g/mol to 50000 g/mol, for example, 6000 g/mol to 20000 g/mol, or 25000 g/mol to 50000 g/mol. If the weight average molecular weight is less than 6000 g / mol, film processing for use as a packaging material may be difficult and may not achieve a desired modulus, and if it exceeds 50000 g / mol, the viscosity may increase and productivity may decrease.

The polyester has a carbon reduction effect by including a repeating unit derived from a tetrahydrofuran derivative obtained from biomass. In addition, since the polyester includes a repeating unit derived from a trihydric or higher polyhydric alcohol having a branched chain, the branched chain causes steric hindrance during polyester polymerization, thereby lowering the crystallinity of the polyester, thereby improving the transparency of the polymer. can be increased

In addition, the polyester including the repeating unit has a lower glass transition temperature (Tg) than conventional PET, and has an excellent Young's modulus, so it can be used for food containers or toys.

According to another embodiment, a polyester comprising a repeating unit represented by the following formula (1) by reacting a mixture containing a tetrahydrofuran derivative represented by the following formula (3) with a trihydric or higher polyhydric alcohol represented by the following formula (4) It provides a method for producing a polyester comprising the step of producing.

[Formula 3]

[Formula 4]

[Formula 1]

In Formulas 1, 3, and 4, A ¹¹ , A ¹² , A ¹³ , R ¹¹ , n ¹¹ , and n ¹² are the same as described in Formula 1, and thus a repetitive description will be omitted.

The tetrahydrofuran derivative represented by Formula 3 may be, for example, biomass-derived dihydroxyalkyl tetrahydrofuran or tetrahydrofuran dicarboxylic acid. For example, the dihydroxyalkyl tetrahydrofuran can be obtained directly from hexoses such as glucose or fructose according to Scheme 1 below. Depending on the synthesis process and the separation step, dihydroxyalkyl tetrahydrofuran may have a cis stereoisomer, a trans stereoisomer, or a mixture thereof (cis:trans = 0.1: 99.9 to 99.9: 0.1 (wt %) ) may be included.

[Scheme 1]

When polyester is produced using the tetrahydrofuran derivative obtained from the biomass, the effect of reducing carbon can be obtained.

The trihydric or higher polyhydric alcohol represented by Formula 4 is, for example, propanetriol, butanetriol, pentanetriol, (hydroxyalkyl)propanediol, (hydroxyalkyl)alkylpropanediol, or pentaerythritolyl can

In addition, the trihydric or higher polyhydric alcohol may be a trihydric or higher polyhydric alcohol substituted with at least one or more C1 to C5 alkyl groups. For example, the trihydric or higher polyhydric alcohol may be alkylpropanetriol, alkylbutanetriol, alkylpentanetriol, or (hydroxyalkyl)alkylpropanediol.

For example, the trihydric or higher polyhydric alcohol is propane-1,2,3-triol (propane-1,2,3-triol), 1-alkyl-propane-1,2,3-triol (1- alkyl-propane-1,2,3-triol), 2-alkyl-propane-1,2,3-triol (2-alkyl-propane-1,2,3-triol), butane-1,2,4 -triol (butane-1,2,4-triol), 1-alkyl-butane-1,2,4-triol (1-alkyl-butane-1,2,4-triol), 2-alkyl-butane -1,2,4-triol (2-alkyl-butane-1,2,4-triol), pentane-1,2,5-triol (pentane-1,2,5-triol), pentane-1 ,3,5-triol (pentane-1,3,5-triol), 1-alkyl-pentane-1,2,5-triol (1-alkyl-pentane-1,2,5-triol), 2 -Alkyl-pentane-1,2,5-triol (2-alkyl-pentane-1,2,5-triol), 3-alkyl-pentane-1,2,5-triol (3-alkyl-pentane- 1,2,5-triol), 1-alkyl-pentane-1,3,5-triol (1-alkyl-pentane-1,3,5-triol), 2-alkyl-pentane-1,3,5 -triol (2-alkyl-pentane-1,3,5-triol), 3-alkyl-pentane-1,3,5-triol (3-alkyl-pentane-1,3,5-triol), 1 -(hydroxyalkyl)propane-1,3-diol (1-(hydroxyalkyl)propane-1,3-diol), 2-(hydroxyalkyl)propane-1,3-diol (2-(hydroxyalkyl)propane- 1,3-diol), 1-(hydroxyalkyl)-2-alkylpropane-1,3-diol (1-(hydroxyalkyl)-2-alkylpropane-1,3-diol), 2-(hydroxyalkyl) -2-alkylpropane-1,3-diol (2-(hydroxyalkyl)-2-alkylpropane-1,3-diol), 1-(hydroxyalkyl)-1-alkylpropane-1,3-diol (1- (hydroxyalkyl)-1-alkylpropane-1,3-diol), 2-(hydroxyalkyl)-1-alkylpropane-1,3-diol (2-(hydrox) yalkyl)-1-alkylpropane-1,3-diol), or pentaerythritol.

Specifically, the trihydric or higher polyhydric alcohol is propane-1,2,3-triol (propane-1,2,3-triol), 1-methyl-propane-1,2,3-triol (1-methyl -propane-1,2,3-triol), 2-methyl-propane-1,2,3-triol (2-methyl-propane-1,2,3-triol), butane-1,2,4- Triol (butane-1,2,4-triol), 1-methyl-butane-1,2,4-triol (1-methyl-butane-1,2,4-triol), 2-methyl-butane- 1,2,4-triol (2-methyl-butane-1,2,4-triol), pentane-1,2,5-triol (pentane-1,2,5-triol), pentane-1, 3,5-triol (pentane-1,3,5-triol), 1-methyl-pentane-1,2,5-triol (1-methyl-pentane-1,2,5-triol), 2- Methyl-pentane-1,2,5-triol (2-methyl-pentane-1,2,5-triol), 3-methyl-pentane-1,2,5-triol (3-methyl-pentane-1) ,2,5-triol), 1-methyl-pentane-1,3,5-triol (1-methyl-pentane-1,3,5-triol), 2-methyl-pentane-1,3,5- Triol (2-methyl-pentane-1,3,5-triol), 3-methyl-pentane-1,3,5-triol (3-methyl-pentane-1,3,5-triol), 1- (hydroxymethyl) propane-1,3-diol (1- (hydroxymethyl) propane-1,3-diol), 2- (hydroxymethyl) propane-1,3-diol (2- (hydroxymethyl) propane-1 ,3-diol), 1-(hydroxymethyl)-2-methylpropane-1,3-diol (1-(hydroxymethyl)-2-methylpropane-1,3-diol), 2-(hydroxymethyl)- 2-methylpropane-1,3-diol (2-(hydroxymethyl)-2-methylpropane-1,3-diol), 1-(hydroxymethyl)-1-methylpropane-1,3-diol (1-( hydroxymethyl)-1-methylpropane-1,3-diol), 2-(hydroxymethyl)-1-methylpropane Pan-1,3-diol (2-(hydroxymethyl)-1-methylpropane-1,3-diol), 1-(hydroxymethyl)-2-ethylpropane-1,3-diol (1-(hydroxymethyl)- 2-ethylpropane-1,3-diol), 2-(hydroxymethyl)-2-ethylpropane-1,3-diol (2-(hydroxymethyl)-2-ethylpropane-1,3-diol), 1-( Hydroxymethyl)-1-ethylpropane-1,3-diol (1-(hydroxymethyl)-1-ethylpropane-1,3-diol), 2-(hydroxymethyl)-1-ethylpropane-1,3- It may be a diol (2-(hydroxymethyl)-1-ethylpropane-1,3-diol) or pentaerythritol, but the present invention is not limited thereto.

As the polyester includes a repeating unit derived from a trihydric or higher polyhydric alcohol having the branched chain, the branched chain causes steric hindrance during polyester polymerization, thereby lowering the crystallinity of the polyester, thereby increasing the transparency of the polymer can do it

In addition, the polyester including the repeating unit has a lower glass transition temperature (Tg) than conventional PET and has an excellent Young's modulus, so it can be used for food containers or toys.

Meanwhile, the mixture may further include an aromatic diol or an aliphatic diol as an additional diol component in addition to the monomer represented by Chemical Formula 3 or Chemical Formula 4.

The aromatic diol may include an aromatic diol compound having 8 to 40 carbon atoms, for example, 8 to 33 carbon atoms. Examples of such an aromatic diol compound include polyoxyethylene-(2.0)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene-(2.0)-2,2-bis(4-hydroxyphenyl) Propane, polyoxypropylene-(2.2)-polyoxyethylene-(2.0)-2,2-bis(4-hydroxyphenyl)propane, polyoxyethylene-(2.3)-2,2-bis(4-hydroxyl Phenyl) propane, polyoxypropylene-(6)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene-(2.3)-2,2-bis(4-hydroxyphenyl)propane, polyoxy Propylene-(2.4)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene-(3.3)-2,2-bis(4-hydroxyphenyl)propane, polyoxyethylene-(3.0)- Bisphenol A derivatives to which ethylene oxide and/or propylene oxide have been added, such as 2,2-bis(4-hydroxyphenyl)propane and polyoxyethylene-(6)-2,2-bis(4-hydroxyphenyl)propane (polyoxyethylene-(n)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene-(n)-2,2-bis(4-hydroxyphenyl)propane or polyoxypropylene-( n)-polyoxyethylene-(n)-2,2-bis(4-hydroxyphenyl)propane, etc. n represents the number of polyoxyethylene or polyoxypropylene units it means.

The aliphatic diol may include an aliphatic diol compound having 2 to 20 carbon atoms, for example, an aliphatic diol compound having 2 to 12 carbon atoms. Examples of such an aliphatic diol compound include ethylene glycol, diethylene glycol, triethylene glycol, propanediol (1,2-propanediol, 1,3-propanediol, etc.), 1,4-butanediol, pentanediol, hexanediol ( 1,6-hexanediol, etc.), neopentyl glycol (2,2-dimethyl-1,3-propanediol), 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanediol and linear, branched or cyclic aliphatic diol components such as methanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol and tetramethylcyclobutanediol.

In addition, the mixture may further include an aromatic dicarboxylic acid or an aliphatic dicarboxylic acid as an additional dicarboxylic acid component in addition to the monomer represented by Chemical Formula 3 or Chemical Formula 4.

The aromatic dicarboxylic acid may be an aromatic dicarboxylic acid having 8 to 20 carbon atoms, preferably 8 to 14 carbon atoms, or a mixture thereof. The aromatic dicarboxylic acid is, for example, isophthalic acid, naphthalenedicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, diphenyl dicarboxylic acid, 4,4'-stilbenedicarboxylic acid, 2, 5-furandicarboxylic acid, or 2,5-thiophenedicarboxylic acid, and the like.

Specifically, the aromatic dicarboxylic acid may include terephthalic acid, and the terephthalic acid is a dicarboxylic acid such as terephthalic acid or an alkyl ester thereof (monomethyl, monoethyl, dimethyl, diethyl or dibutyl ester, etc. having 1 to 4 carbon atoms). of a lower alkyl ester) and/or an acid anhydride thereof, and may react with a diol component to form a dicarboxylic acid moiety such as a terephthaloyl moiety.

The aliphatic dicarboxylic acid is malonic acid, succinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, fumaric acid, 2,2-dimethylglutaric acid, suberic acid, maleic acid, itaconic acid, or maleic acid.

The mixture may include the additional dicarboxylic acid or diol component in an amount of 10 mol% to 90 mol%, or 40 mol% to 85 mol% based on the total amount of the mixture. When the additional dicarboxylic acid or diol component is further included, mechanical properties and heat resistance of the polyester may be further improved.

The reaction includes esterifying a mixture comprising the tetrahydrofuran derivative represented by Formula 3 and a trihydric or higher polyhydric alcohol represented by Formula 4, and polycondensing the esterification reaction product in the presence of a polycondensation catalyst. It may include a step of merging.

The esterification step may be performed by reacting the diol component and the dicarboxylic acid component at a pressure of 0 kg/cm ² to 10.0 kg/cm ² and a temperature of 150° C. to 270° C. The esterification reaction conditions may be appropriately adjusted according to the specific characteristics of the polyester to be prepared, the molar ratio of the dicarboxylic acid component to the diol, or process conditions. Specifically, a preferred example of the esterification reaction conditions may include a temperature of 200 °C to 270 °C, or 220 °C to 260 °C.

If the temperature of the esterification reaction is too low, the reaction yield may be low or a sufficient reaction may not occur, so that the physical properties of the finally prepared polyester may be reduced. If the temperature of the esterification reaction is too high, the possibility that the appearance of the polyester to be produced will be yellow is increased or the depolymerization reaction may proceed so that the polyester resin may not be synthesized in the production method.

The esterification exchange reaction may be performed in a batch or continuous manner, and each raw material may be added separately, but for example, it may be added in the form of a slurry in which the diol component is mixed with a dicarboxylic acid component. there is. In addition, the diol component, which is a solid component at room temperature, may be dissolved in water or a solvent such as ethylene glycol, and then mixed with the dicarboxylic acid component to form a slurry.

The molar ratio of the dicarboxylic acid component and the diol component participating in the esterification reaction may be 1:1.05 to 1:3.0. If the molar ratio of the dicarboxylic acid component to the diol component is less than 1.05, unreacted dicarboxylic acid component may remain during the polymerization reaction, thereby reducing the transparency of the polymer, and if the molar ratio exceeds 3.0, the polymerization reaction rate may decrease may be lowered or the productivity of the polymer may be reduced.

The esterification reaction may be performed in the presence of an esterification reaction catalyst including a zinc-based compound. The zinc-based compound may be, for example, zinc acetate, zinc acetate dihydrate, zinc chloride, zinc sulfate, zinc sulfide, zinc carbonate, zinc citrate, zinc gluconate, or a mixture thereof.

The esterification reaction catalyst may be used in an amount of 1 ppm to 100 ppm based on a central metal atom in the synthesized polyester. If the content of the esterification reaction catalyst is too small, it may be difficult to greatly improve the efficiency of the esterification reaction, and the amount of reactants not participating in the reaction may be greatly increased. In addition, if the content of the esterification reaction catalyst is too large, the physical properties of the polyester to be produced may be deteriorated.

Polycondensation of the resultant of the esterification reaction may be performed in the presence of a polycondensation catalyst at a pressure of 600 mmHg to 0.01 mmHg and a temperature of 150° C. to 290° C. for 0.5 hours to 2.75 hours.

When the polycondensation reaction proceeds at less than 150° C., glycol, a by-product of the polycondensation reaction, cannot be effectively removed out of the system, and thus the intrinsic viscosity of the final reaction product is low, thereby reducing the physical properties of the polyester produced. When the polycondensation reaction proceeds in excess of 290 °C, the possibility that the appearance of the prepared polyester becomes yellow is increased or the depolymerization reaction proceeds so that the polyester may not be synthesized.

The polycondensation catalyst may be added to the product of the esterification reaction before the start of the polycondensation reaction, and may be added to a mixture including the diol component and the dicarboxylic acid component before the esterification reaction, and the ester It may be added during the reaction step.

As the polycondensation catalyst, a titanium-based compound, a germanium-based compound, an antimony-based compound, an aluminum-based compound, a tin-based compound, or a mixture thereof may be used.

Examples of the titanium-based compound include tetraethyl titanate, acetyl tripropyl titanate, tetrapropyl titanate, tetrabutyl titanate, polybutyl titanate, 2-ethylhexyl titanate, octylene glycol titanate, and lactate titanate. , triethanolamine titanate, acetylacetonate titanate, ethylacetoacetic ester titanate, isostearyl titanate, titanium dioxide, titanium dioxide/silicon dioxide copolymer, titanium dioxide/zirconium dioxide copolymer, and the like.

As the germanium-based compound, germanium dioxide (GeO2), germanium tetrachloride (GeCl ₄ ), germanium ethyleneglycoxide (germanium ethyleneglycoxide), germanium acetate (germanium acetate), copolymers using them, and their mixtures, and the like.

On the other hand, in the production method, before or during the esterification reaction, or in the middle of the polycondensation reaction, a stabilizer or a colorant may be optionally added further.

The stabilizer may be selected in consideration of the physical properties of the finally manufactured polyester, for example, a phosphorus-based stabilizer may be used. Examples of the phosphorus-based stabilizer include phosphoric acid, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, triethyl phosphono acetate, or a mixture of two or more thereof. The stabilizer may be used in an amount of 10 ppm to 300 ppm, or 20 ppm to 200 ppm, based on the total weight of the polymer to be synthesized.

The colorant may be a cobald compound such as cobalt acetate or an organic colorant. The organic colorant may include an anthraquinone-based compound, an azo-based compound, a perinone-based compound, a methine-based compound, a phthalocyanine-based compound, an anthrapyridone-based compound, a perimidine-based compound, or a mixture of two or more thereof. The colorant may be used in an amount of 1 ppm to 100 ppm based on the total weight of the resin to be prepared.

Hereinafter, specific embodiments of the invention are presented. However, the examples described below are only for specifically illustrating or explaining the invention, and thus the scope of the invention is not limited thereto.

[Production Example: Synthesis of Polymer]

(Example 1: Synthesis of polyester)

In a 10 L reactor, 3737.5 g (53.5 mol%) of tetrahydrofuran-2,5-dicarboxylic acid and 1-methyl-propane-1,2,3-triol (1 -methyl-propane-1,2,3-triol) 3250 g (46.5 mol%) was mixed to form a slurry.

The slurry was filled in the reactor by bubbling nitrogen up to 1.5 bar at room temperature, and then the process of lowering the slurry to atmospheric pressure was repeated for 5 minutes (repeated 5 times). Then, after the above process, the inside of the reactor was depressurized to 10 torr to 100 torr, and a vacuum pump was connected to remove dissolved oxygen in the slurry for 5 minutes. This process was repeated 3 times.

Then, 50 ppm of a zinc acetate catalyst was added to the slurry in which the dicarboxylate and diol were mixed, and then the esterification reaction was performed at 240° C. for 1.5 hours.

After transferring the result of the esterification reaction to a polycondensation reactor equipped with a vacuum facility, the temperature is raised to 290 ℃ and the pressure is gradually reduced to 1 torr or less over 1 hour to remove the low molecular weight by-products generated during condensation. A polymerization reaction was carried out. After the polycondensation reaction was completed at the point where the viscosity rapidly increased, a polyester polymer including a repeating unit represented by the following Chemical Formula 5 was prepared (n=40).

[Formula 5]

(Example 2: Synthesis of polyester)

In a 10 L reactor, tetrahydrofurandimethanol (THFDM) 3737.5 g (53.5 mol%) and 1-methyl-propane-1,2,3-triol (1-methyl-propane-1,2,3-triol) ) 3250 g (46.5 mol%) were mixed to form a slurry.

The slurry was filled in the reactor by bubbling nitrogen up to 1.5 bar at room temperature, and then the process of lowering the slurry to atmospheric pressure was repeated for 5 minutes (repeated 5 times). Then, after the above process, the inside of the reactor was depressurized to 10 torr to 100 torr, and a vacuum pump was connected to remove dissolved oxygen in the slurry for 5 minutes. This process was repeated 3 times.

Then, 50 ppm of a zinc acetate catalyst was added to the slurry in which the reactants were mixed, and then an esterification reaction was performed at 240° C. for 1.5 hours.

After transferring the result of the esterification reaction to a polycondensation reactor equipped with a vacuum facility, the temperature is raised to 290 ℃ and the pressure is gradually reduced to 1 torr or less over 1 hour to remove the low molecular weight by-products generated during condensation. A polymerization reaction was carried out. The polycondensation reaction was completed at the point where the viscosity rapidly increased, and a polyester polymer including a repeating unit represented by the following Chemical Formula 6 was prepared (n=40).

[Formula 6]

(Comparative Example 1: Synthesis of polyethylene terephthalate)

Except that in Example 1, ethylene glycol was used instead of 1-methyl-propane-1,2,3-triol and terephthalic acid was used instead of tetrahydrofuran-2,5-dicarboxylic acid Then, in the same manner as in Example 1, polyethylene terephthalate (PET) including a repeating unit represented by the following Chemical Formula 7 was prepared (n=40).

[Formula 7]

[Experimental Example: Measurement of Physical Properties of Polyester]

The electron distribution of the polymers prepared in Example 1 and Comparative Example 1 was measured using Jaguar (B3LYP/6-31G**, 298.15 K, 1 atm), and the results are shown in FIGS. 1 to 4 and Table 1 shown in

1 is a HOMO electron cloud distribution diagram of the three-dimensional structural formula of Chemical Formula 5, FIG. 2 is a LUMO electron cloud distribution diagram of the three-dimensional structural formula of Chemical Formula 5, FIG. 3 is a HOMO electron cloud distribution diagram of the three-dimensional structural formula of Chemical Formula 7, FIG. 4 is Chemical Formula 7 LUMO electron cloud distribution diagram of the three-dimensional structure of

In addition, the glass transition temperature and Young's modulus of the polymers prepared in Example 1 and Comparative Example 1 were measured, and the results are also shown in Table 1.

The glass transition temperature was measured using a differential scanning calorimeter (DSC) after sampling a portion of the polymer polymer. Specifically, the analysis conditions were 25 °C to 200 °C, and a temperature increase rate of 10 °C/min under a nitrogen stream. It was decided.

The polymer Young's modulus was measured using a universal testing machine (UTM) according to the ASTM D 412 method. Specifically, the slope of the initial 0.5% strain section on the stress-strain curve analyzed at a speed of 500 mm/min using a film made of a polymer polymer as a specimen was calculated.

	Example 1	Comparative Example 1
Glass transition temperature (K)	330	460
Young's modulus (GPa)	3.0	1.50
HOMO-LUMO Gap (Hatrees)	0.247	0.176
Activation energy (ΔG ‡ , kcal/mol)	49.78 [reaction rate(1/min): 1.20 X 10 -22 ]	51.91 [reaction rate(1/min): 3.32 X 10 -24 ]

1 to 4 and Table 1, it can be seen that the polyester prepared in Example 1 has a low glass transition temperature and a high Young's modulus as compared to the polyethylene terephthalate prepared in Comparative Example 1, In Example 1, polyester was obtained in a higher yield than in Comparative Example 1. As a result, the polyester of the present invention contains a bio-derived monomer and has a carbon reduction effect, and has an excellent Young's modulus compared to conventional polyethylene terephthalate. Therefore, it can be used for food containers or toys.

The present invention relates to a polyester containing a biomass-derived component and a method for manufacturing the same, and can be utilized as a novel biomass PET for packaging.

Claims (16)

1. Polyester comprising a repeating unit represented by the following formula (1):

   [Formula 1]

   

   In Formula 1,

   A ¹¹ and A ¹² are each independently a linear or branched divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms, a ketone group (C(=O)), or a combination thereof,

   Wherein A ¹³ is a divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms including a hydroxyl group or an alkoxy group,

   Wherein R ¹¹ is a halogen group, a hydroxyl group, an alkoxy group, or an alkyl group,

   Wherein n ¹¹ is the number of repetitions of the repeating unit,

   Wherein n ¹² is an integer of 0 to 6.
2. In claim 1,

   Wherein A ¹³ is a divalent aliphatic hydrocarbon group having 2 to 15 carbon atoms further comprising a hydroxy group or an alkoxy group and a branched chain having 1 to 5 carbon atoms.
3. In claim 1,

   The A ¹³ is -CH ₂ CH(OH)CH ₂ -, -CHR'CH(OH)CH ₂ -, -CH ₂ C(OH)R'CH ₂ -, -CH ₂ CH(OH)CH ₂ CH ₂ -, -CHR'CH(OH)CH ₂ CH ₂ -, -CH ₂ C(OH)R'CH ₂ CH ₂ -, -CH ₂ CH(OH)CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH(OH)CH ₂ CH ₂ -, -CHR'CH(OH)CH ₂ CH ₂ CH ₂ -, -CH ₂ C(OH)R'CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(OH)CHR 'CH ₂ CH ₂ -, -CHR'CH ₂ CH(OH)CH ₂ CH ₂ -, -CH ₂ CHR'CH(OH)CH ₂ CH ₂ -, -CH ₂ CH ₂ C(OH)R'CH ₂ CH ₂ -, -CH ₂ CH(OR')CH ₂ -, -CH(OR')CH ₂ CH ₂ -, -CH(OR')CHR"CH ₂ -, -CH ₂ C(OR')R" CH ₂ -, -C(OR')R"CH ₂ CH ₂ -, -CHR"CH(OR')CH ₂ -, or -CH ₂ C(OR')(OR")CH ₂ - (wherein R' and R" is each independently an alkyl group).
4. In claim 1,

   The repeating unit represented by Formula 1 is a polyester represented by Formula 2 below:

   [Formula 2]

   

   In Formula 2,

   A ¹¹ and A ¹² are each independently a linear or branched divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms, a ketone group (C(=O)), or a combination thereof,

   Wherein R ¹¹ is a halogen group, a hydroxyl group, an alkoxy group, or an alkyl group,

   wherein R ²¹ to R ²⁶ are each independently a hydrogen group, a halogen group, a hydroxyl group, an alkoxy group, or an alkyl group, at least one of which is a hydroxyl group,

   Wherein n ¹¹ is the number of repetitions of the repeating unit,

   Wherein n ¹² is an integer of 0 to 6.
5. In claim 1,

   The polyester comprises 60 mol% or more of the repeating unit represented by Formula 1 with respect to the entire polyester.
6. In claim 5,

   wherein the polyester further comprises repeating units derived from an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, an aromatic diol, an aliphatic diol, or a mixture thereof.
7. In claim 1,

   The polyester has a glass transition temperature (Tg) of 40 ℃ to 100 ℃,

   A polyester having a weight average molecular weight of 6000 g/mol to 50000 g/mol.
8. A tetrahydrofuran derivative represented by the following formula (3),

   By reacting a mixture containing a trihydric or higher polyhydric alcohol represented by the following formula (4),

   A method for producing a polyester, comprising the step of preparing a polyester comprising a repeating unit represented by the following formula (1):

   [Formula 3]

   

   [Formula 4]

   

   [Formula 1]

   

   In Formula 1, Formula 3 and Formula 4,

   A ¹¹ and A ¹² are each independently a linear or branched divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms, a ketone group (C(=O)), or a combination thereof,

   Wherein A ¹³ is a branched C 1 to C 15 divalent aliphatic hydrocarbon group including a hydroxyl group or an alkoxy group,

   Wherein R ¹¹ is a halogen group, a hydroxyl group, an alkoxy group, or an alkyl group,

   Wherein n ¹¹ is the number of repetitions of the repeating unit,

   Wherein n ¹² is an integer of 0 to 6.
9. In claim 8,

   The method for producing a polyester, wherein the trihydric or higher polyhydric alcohol is a trihydric or higher polyhydric alcohol substituted with at least one or more C1 to C5 alkyl groups.
10. In claim 8,

    The trihydric or higher polyhydric alcohol is propanetriol, alkylpropanetriol, butanetriol, alkylbutanetriol, pentanetriol, alkylpentanetriol, (hydroxyalkyl)propanediol, (hydroxyalkyl)alkylpropanediol , or pentaerythritol, a method for producing polyester.
11. In claim 8,

    The trihydric or higher polyhydric alcohol is propane-1,2,3-triol (propane-1,2,3-triol), 1-methyl-propane-1,2,3-triol (1-methyl-propane- 1,2,3-triol), 2-methyl-propane-1,2,3-triol (2-methyl-propane-1,2,3-triol), butane-1,2,4-triol ( butane-1,2,4-triol), 1-methyl-butane-1,2,4-triol (1-methyl-butane-1,2,4-triol), 2-methyl-butane-1,2 ,4-triol (2-methyl-butane-1,2,4-triol), pentane-1,2,5-triol (pentane-1,2,5-triol), pentane-1,3,5 -triol (pentane-1,3,5-triol), 1-methyl-pentane-1,2,5-triol (1-methyl-pentane-1,2,5-triol), 2-methyl-pentane -1,2,5-triol (2-methyl-pentane-1,2,5-triol), 3-methyl-pentane-1,2,5-triol (3-methyl-pentane-1,2, 5-triol), 1-methyl-pentane-1,3,5-triol (1-methyl-pentane-1,3,5-triol), 2-methyl-pentane-1,3,5-triol ( 2-methyl-pentane-1,3,5-triol), 3-methyl-pentane-1,3,5-triol (3-methyl-pentane-1,3,5-triol), 1- (hydroxy Methyl) propane-1,3-diol (1- (hydroxymethyl) propane-1,3-diol), 2- (hydroxymethyl) propane-1,3-diol (2- (hydroxymethyl) propane-1,3- diol), 1-(hydroxymethyl)-2-methylpropane-1,3-diol (1-(hydroxymethyl)-2-methylpropane-1,3-diol), 2-(hydroxymethyl)-2-methyl Propane-1,3-diol (2-(hydroxymethyl)-2-methylpropane-1,3-diol), 1-(hydroxymethyl)-1-methylpropane-1,3-diol (1-(hydroxymethyl)- 1-methylpropane-1,3-diol), 2-(hydroxymethyl)-1-methylpropane-1,3-diol Ol (2-(hydroxymethyl)-1-methylpropane-1,3-diol), 1-(hydroxymethyl)-2-ethylpropane-1,3-diol (1-(hydroxymethyl)-2-ethylpropane-1, 3-diol), 2-(hydroxymethyl)-2-ethylpropane-1,3-diol (2-(hydroxymethyl)-2-ethylpropane-1,3-diol), 1-(hydroxymethyl)-1 -Ethylpropane-1,3-diol (1-(hydroxymethyl)-1-ethylpropane-1,3-diol), 2-(hydroxymethyl)-1-ethylpropane-1,3-diol (2-(hydroxymethyl) ) -1-ethylpropane-1,3-diol), or pentaerythritol (pentaerythritol), a method for producing a polyester.
12. In claim 8,

    The method for producing a polyester, wherein the mixture further comprises an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, an aromatic diol, an aliphatic diol, or a mixture thereof.
13. In claim 8,

    The reaction includes esterifying a mixture comprising the tetrahydrofuran derivative represented by Formula 3 and a trihydric or higher polyhydric alcohol represented by Formula 4; and

    A method for producing a polyester, comprising the step of polycondensing the esterification reaction product in the presence of a polycondensation catalyst.
14. In claim 13,

    The esterification reaction is made at a pressure of 0 kg/cm ² to 10.0 kg/cm ² and a temperature of 150° C. to 270° C., a method for producing polyester.
15. In claim 13,

    The polycondensation is made for 0.5 hours to 2.75 hours at a pressure of 600 mmHg to 0.01 mmHg and a temperature of 150 °C to 290 °C.
16. In claim 13,

    The polycondensation catalyst comprises a titanium-based compound, a germanium-based compound, an antimony-based compound, an aluminum-based compound, a tin-based compound, or a mixture thereof, a method for producing a polyester.

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