KR20240107786A - 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, according to one embodiment of the present invention, it is a polyester resin comprising a dicarboxylic acid repeating unit and a diol repeating unit, wherein the diol repeating unit is from bicyclo[2.2.2]octane-1,4-dimethanol. Polyester resins comprising derived repeat units are provided.

Additionally, according to one embodiment of the present invention, a dicarboxylic acid component; A diol component including bicyclo[2.2.2]octane-1,4-dimethanol; and mixing a polymerization catalyst and melting it by raising the temperature, and polymerizing the molten mixture at a pressure of 10 torr or less and a temperature of 160°C to 200°C.

Additionally, according to one embodiment of the present invention, a dicarboxylic acid component; and carrying out an esterification or transesterification reaction of a diol component containing bicyclo[2.2.2]octane-1,4-dimethanol at a pressure of 700 to 800 torr and a temperature of 200 to 300° C. in the presence of a polymerization catalyst. , and subjecting the reaction mixture to a polycondensation reaction at a pressure of 0.1 to 400 torr and a temperature of 240 to 300 ° C. A method for producing a polyester resin is provided.

The polyester resin of the present invention contains a repeating unit derived from bicyclo[2.2.2]octane-1,4-dimethanol and exhibits a high glass transition temperature, so it can be suitably used in fields requiring high heat resistance. there is.

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.

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 derived from bicyclo[2.2.2]octane-1,4-dimethanol. A polyester resin comprising repeating units is provided.

The present inventors made efforts to develop a polyester resin that can exhibit excellent heat resistance properties at the level of polycarbonate, and as a result, polyester resin contains bicyclo[2.2.2]octane-1,4-dimethanol as a diol repeating unit. The present invention was completed by confirming that the glass transition temperature increased significantly when the derived repeating unit was included, resulting in excellent heat resistance properties.

Bicyclo[2.2.2]octane-1,4-dimethanol (BOD) is a compound having the structure of Formula 1 below:

[Formula 1]

The repeating unit derived from the BOD exhibits steric hindrance due to the bicyclo[2.2.2]octane ring, and the rotation of the bond is not free, thereby increasing the rigidity of the polymer chain. Shows effect. As a result, polyester resins containing BOD exhibit a significantly improved glass transition temperature (Tg) compared to existing polyester resins such as PETG, and are therefore used in fields that require high heat resistance, such as heat-resistant containers for food and architectural protection. It can be suitably used as a material for sheets, protective cases for electronic products, or parts for various home appliances.

In addition, BOD 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, so it can be suitably used in the manufacture of high-quality products.

The repeating unit derived from the BOD is 1 mol% or more, or 3 mol% or more, or 5 mol% or more, and is 40 mol% or less, or 35 mol%, out of the total 100 mol% of diol-derived repeating units contained in the polyester resin. It may be preferable to include less than or equal to 31 mol%. If the repeating unit derived from BOD among the diol repeating units is less than 1 mol%, a sufficient effect of improving the glass transition temperature cannot be obtained, and if it exceeds 40 mol%, the degree of polymerization may decrease and the molecular weight of the polyester resin may be lowered.

The polyester resin may further include repeating units derived from various diol compounds commonly used in the production of polyester resins in addition to repeating units derived from the BOD as diol repeating units.

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 1 mol% or more, 3 mol% or more, 5 mol% or more, 10 mol% or more, 15 mol% or more, or 20 mol% or more out of 100 mol% of the diol repeating unit, and 55 mole. % or less, 40 mol% or less, or 38 mol% or less.

The repeating unit derived from 1,4-cyclohexanedimethanol is 10 mol% or more, 30 mol% or more, or 40 mol% or more out of 100 mol% of diol repeating units, but is 65 mol% or less, 63 mol% or less, 60 mol% or more. It may be included in mol% or less, 56 mol% or less, or 50 mol% or less.

The polyester resin according to one embodiment of the present invention may include a repeating unit derived from BOD, a repeating unit derived from ethylene glycol, and a repeating unit derived from 1,4-cyclohexanedimethanol as diol repeating units. there is.

In one embodiment, 100 mol% of the diol repeating units of the polyester resin include 1 to 40 mol% of repeating units derived from BOD, 1 to 55 mol% of repeating units derived from ethylene glycol, and the balance of 1,4- It may contain repeating units derived from cyclohexanedimethanol.

Alternatively, 100 mol% of diol repeating units of the polyester resin may include 5 to 31 mol% of repeating units derived from BOD, 20 to 38 mol% of repeating units derived from ethylene glycol, and the balance of 1,4-cyclohexanedi. It may contain repeating units derived from methanol.

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. It may further include a repeating unit derived from ,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 mol% or more, 15 mol% or more, or 20 mol% or more, and 40 mol% or less, 35 mol% or less, or 30 mol% of the total 100 mol% of the diol component in the polyester resin. It is preferable that it is included in % or less.

On the other hand, when it includes a repeating unit derived from BHT, the repeating unit derived from BOD is 1 mol% or more, or 3 mol% or more, or 5 mol% or more, and 20 mol% or less out of 100 mol% of the diol repeating unit. , or 15 mol% or less may be preferable.

The polyester resin according to one embodiment of the present invention contains, as diol repeating units, a repeating unit derived from BOD, a repeating unit derived from ethylene glycol, a repeating unit derived from BHT, and a repeating unit derived from 1,4-cyclohexanedimethanol. may contain repeated units.

For example, the polyester resin contains, as diol repeating units, 1 to 20 mol% of repeating units derived from BOD, 1 to 20 mol% of repeating units derived from ethylene glycol, 10 to 30 mol% of repeating units derived from BHT, and The remainder may contain repeating units derived from 1,4-cyclohexanedimethanol.

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-described polyester resin contains a repeating unit derived from BOD as a diol repeating unit, and exhibits 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 90 ℃ or higher, or 95 ℃ or higher, or 98 ℃ or higher, or 100 ℃ or higher, and is 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 including bicyclo[2.2.2]octane-1,4-dimethanol (BOD); 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 BOD, the content of which is 5 mol% or more, 10 mol% or more, or 15 mol% or more, and 45 mol% or less, 40 mol% or less, 35 mol% or more, based on 100 mol% of the diol component. It may be less than mol%, or less than 30 mol%.

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

The ethylene glycol is 20 mol% or more, 30 mol% or more, 40 mol% or more, or 45 mol% or more, and 90 mol% or less, 80 mol% or less, 70 mol% or less, or 50 mol% of 100 mol% of the diol component. It may be included in less than %.

The 1,4-cyclohexanedimethanol is 5 mol% or more, 10 mol% or more, 15 mol% or more, or 20 mol% or more, and 50 mol% or less, 45 mol% or less, or 40 mol% or more of 100 mol% of the diol component. It may be included in mole percent 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, BHT may be included in an amount of 5 mol% or more, or 10 mol% or more, and 30 mol% or less, or 20 mol% or less, based on 100 mol% of the diol component.

In one embodiment, 100 mol% of the diol component may be comprised of 5 mol% to 45 mol% of BOD, 20 mol% to 90 mol% of ethylene glycol, and the balance of 1,4-cyclohexanedimethanol.

In another embodiment, 100 mol% of the diol component includes 5 mol% to 30 mol% of BOD, 20 to 50 mol% of ethylene glycol, 5 mol% to 30 mol% of BHT, and the balance of 1,4-cyclohexanedimethanol. It can be composed of:

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 speed of the polymerization reaction may decrease. Since it is too slow and productivity may decrease, it is desirable 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 carrying out an esterification or transesterification reaction of a diol component containing bicyclo[2.2.2]octane-1,4-dimethanol at a pressure of 700 to 800 torr and a temperature of 200 to 300° C. in the presence of a polymerization catalyst. , and 2) subjecting the reaction mixture to a polycondensation reaction at a pressure of 0.1 to 400 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, under normal pressure of 700 to 800 torr, or 750 to 800 torr. 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 120 minutes 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]

Examples 1 to 4 and Comparative Examples 1 to 2

The acid component and diol component were added to the reactor in the composition and content shown in Table 1 below. At this time, the acid component and diol component were added at a molar ratio of 1:1.3. As a catalyst, monobutyltin hydroxide oxide (PMC, Fascat-9100 ^® ) was added in an amount of 200 ppm based on the central metal (Sn) based on the total weight of the acid and diol components, and then incubated at room temperature (25°C). ) was purged with nitrogen gas for 1 hour.

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.

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

BOD: Bicyclo[2.2.2]octane-1,4-dimethanol

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, maintained at 310°C for 10 minutes, then the temperature was lowered to 30°C at -300°C/min, and then 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 concentration of 1% in hexafluoro-2-propanol at 25°C, 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 Example 2 Example 3 Comparative Example 1 acid composition DMT (mol%) 100 100 100 100 Dior ingredient EG (mol%) 80 70 60 90 CHDM (mol%) 30 30 30 40 BOD (mol%) 20 30 40 - Diol composition in resin EG (mol%) 37.64 30.61 23.84 60.4 CHDM (mol%) 46.33 46.27 46.02 39.6 BOD (mol%) 16.03 23.11 30.14 - Tg (℃) 98.0 105.3 115.3 80.7 IV (dl/g) 0.68 0.63 0.63 0.64

Example 4 Comparative example 2 acid composition DMT (mol%) 100 100 Dior ingredient EG (mol%) 30 30 CHDM (mol%) 30 40 BOD (mol%) 10 - BHT (mol%) 30 30 Diol composition in resin EG (mol%) 5.7 7 CHDM (mol%) 55.7 63 BOD (mol%) 8.6 - BHT (mol%) 30.0 30 Tg (℃) 103.25 85.36 IV (dl/g) 0.28 0.26

Referring to Tables 1 and 2, Examples 1 to 4, which contain repeating units derived from bicyclo[2.2.2]octane-1,4-dimethanol, have significantly improved heat resistance compared to Comparative Examples 1 and 2. You can check what it represents.

Claims (14)

A polyester resin comprising a dicarboxylic acid repeating unit and a diol repeating unit,
A polyester resin, wherein the diol repeating unit includes a repeating unit derived from bicyclo[2.2.2]octane-1,4-dimethanol.
According to paragraph 1,
A polyester resin comprising 1 mol% to 40 mol% of a repeating unit derived from bicyclo[2.2.2]octane-1,4-dimethanol out of 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 1 mol% to 55 mol% of a repeating unit derived from ethylene glycol out of 100 mol% of the diol repeating unit.
According to paragraph 1,
A polyester resin comprising 10 mol% to 65 mol% of a repeating unit derived from 1,4-cyclohexanedimethanol among 100 mol% of the diol repeating units.
According to paragraph 1,
The diol repeating unit further includes a repeating unit derived from 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane. Containing polyester resin.
According to clause 6,
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 mol% to 40 mol% of the unit.
According to paragraph 1,
A polyester resin comprising 50 mol% to 100 mol% of repeating units derived from terephthalic acid or a derivative thereof, out of 100 mol% of the dicarboxylic acid repeating units.
According to paragraph 1,
A polyester resin with a glass transition temperature of 90°C or higher.
Dicarboxylic acid component; A diol component including bicyclo[2.2.2]octane-1,4-dimethanol; 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 carrying out an esterification or transesterification reaction of a diol component containing bicyclo[2.2.2]octane-1,4-dimethanol at a pressure of 700 to 800 torr 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 0.1 to 400 torr and a temperature of 240 to 300 °C.
According to claim 10 or 11,
The diol component includes 5 mol% to 45 mol% of bicyclo[2.2.2]octane-1,4-dimethanol based on a total of 100 mol% of the diol component.
According to claim 10 or 11,
A method for producing a polyester resin, wherein the diol component includes ethylene glycol, 1,4-cyclohexanedimethanol, or a combination thereof.
According to claim 10 or 11,
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.