KR20240107784A - Polyester resin and preparation method thereof - Google Patents

Abstract

The present invention relates to a polyester resin that can be suitably used in products that require high heat resistance due to its high glass transition temperature, and a method for manufacturing the same.

Description

Polyester resin and its manufacturing method {POLYESTER RESIN AND PREPARATION METHOD THEREOF}

The present invention relates to a polyester resin exhibiting high heat resistance and a method for producing the same.

Polyester resin has excellent mechanical strength, chemical stability, and gas barrier properties, and is widely used as a material for packaging containers, fibers, sheets, and films. A representative polyester resin is polyethylene terephthalate (PET), which is manufactured by polymerizing terephthalic acid and ethylene glycol. However, PET is crystalline, has poor formability, and has limitations in improving heat resistance.

In order to compensate for the shortcomings of PET, glycol-modified polyethylene terephthalate (PETG), which further contains 1,4-cyclohexanedimethanol (CHDM) as a diol component in addition to ethylene glycol, was developed. PETG has higher thermal and chemical stability and impact strength than PET due to CHDM, has excellent processability, and is non-crystalline, so transparent products can be produced without whitening due to crystallization. However, PETG has a glass transition temperature (Tg) of 80 to 88 ℃, making it difficult to use in fields that require high heat resistance.

The purpose of the present invention is to provide a new polyester resin with excellent heat resistance and a method for producing the same.

Accordingly, the present invention is a polyester resin containing a dicarboxylic acid repeating unit and a diol repeating unit,

The diol repeating unit is a repeating unit derived from a compound represented by the following formula 1 and 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5 , 5] provides a polyester resin comprising repeating units derived from undecane:

[Formula 1]

In Formula 1,

R ₁ and R ₂ are each independently substituted or unsubstituted C _1-10 alkylene.

Additionally, the present invention provides a dicarboxylic acid component; A diol component containing a compound represented by Formula 1; and preparing a molten mixture of a polymerization catalyst, and polymerizing the molten mixture at a pressure of 10 torr or less and a temperature of 160°C to 200°C.

Additionally, the present invention provides a dicarboxylic acid component; and performing an esterification or transesterification reaction of a diol component containing the compound represented by Formula 1 at normal pressure and a temperature of 200 to 300° C. in the presence of a polymerization catalyst, and heating the reaction mixture at a pressure of 0.01 to 0.1 torr and 240° C. A method for producing a polyester resin is provided including the step of carrying out a polycondensation reaction at a temperature of 300° C. to 300° C.

The polyester resin of the present invention contains a repeating unit derived from 1,4-cyclohexanedione glycerol diketal and exhibits a high glass transition temperature, and therefore can be suitably used in fields requiring high heat resistance.

The terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to limit the invention. Singular expressions include plural expressions unless the context clearly dictates otherwise.

In this specification, terms such as “comprise,” “comprise,” or “have” are intended to designate the presence of implemented features, steps, components, or a combination thereof, and are intended to indicate the presence of one or more other features or steps, It should be understood that the existence or addition possibility of components or combinations thereof is not excluded in advance.

Since the present invention can be subject to various changes and can take various forms, specific embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to a specific disclosed form, and should be understood to include all changes, equivalents, and substitutes included in the spirit and technical scope of the present invention.

In this specification, the term "substitution" refers to the bonding of another functional group in place of a hydrogen atom in a compound, and the position to be substituted is not limited as long as it is the position where the hydrogen atom is substituted, that is, a position where the substituent can be substituted, and if two or more substitutions are made, , two or more substituents may be the same or different from each other.

As used herein, the term “substituted or unsubstituted” refers to deuterium; halogen group; Cyano group; nitro group; hydroxyl group; carbonyl group; ester group; imide group; amide group; amino group; carboxyl group; sulfonic acid group; sulfonamide group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkylthioxy group; Arylthioxy group; Alkyl sulphoxy group; Aryl sulfoxy group; silyl group; boron group; Alkyl group; Cycloalkyl group; alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Arylphosphine group; or substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups containing one or more of N, O and S atoms, or substituted or unsubstituted with two or more of the above-exemplified substituents linked. . For example, “a substituent group in which two or more substituents are connected” may be a biphenyl group. That is, the biphenyl group may be an aryl group, or it may be interpreted as a substituent in which two phenyl groups are connected.

Hereinafter, the present invention will be described in detail.

polyester resin

According to one embodiment of the present invention, a polyester resin comprising a dicarboxylic acid repeating unit and a diol repeating unit, wherein the diol repeating unit is a repeating unit derived from a compound represented by the following formula (1) and 3,9-bis Provided is a polyester resin comprising repeating units derived from (1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane:

[Formula 1]

In Formula 1,

R ₁ and R ₂ are each independently substituted or unsubstituted C _1-10 alkylene.

The present inventors have made efforts to develop a polyester resin that can exhibit excellent heat resistance properties at the level of polycarbonate, and as a result, the polyester resin contains a repeating unit derived from the compound represented by Formula 1 and 3,9 as a diol repeating unit. -When a repeating unit derived from bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane is included, the glass transition temperature increases significantly. The present invention was completed by confirming that it exhibited excellent heat resistance properties.

The compound represented by Formula 1 is a reaction product of 1,4-cyclohexanedione, a diketone, and a glycol component.

Preferably, in Formula 1, R ₁ and R ₂ are each independently methylene, ethylene, or propylene. More preferably, the compound represented by Formula 1 is a compound represented by the following Formula 1-1:

[Formula 1-1]

The compound represented by Formula 1-1 is 1-4-cyclohexanedione glycerol diketal (1,4-CHGD).

The repeating unit derived from the compound represented by Formula 1 exhibits steric hindrance due to the ring in the compound structure, and the rotation of the bond is not free due to the polycyclic ring structure, and thus the polymer chain It has the effect of increasing the rigidity. As a result, the polyester resin containing the compound represented by Formula 1 exhibits a significantly improved glass transition temperature (Tg) compared to existing polyester resins such as PETG, and is therefore suitable for use in fields requiring high heat resistance, such as food use. It can be suitably used as a material for heat-resistant containers, protective sheets for construction, protective cases for electronic products, or parts for various home appliances.

In addition, the compound represented by Formula 1 does not contain -hydrogen, so there is no problem of lowering the degree of polymerization due to -elimination during the polymerization step, and it does not impair the transparency and color characteristics of polyester resin, making it suitable for the manufacture of high-quality products. It can be used effectively.

The repeating unit derived from the compound represented by Formula 1 is 1.0 mol% or more, or 3.0 mol% or more, or 4.0 mol% or more, and 20.0 mol% or less, out of the total 100 mol% of diol-derived repeating units contained in the polyester resin. , or 18.0 mol% or less, or 15.0 mol% or less. If the repeating unit derived from the compound represented by Formula 1 among the diol repeating units is less than 1.0 mol%, sufficient glass transition temperature improvement effect may not be obtained, and if it exceeds 20 mol%, the degree of polymerization decreases and the molecular weight decreases. There may be.

In addition, the polyester resin contains 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane (3) as a diol repeating unit. ,9-Bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, BHT).

When repeating units derived from BHT are included, the rigidity of the polymer chain is further improved and higher heat resistance characteristics can be secured. However, if too many repeating units derived from BHT are included, the crystallinity of the polyester resin may become too high and the polymer may not melt even under high temperature conditions. Therefore, the repeating unit derived from BHT is 10.0 mol% or more, 15.0 mol% or more, or 20.0 mol% or more, and 35.0 mol% or less, 30.0 mol% or less, or 28.0 mol% of the total 100 mol% of the diol component in the polyester resin. It is preferable that it is included in % or less.

The polyester resin is a diol repeating unit, represented by Formula 1 In addition to repeating units derived from the compound and repeating units derived from 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane , it may further include repeating units derived from various diol compounds commonly used in the production of polyester resins.

For example, the polyester resin may include a repeating unit derived from one or more aliphatic diols having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms. Examples of the aliphatic diol include ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, 1,4-butanediol, 2,3-butanediol, 1,3-butanediol, pentanediol (1,5- pentanediol, etc.), hexanediol (1,6-hexanediol, etc.), neopentyl glycol (2,2-dimethyl-1,3-propanediol), 1,2-cyclohexanediol, 1,4-cyclohexanediol , 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tetramethylcyclobutanediol, etc., but is not limited thereto.

Specifically, the diol repeating unit of the polyester resin includes a repeating unit derived from ethylene glycol (EG) and a repeating unit derived from 1,4-cyclohexane dimethanol (CHDM). It may further include one or more of these.

The repeating unit derived from ethylene glycol is 5.0 mol% or more, 7.0 mol% or more, 9.0 mol% or more, or 10.0 mol% or more, and 55.0 mol% or less, 45.0 mol% or less, or 35.0 mol% or less of the diol repeating unit of 100 mol%. It may be contained in mole percent or less.

In addition, the repeating unit derived from 1,4-cyclohexanedimethanol is 10.0 mol% or more, 30.0 mol% or more, or 40.0 mol% or more, and 65.0 mol% or less, 63.0 mol% or less, out of 100 mol% of diol repeating units. , or may be included in an amount of 60.0 mol% or less.

If the ethylene glycol content is too low, the polymer may become brittle, and if it is too high, the effect of increasing the glass transition temperature may be minimal. If the content of cyclohexanedimethanol is too low, the degree of polymerization may decrease and the molecular weight may be low, and if it is too high, the polymer may become opaque and brittle due to high crystallinity.

The polyester resin according to one embodiment of the present invention contains, as a diol repeating unit, 1.0 to 20.0 mol% of repeating units derived from the compound represented by Formula 1, 5.0 to 55.0 mol% of repeating units derived from ethylene glycol, 1,4 - may include 10.0 to 65.0 mol% of repeating units derived from cyclohexanedimethanol, and 10.0 to 35.0 mole% of repeating units derived from BHT.

The dicarboxylic acid repeating unit of the polyester resin refers to a repeating unit derived from dicarboxylic acid and/or its derivatives. Derivatives of the dicarboxylic acid include alkyl esters of dicarboxylic acid (lower alkyl esters with 1 to 4 carbon atoms such as monomethyl, monoethyl, dimethyl, diethyl, or dibutyl ester) and acid anhydrides of dicarboxylic acid ( acid anhydride), etc.

The polyester resin according to one embodiment of the present invention may include a repeating unit derived from terephthalic acid or a derivative thereof as a dicarboxylic acid repeating unit. At this time, the content of the repeating unit derived from terephthalic acid among 100 mol% of the dicarboxylic acid repeating unit is 50 mol% or more, 60 mol% or more, or 70 mol% or more, and is 100 mol% or less, 90 mol% or less, Alternatively, it may be 80 mol% or less. If the content of repeating units derived from terephthalic acid or its derivatives among dicarboxylic acid repeating units is too small (less than 50 mol%), the physical properties of the polyester resin, such as heat resistance, chemical resistance, and weather resistance, may be reduced.

Meanwhile, the dicarboxylic acid repeating unit may further include repeating units derived from other aromatic dicarboxylic acids, aliphatic dicarboxylic acids, or derivatives thereof, in addition to repeating units derived from terephthalic acid or derivatives thereof.

Examples of the aromatic dicarboxylic acids include naphthalenedicarboxylic acids such as phthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid, diphenyl dicarboxylic acid, and 4,4'-stilbendicarboxylic acid; 2,5-furandicarboxylic acid, 2,5-thiophenedicarboxylic acid, etc. are mentioned.

Examples of the aliphatic dicarboxylic acids include cyclohexanedicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and 1,3-cyclohexanedicarboxylic acid, sebacic acid, succinic acid, isodecylsuccinic acid, and maleic acid. , fumaric acid, adipic acid, glutaric acid, and azelaic acid.

The total content of repeating units derived from the other aromatic dicarboxylic acids, aliphatic dicarboxylic acids, or derivatives thereof is 50 mol% or less, 40 mol% or less out of the total 100 mol% of dicarboxylic acid repeating units, or It may be 30 mol% or less, 0 mol% or more, 10 mol% or more, or 20 mol% or more.

The molar ratio of the dicarboxylic acid repeating unit and the diol repeating unit of the polyester resin is not particularly limited, but may range from 1:1 to 1:3, or 1:1 to 1:2, for example.

The above-mentioned polyester resin is a diol repeating unit derived from a compound represented by Formula 1 and 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetra Contains a repeating unit derived from oxaspiro[5,5]undecane, showing improved heat resistance compared to existing polyester resins. Specifically, the glass transition temperature (Tg) of the polyester resin according to one embodiment of the present invention is 80 ℃ or higher, or 85 ℃ or higher, or 90 ℃ or higher, or 95 ℃ or higher, and 130 ℃ or lower, 125 ℃ or lower, Or below 120°C, it exhibits excellent heat resistance properties comparable to that of polycarbonate. Accordingly, the polyester resin can be suitably used in fields that require high heat resistance.

The method for measuring the glass transition temperature of the polyester resin is explained in detail in the examples below.

Manufacturing method of polyester resin

According to one embodiment of the present invention, a method for producing the polyester resin is provided.

Specifically, the polyester resin includes a dicarboxylic acid component; A diol component containing a compound represented by Formula 1; and preparing a molten mixture of a polymerization catalyst, and polymerizing the molten mixture at a pressure of 10 torr or less and a temperature of 160°C to 200°C.

The melt polymerization is performed as a one-step reaction without distinction between esterification reaction and polycondensation reaction, and can be more effectively used when producing low molecular weight polyester resin.

For the melt polymerization, the dicarboxylic acid component, diol component, and polymerization catalyst are first mixed and then melted by raising the temperature.

The dicarboxylic acid component is dicarboxylic acid, its alkyl ester (lower alkyl ester with 1 to 4 carbon atoms, such as monomethyl, monoethyl, dimethyl, diethyl, or dibutyl ester), and/or their It is used to include acid anhydride. The dicarboxylic acid component reacts with the diol component to form a dicarboxylic acid repeating unit.

The dicarboxylic acid component is 50 mol% or more, 60 mol% or more, or 70 mol% or more of terephthalic acid and/or its derivatives out of 100 mol%, and 100 mol% or less, 90 mol% or less, or 80 mol% or less. and may include the remaining aromatic dicarboxylic acids, aliphatic dicarboxylic acids, or derivatives thereof as described above.

The diol component includes a compound represented by Formula 1, and its content is 1.0 mol% or more, 3.0 mol% or more, or 4.0 mol% or more, and 20.0 mol% or less, 18.0 mol% or more, based on 100 mol% of the diol component. It may be mol% or less, or 15.0 mol% or less.

Additionally, the diol component may include the various diol compounds described above in addition to the compound represented by Formula 1. Specifically, the diol component may further include ethylene glycol, 1,4-cyclohexanedimethanol, or a combination thereof in addition to the compound represented by Formula 1.

The ethylene glycol is 5 mol% or more, 10 mol% or more, 15 mol% or more, 20 mol% or more, or 25 mol% or more, and 60 mol% or less, 50 mol% or less, and 45 mol% of 100 mol% of the diol component. It may be included in an amount of 40 mol% or less, or 35 mol% or less.

The 1,4-cyclohexanedimethanol is present in 5 mol% or more, 10 mol% or more, 15 mol% or more, 20 mol% or more, or 25 mol% or more, and 70 mol% or less, 65 mol%, based on 100 mol% of the diol component. % or less, 60 mol% or less, 55 mol% or less, or 50 mol% or less.

In addition, the diol component may further include 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane (BHT). You can. In this case, the BHT content is 5 mol% or more, 10 mol% or more, 15 mol% or more, or 20 mol% or more, and 45 mol% or less, 40 mol% or less, or 35 mol% or less out of 100 mol% of the diol component. may be included.

In another embodiment, 100 mol% of the diol component includes 4 mol% to 20 mol% of the compound represented by Formula 1, 20 to 50 mol% of 1,4-cyclohexanedimethanol, 20 to 35 mol% of BHT, and a balance of ethylene glycol.

The molar ratio of the dicarboxylic acid component and the diol component may be in the range of 1:1 to 1:3, or 1:1 to 1:2. If the molar ratio of the dicarboxylic acid component and the diol component is less than 1:1, unreacted acid components may remain during the polymerization reaction, which may reduce the transparency of the polyester resin. If it exceeds 1:3, the terminals may have hydroxyl groups. Since it may be difficult to obtain a high molecular weight polymer due to its presence only, it is preferable to satisfy the above range.

The polymerization catalyst may include titanium (Ti), aluminum (Al), tin (Sn), germanium (Ge), and antimony (Sb)-based catalysts that are generally used in esterification or transesterification reactions.

Specifically, titanium-based catalysts include tetraethyl titanate, acetyltripropyl titanate, tetrapropyl titanate, tetrabutyl titanate, polybutyl titanate, 2-ethylhexyl titanate, octylene glycol titanate, and lactate. Examples include titanate, triethanolamine titanate, acetyl acetonate titanate, ethyl acetoacetic ester titanate, isostearyl titanate, titanium dioxide, titanium dioxide/silicon dioxide copolymer, titanium dioxide/zirconium dioxide copolymer, etc. can do. In addition, germanium-based catalysts include germanium dioxide and copolymers using it, and tin-based catalysts include monobutyltin hydroxide oxide, tetrabutyldibutoxytin oxide, dibutyltin oxide, and dibutyltin dilaurate. etc. can be mentioned. These catalysts can be used alone or in combination.

The catalyst is preferably used in an amount of 10 to 500 ppm, 50 to 400 ppm, or 100 to 300 ppm based on the central metal of the catalyst, based on the total weight of the dicarboxylic acid component and diol component as raw materials. If the catalyst content is less than 10 ppm, the reaction rate may be slow due to insufficient catalyst amount. In addition, if the catalyst content exceeds 500 ppm, side reactions may occur or the catalyst may remain in the polyester resin being manufactured, which may lead to yellowing of the resin, so it is preferable to satisfy the above range.

The temperature for melting each of the above components is not particularly limited. For example, a molten mixture can be prepared by mixing the dicarboxylic acid component, diol component, and polymerization catalyst, raising the temperature to 150 to 180° C., and stirring.

Next, the molten mixture is polymerized at a pressure of 10 torr or less and a temperature of 160°C to 200°C to prepare a polyester resin. Specifically, after raising the temperature of the molten mixture to the desired reaction temperature, the reactor pressure can be lowered to 10 torr or less using a vacuum pump, and then melt polymerization can be performed.

Preferably, the temperature of the polymerization step may be 160°C or higher, or 170°C or higher, or 180°C or higher, and may be 200°C or lower, or 190°C or lower, and the pressure may be 10 torr or lower, 5 torr or lower, or 1 torr or lower. However, it may be 0.05 torr or more.

The performance time of the melt polymerization step may vary depending on the reaction temperature, pressure, and composition of the raw materials, but may be performed for 1 to 15 hours, or 5 to 12 hours, for example. In addition, during the melt polymerization, it is desirable to continuously discharge water or alcohol generated as a by-product out of the reactor to increase the reaction progress rate.

Meanwhile, instead of the above melt polymerization, 1) dicarboxylic acid component; and esterification or transesterification of a diol component containing 1,4-cyclohexanedione glycerol diketal at normal pressure and a temperature of 200 to 300° C. in the presence of a polymerization catalyst, and 2) the reaction mixture with a concentration of 0.01 to 0.01. A polyester resin can be produced through a production method including the step of conducting a polycondensation reaction at a pressure of 0.1 torr and a temperature of 240 to 300 ° C. According to the above production method, a polyester resin with a higher molecular weight can be produced compared to melt polymerization.

The dicarboxylic acid component, diol component, and polymerization catalyst are as described above.

The esterification reaction may be performed at a temperature of 200 to 300 °C, preferably 220 to 280 °C, and more preferably 235 to 265 °C. At this time, it is desirable to continuously discharge water or alcohol generated as a by-product during the esterification reaction out of the reactor to increase the reaction progress rate.

The esterification reaction time may generally be 100 minutes to 10 hours, preferably 2 hours to 500 minutes, and may vary depending on the reaction temperature, pressure, and molar ratio of the dicarboxylic acid component and diol component used.

A phosphorus-based stabilizer such as phosphoric acid, trimethyl phosphate, or triethyl phosphate may be further added to the esterification reaction. The amount of the phosphorus-based stabilizer added may be 30 to 500 ppm, or 50 to 300 ppm, based on the amount of elemental phosphorus, relative to the total amount of raw materials. If the amount of the stabilizer added is less than 30 ppm, the stabilizing effect is insufficient, and the color of the polyester resin may turn yellow. If it exceeds 500 ppm, there is a risk that a polymer with the desired high degree of polymerization may not be obtained.

After completion of the esterification reaction, a polycondensation reaction is performed. The polycondensation reaction is carried out at a temperature of 230 to 300 °C, preferably 240 to 290 °C, more preferably 250 to 280 °C, and reduced pressure of 400 to 0.1 torr. The reduced pressure conditions of 400 to 0.1 torr are for removing diols and oligomers that are by-products of the polycondensation reaction. The polycondensation reaction is carried out for the necessary time until the desired intrinsic viscosity is reached, for example, 1 to 10 hours, or 3 to 5 hours.

Hereinafter, the present invention will be described in more detail through the following examples. However, the following examples are only for illustrating the present invention and the scope of the present invention is not limited to these only.

[Example]

Example 1-1 to Example 1-3

The acid component and diol component were added to the reactor in the composition and content shown in Table 1 below, and monobutyltin hydroxide oxide (PMC, Fascat-9100 ^® ) as a catalyst was added as the central metal relative to the total weight of the acid component and diol component. It was added at a content of 200 ppm based on (Sn), and then purged with nitrogen gas for 1 hour at room temperature (25°C).

The temperature of the reactor was raised to 160°C, the reactants were dissolved by stirring for 1 hour using a magnetic bar, and then the temperature was raised to 190°C at a rate of 5°C/30 minutes. After the reactor temperature reached 190°C, melt polymerization was performed for 12 hours while maintaining the internal pressure of the reactor at 0.1 torr using a vacuum pump to prepare a polyester resin.

Example 2

The acid component and diol component were added in the composition and content shown in Table 1 below into a reactor equipped with a methanol trap and cooling pipe, and monobutyltin hydroxide oxide (PMC, Fascat-9100 ^® ) was used as a catalyst to react with the acid component and diol. The total weight of the ingredients was added at a content of 200 ppm based on the central metal (Sn), and then purged with nitrogen gas for 1 hour at room temperature (25°C).

After raising the temperature of the reactor to 160°C, the reactants and catalyst were stirred and dissolved using a magnetic bar for 1 hour. Afterwards, the reactor temperature was raised to 240°C at a rate of 15°C/30 minutes, and when the reactor temperature reached 240°C, the reaction proceeded until the volume of methanol collected in the methanol trap reached 8.09 mL. Afterwards, the reaction was terminated and cooled to room temperature to obtain an -OH terminal product.

The -OH terminal product was introduced into the reactor and purged with nitrogen gas while raising the reactor temperature to 250°C. When the reactor temperature reached 250°C, the reactor temperature was brought to 280°C and the pressure was lower than 0.1 torr over 150 minutes while stirring at a speed of 50 rpm, and then reacted for 3 hours to prepare a polyester resin.

Comparative Example 1

Polyester resin was prepared in the same manner as in Examples 1-1 to 1-3, except that the acid component and diol component were used in the amounts shown in Table 1 below.

The acid components and diol components used in the above examples and comparative examples are as follows.

DMT: dimethyl terephthalate

EG: ethylene glycol

CHDM: 1,4-cyclohexanedimethanol

BHT: 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane

1,4-CHGD: 1,4-cyclohexanedione glycerol diketal

Experiment example

(1) Measurement of diol composition in the prepared polyester resin

The polyester resin was dissolved in a CDCl ₃ solvent at a concentration of 25 mg/mL, and then a spectrum was obtained using a 400 MHz nuclear magnetic resonance spectrometer (NMR). From the above spectrum, the diol composition in the polyester resin was quantitatively analyzed.

(2) Glass transition temperature (Tg)

The glass transition temperature of the polyester resin of each Example and Comparative Example was measured using a differential scanning calorimeter (DSC).

Specifically, the sample (resin) was filled in an aluminum pan, the temperature was raised to 310°C at 10°C/min, the temperature was maintained at 310°C for 10 minutes, the temperature was lowered to 30°C at -300°C/min, and then the temperature was lowered to 30°C at 10°C/min. The glass transition temperature (Tg) was measured from the heat flow obtained when the temperature was raised to 310 °C.

(3) Intrinsic viscosity (IV)

After dissolving the polyester resin at a 1% concentration in hexafluoro-2-propanol at room temperature, the intrinsic viscosity was measured using an Ubbelrod-type viscometer in a constant temperature bath at 35°C.

At this time, the temperature of the viscosity tube is maintained at 35°C, the time it takes for the solvent to pass through the inner section ab of the viscosity tube (efflux time) is t, and the time it takes for the solution to pass through is t. When t ₀ , specific viscosity is defined as Equation 1 below, and intrinsic viscosity was calculated using Equation 2 below.

[Equation 1]

[Equation 2]

In Equation 2, A is the Huggins constant, which is 0.247, and c is the concentration value, which is 1.2 g/dl.

Example 1-1 Example 1-2 Example 1-3 Example 2 Comparative Example 1 acid composition DMT (mol%) 90.9 90.9 90.9 90.9 90.9 Dior ingredient EG (mol%) 30 30 30 30 30 CHDM (mol%) 30 30 30 30 40 BHT (mol%) 30 35 25 30 30 1,4-CHGD (mol%) 10 5 15 10 - Diol composition in resin EG (mol%) 9.7 9.9 6.6 17.6 CHDM (mol%) 55.8 56.2 50.7 48.6 BHT (mol%) 26.2 29.8 27.9 25.4 1,4-CHGD (mol%) 8.3 4.3 14.7 8.5 Tg (℃) 108.59 95.43 98.89 105.66 86.28 IV (dl/g) 0.50 0.31 0.41 0.65 0.21

As can be seen in Table 1, the polyester resin containing a repeating unit derived from the compound represented by Formula 1 of the present invention has a higher glass transition temperature and higher intrinsic viscosity than the polyester resin of the comparative example, and has excellent heat resistance. could be confirmed.

Claims (15)

A polyester resin comprising a dicarboxylic acid repeating unit and a diol repeating unit,
The diol repeating unit is a repeating unit derived from a compound represented by the following formula 1 and 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5 ,5]Polyester resin comprising repeating units derived from undecane:
[Formula 1]

In Formula 1,
R ₁ and R ₂ are each independently substituted or unsubstituted C _1-10 alkylene.
According to paragraph 1,
R ₁ and R ₂ are each independently methylene, ethylene, or propylene,
Polyester resin.
According to paragraph 1,
The compound represented by Formula 1 is a polyester resin, which is a compound represented by the following Formula 1-1:
[Formula 1-1]

According to paragraph 1,
A polyester resin comprising 1.0 mol% to 20.0 mol% of a repeating unit derived from the compound represented by Formula 1 among 100 mol% of the diol repeating units.
According to paragraph 1,
The diol repeating unit is a polyester resin comprising at least one of a repeating unit derived from ethylene glycol and a repeating unit derived from 1,4-cyclohexanedimethanol.
According to paragraph 1,
A polyester resin comprising 5.0 to 55.0 mol% of a repeating unit derived from ethylene glycol, based on 100 mol% of the diol repeating unit.
According to paragraph 1,
A polyester resin comprising 10.0 to 65.0 mol% of a repeating unit derived from 1,4-cyclohexanedimethanol out of 100 mol% of the diol repeating units.
According to paragraph 1,
Among 100 mol% of the diol repeat units, repeats derived from 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane A polyester resin comprising 10.0 to 35.0 mol% of the unit.
According to paragraph 1,
A polyester resin comprising 50.0 to 100.0 mol% of a repeating unit derived from terephthalic acid or a derivative thereof, out of 100 mol% of the dicarboxylic acid repeating unit.
According to paragraph 1,
A polyester resin with a glass transition temperature of 80°C or higher.
Dicarboxylic acid component; A diol component containing a compound represented by Formula 1; and preparing a molten mixture of the polymerization catalyst, and
A method for producing a polyester resin, comprising the step of polymerizing the molten mixture at a pressure of 10 torr or less and a temperature of 160 ℃ to 200 ℃.
Dicarboxylic acid component; and subjecting a diol component containing the compound represented by Formula 1 to an esterification reaction or transesterification reaction at normal pressure and a temperature of 200 to 300° C. in the presence of a polymerization catalyst, and
A method for producing a polyester resin comprising subjecting the reaction mixture to a polycondensation reaction at a pressure of 0.01 to 0.1 torr and a temperature of 240 to 300 °C.
According to claim 11 or 12,
The diol component is a method for producing a polyester resin, comprising 1.0 mol% to 20.0 mol% of a compound represented by Formula 1 out of a total of 100 mol% of the diol component.
According to claim 11 or 12,
The diol component is ethylene glycol, 1,4-cyclohexanedimethanol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5,5 ]Method for producing polyester resin, comprising undecane or a combination thereof.
According to claim 11 or 12,
A method for producing a polyester resin, wherein the molar ratio of the dicarboxylic acid component and the diol component is 1:1 to 1:3.