JP2022109838A - Polyester composition and uses of the same - Google Patents

Abstract

To provide a polyester composition having excellent storage properties (namely, few precipitates) and excellent heat resistance.SOLUTION: A polyester composition includes a polyester and a first component. When the polyester composition is characterized by gas chromatography (GC), the first component is flowed out with a holding time in the range of 36.38 minutes to 36.98 minutes; and the first component shown by chromatographic peaks with the holding time in a GC spectrum has an area of chromatographic peaks in the range of 1.5% to 7.0% relative to the whole area of chromatographic peaks of the polyester composition.SELECTED DRAWING: None

Description

The present invention relates to polyester compositions, particularly polyester compositions containing specific ingredients in specific amounts. The polyester composition of the present invention can be used as a plasticizer for thermoplastic polymers.

Plasticizers can be used to improve the physical properties of thermoplastic polymers, such as plasticity, flexibility, flexibility, toughness, and the like. Examples of thermoplastic polymers include, but are not limited to, phthalates, aliphatic esters, carboxylic acid esters, phosphates, epoxides, polyesters, and the like.

Polyesters are generally obtained by reacting diacids and diols. However, the polyesters obtained therefrom usually have precipitation problems due to the presence of by-products. Precipitation adversely affects the appearance, physical and mechanical properties of articles obtained from polyester.

The present invention provides polyester compositions with good shelf life (ie, low sedimentation) and heat resistance. The polyester composition of the present invention can be used as a plasticizer for thermoplastic polymers to impart suitable properties such as tensile strength, elongation and 100% tensile stress to the thermoplastic polymer.

Accordingly, an object of the present invention is to provide a polyester composition containing a polyester and a first component. Thereby, when characterizing the polyester composition by gas chromatography (GC), the first component is eluted with a retention time in the range of 36.38 minutes to 36.98 minutes, and the chromatographic has a chromatographic peak area ranging from 1.5% to 7.0% of the total chromatographic peak area of the polyester composition.

In some embodiments of the present invention, the polyester composition further comprises a second component. When characterizing the polyester composition by GC, the second component was eluted with a retention time in the range of 37.56 minutes to 38.29 minutes, with the second component indicated by a chromatographic peak at said retention time in the GC spectrum. has a chromatographic peak area ranging from 3.5% to 7.7% relative to the total chromatographic peak area of the polyester composition.

In some embodiments of the present invention, when the polyester composition is characterized by gas chromatography-mass spectrometry (GC-MS), the first component has a retention time ranging from 28.900 minutes to 29.000 minutes. The fragment pattern of the eluted first component is one or more signals of mass/charge number (m/z) selected from the group consisting of

In some embodiments of the present invention, the fragment pattern of the first component comprises signals at m/z of 41, 55, 56, 83, 111, 114, 127, 129, 141 and 201.

In some embodiments of the present invention, when characterizing the polyester composition by GC-MS, the second component is eluted with retention times ranging from 29.101 minutes to 29.200 minutes, and the fragmentation pattern of the second component is is m/ Contains one or more signals of z.

In some embodiments of the present invention, the fragment pattern of the second component comprises signals at m/z of 41, 55, 56, 69, 83, 111, 129, 141, 155 and 215.

〔式中、Ｒ_１は、以下の基である。

Ｒ_２は、以下の基である。

＊は、結合位置を示す。〕 In some embodiments of the present invention, the first component is a compound of formula (I) below and the second component is a compound of formula (II) below.

[In the formula, R ₁ is the following group.

R ₂ is the following group.

* indicates the binding position. ]

In some embodiments of the present invention, the polyester is polyadipate.

In some embodiments of the present invention, the polyester composition has a viscosity in the range of 2000cps to 4000cps at 25°C.

In some embodiments of the present invention, the polyester composition has an acid number ranging from 0.1 mg KOH/g to 0.7 mg KOH/g.

In some embodiments of the present invention, the polyester composition has a hydroxyl value in the range of 5.0 mg KOH/g to 15.0 mg KOH/g.

In some embodiments of the present invention, the polyester composition further comprises a third component. When characterizing the polyester composition by GC, the third component was eluted with a retention time ranging from 36.99 minutes to 37.55 minutes, and the third component indicated by the chromatographic peak at said retention time in the GC spectrum. has a chromatographic peak area in the range of 8.0% to 10.0% relative to the total chromatographic peak area of the polyester composition.

〔式中、Ｒ_３は、以下の基である。

Ｒ_４は、以下の基である。

＊は、結合位置を示す。〕 In some embodiments of the present invention, the third component is a compound of formula (III) below.

[In the formula, R ₃ is the following group.

R ₄ is the following group.

* indicates the binding position. ]

In some embodiments of the present invention, when characterizing the polyester composition by GC-MS, the third component is eluted with retention times ranging from 29.001 minutes to 29.100 minutes, and the fragmentation pattern of the third component is is of m/z selected from the group consisting of 29, 41, 55, 56, 69, 83, 101, 111, 114, 127, 129, 141, 155, 183, 201, 215, 287, 319 and 414 Contains one or more signals.

In some embodiments of the present invention, the fragment pattern of the third component comprises signals at m/z of 41, 55, 56, 69, 111, 127, 129, 141, 201 and 215.

In some embodiments of the present invention, in the GC described above, the polyester composition is loaded into a SGE BPI capillary column of 60 m length, 530 μm inner diameter and 3 μm film thickness under the following conditions: 100% dimethylpolysiloxane immobilization phase, carrier gas of nitrogen at a flow rate of 12 ml/min, 5 min at 50° C., ramping from 50° C. to 300° C. at a rate of 10° C./min, continuous stepping temperature at 300° C. for 40 min, inlet temperature It is characterized by the use of a 340°C, 1 µl sample injection volume of the polyester composition, and a flame ionization detector operated at 340°C.

In some embodiments of the present invention, in the GC-MS described above, the polyester composition is loaded into a ZB-1 capillary column of 30 m length, 250 μm inner diameter and 0.25 μm film thickness, under the following conditions: 100% Stationary phase of dimethylpolysiloxane, carrier gas of helium at a flow rate of 1.8 ml/min, 5 min at 50° C., ramping from 50° C. to 330° C. at a rate of 10° C./min, continuous at 330° C. for 27 min. entrance temperature 340° C., electron energy 70 eV (electron volts), ion source temperature 250° C., use of quadrupole mass filter, interface temperature 340° C., mass scan range from 29.0 m/z to 900 m/z. , and a solvent delay time of 1.5 minutes.

Another object of the present invention is to provide a thermoplastic polymeric material containing a plasticizer containing the above polyester composition and a thermoplastic polymer.

In some embodiments of the present invention, the thermoplastic polymer is a homopolymer of vinyl chloride or a copolymer of vinyl chloride.

In order to make the above problems, technical features and advantages of the present invention clearer, the present invention will be described in detail below with reference to several embodiments.

FIG. 1 is a GC spectrum of an embodiment of the polyester composition of the present invention. FIG. 2 is a partially enlarged schematic diagram of FIG. FIG. 3 is a GC-MS spectrum of an embodiment of the polyester composition of the present invention. 4 is a partially enlarged schematic view of FIG. 3. FIG. FIG. 5 is a schematic representation of the area division of a chromatographic peak.

Several embodiments of the present invention are described in detail below. This invention may, however, be embodied in various embodiments and should not be limited to the embodiments set forth herein.

Unless otherwise stated, the phrases "a", "the", etc. used in this specification and claims shall include both singular and plural forms.

Unless otherwise stated, the terms "first", "second", etc. used in the specification and claims have no special meaning and are used to distinguish between indicated elements or components. is simply used for These expressions are not intended to indicate any preference.

Unless otherwise stated, the expression "viscosity" used in the specification and claims means viscosity measured at 25°C.

Unless otherwise stated, the expression "atmospheric" in the specification and claims means 1 atmosphere (ie, 760 Torr).

As used herein, the expression that a specific component is eluted within a specific retention time range means that the peak (peak value) of the chromatographic peak wave indicating the specific component falls within a specific retention time range. means. That is, if the peak value falls within the retention time range, the chromatographic peak can be determined as the chromatographic peak indicative of that particular component.

As used herein, in GC spectra, the areas of chromatographic peaks are determined as follows. As shown in FIG. 5, a BVB (baseline-trough-baseline) approach is used. The same baseline is set for all chromatographic peaks and the valley point of a particular chromatographic peak is drawn down perpendicular to the baseline to determine the area of the particular chromatographic peak to be integrated. . Baseline refers to the carrier gas signal detected when the test sample does not pass the detector.

The benefits of the present invention are based on polyester compositions that have good shelf life (ie, low sedimentation) and heat resistance. The polyester compositions of the present invention and related applications are described in detail below.

1. Polyester Composition The polyester composition of the present invention has specific characteristics in the GC spectrum and comprises a polyester and a first component. The polyester compositions of the present invention may optionally contain other components, such as secondary and/or tertiary components. In some embodiments of the present invention, the polyester composition also has certain characteristics of GC-MS spectra.

Examples of polyesters include, but are not limited to, polyadipates, polysuccinates, polyglutarates, polypimelates, polyberinates, polysebacates, polyundecanoates, and polydecanoates. In some embodiments of the present invention, the polyester is a polyester derived from polyadipates such as adipic acid, neopentyl glycol and propylene glycol. The molecular weight of polyester is not particularly limited. Generally, the polyester number average molecular weight can be from 1200 to 4000, such as 1250, 1300, 1350, 1400, 1450, 1500, 1550, 1600, 1650, 1700, 1750, 1800, 1850, 1900, 1950. , 2000, 2050, 2100, 2150, 2200, 2250, 2300, 2350, 2400, 2450, 2500, 2550, 2600, 2650, 2700, 2750, 2800, 2850, 2900, 2950, 3000, 3050, 3100, 3150, 3200 , 3250, 3300, 3350, 3400, 3450, 3500, 3550, 3600, 3650, 3700, 3750, 3800, 3850, 3900 or 3950, or any range between these two recited values.

1.1. Spectral Analysis of Polyester Compositions When characterizing polyester compositions by GC, the first component is effluent with retention times ranging from 36.38 minutes to 36.98 minutes. That is, the chromatographic wave peaks (peak values) of the first component are 36.38 minutes, 36.39 minutes, 36.40 minutes, 36.41 minutes, 36.42 minutes, 36.43 minutes, 36.43 minutes, and 36.43 minutes. 44 minutes, 36.45 minutes, 36.46 minutes, 36.47 minutes, 36.48 minutes, 36.49 minutes, 36.50 minutes, 36.51 minutes, 36.52 minutes, 36.53 minutes, 36.53 minutes. 54 minutes, 36.55 minutes, 36.56 minutes, 36.57 minutes, 36.58 minutes, 36.59 minutes, 36.60 minutes, 36.61 minutes, 36.62 minutes, 36.63 minutes, 36.63 minutes. 64 minutes, 36.65 minutes, 36.66 minutes, 36.67 minutes, 36.68 minutes, 36.69 minutes, 36.70 minutes, 36.71 minutes, 36.72 minutes, 36.73 minutes, 36.73 minutes. 74 minutes, 36.75 minutes, 36.76 minutes, 36.77 minutes, 36.78 minutes, 36.79 minutes, 36.80 minutes, 36.81 minutes, 36.82 minutes, 36.83 minutes, 36.83 minutes. 84 minutes, 36.85 minutes, 36.86 minutes, 36.87 minutes, 36.88 minutes, 36.89 minutes, 36.90 minutes, 36.91 minutes, 36.92 minutes, 36.93 minutes, 36.93 minutes. 94 minutes, 36.95 minutes, 36.96 minutes, 36.97 minutes or 36.98 minutes, or any range between these two stated values. In addition, the first component is indicated by a chromatographic peak with a corresponding retention time in the GC spectrum. The first component has a chromatographic peak area in the range of 1.5% to 7.0% relative to the total chromatographic peak area of the polyester composition. FIG. 1 is a GC spectrum of an embodiment of the polyester composition of the present invention, more specifically, a GC spectrum of the polyester composition of Synthesis Example 4. FIG. FIG. 2 is a partially enlarged schematic diagram of FIG. 1 at retention times ranging from 34.5 minutes to 40.5 minutes.

In some embodiments of the present invention, the polyester composition further comprises a second component. When characterizing the polyester composition by GC, the second component is eluted with retention times ranging from 37.56 minutes to 38.29 minutes. That is, the chromatographic wave peaks (peak values) of the second component are 37.56 minutes, 37.57 minutes, 37.58 minutes, 37.59 minutes, 37.60 minutes, 37.61 minutes, 37.61 minutes, and 37.56 minutes. 62 minutes, 37.63 minutes, 37.64 minutes, 37.65 minutes, 37.66 minutes, 37.67 minutes, 37.68 minutes, 37.69 minutes, 37.70 minutes, 37.71 minutes, 37.71 minutes. 72 minutes, 37.73 minutes, 37.74 minutes, 37.75 minutes, 37.76 minutes, 37.77 minutes, 37.78 minutes, 37.79 minutes, 37.80 minutes, 37.81 minutes, 37.81 minutes. 82 minutes, 37.83 minutes, 37.84 minutes, 37.85 minutes, 37.86 minutes, 37.87 minutes, 37.88 minutes, 37.89 minutes, 37.90 minutes, 37.91 minutes, 37.91 minutes. 92 min, 37.93 min, 37.94 min, 37.95 min, 37.96 min, 37.97 min, 37.98 min, 37.99 min, 38.00 min, 38.01 min, 38.01 min. 02 minutes, 38.03 minutes, 38.04 minutes, 38.05 minutes, 38.06 minutes, 38.07 minutes, 38.08 minutes, 38.09 minutes, 38.10 minutes, 38.11 minutes, 38.11 minutes 12 minutes, 38.13 minutes, 38.14 minutes, 38.15 minutes, 38.16 minutes, 38.17 minutes, 38.18 minutes, 38.19 minutes, 38.20 minutes, 38.21 minutes, 38.21 minutes. 22 minutes, 38.23 minutes, 38.24 minutes, 38.25 minutes, 38.26 minutes, 38.27 minutes, 38.28 minutes or 38.29 minutes, or any range between these two stated values can go inside. In addition, the second component is indicated by a chromatographic peak with a corresponding retention time in the GC spectrum. The second component has a chromatographic peak area in the range of 3.5% to 7.5% relative to the total chromatographic peak area of the polyester composition.

The GC analysis described above is performed as follows. First, the polyester composition is loaded into a SGE BPI capillary column of length 60 m, internal diameter 530 μm and film thickness 3 μm. GC analysis was then performed under the following conditions: stationary phase of 100% dimethylpolysiloxane, carrier gas of nitrogen at a flow rate of 12 ml/min at 50°C for 5 minutes, from 50°C to 300°C at a rate of 10°C/min. of 300°C for 40 minutes, an inlet temperature of 340°C, a sample injection volume of 1 µl of the polyester composition, and the use of a flame ionization detector operated at 340°C.

Prior to conducting the GC analysis, it is preferred to subject the sample of the polyester composition to be analyzed to pretreatment in the following method. First, a sample of the polyester composition is heated in an oven at 70° C. for 1 hour to homogenize the sample. Next, the sample is mixed with acetone (solvent) to prepare a solution with a concentration of 5% by weight.

In some embodiments of the present invention, when characterizing the polyester composition by GC-MS, the first component is eluted with retention times ranging from 28.900 minutes to 29.000 minutes. The fragment pattern of the first component is the group consisting of: containing one or more signals of mass/charge number (m/z) selected from Preferably, the fragment pattern of the first component comprises signals at m/z of 41, 55, 56, 83, 111, 114, 127, 129, 141 and 201. The second component is eluted with a retention time ranging from 29.101 minutes to 29.200 minutes. The fragment pattern of the second component is the group consisting of comprising one or more signals of m/z selected from Preferably, the fragment pattern of the second component comprises signals at m/z of 41, 55, 56, 69, 83, 111, 129, 141, 155 and 215. FIG. 3 is a GC-MS spectrum of one embodiment of the polyester composition of the present invention, more specifically, a GC-MS spectrum of the polyester composition of Synthesis Example 4. FIG. 4 is a partially enlarged schematic diagram of FIG. 3 with retention times ranging from 26.5 minutes to 32 minutes.

The GC-MS analysis described above is performed as follows. First, the polyester composition is loaded into a ZB-1 capillary column with a length of 30 m, an internal diameter of 250 μm and a film thickness of 0.25 μm. GC analysis was then performed under the following conditions: stationary phase of 100% dimethylpolysiloxane, carrier gas of helium at a flow rate of 1.8 ml/min at 50°C for 5 minutes, from 50°C to 330°C at a rate of 10°C/min. 330° C. for 27 minutes in a series of temperature steps, inlet temperature 340° C., electron energy 70 eV (electron volts), ion source temperature 250° C., use of quadrupole mass filter, interface temperature 340° C., A mass scan range of 29.0 m/z to 900 m/z and a solvent delay time of 1.5 minutes are performed.

Prior to conducting the GC-MS analysis, it is preferred to subject the sample of the polyester composition to be analyzed to pretreatment in the following method. First, a sample of the polyester composition is heated in an oven at 70° C. for 1 hour to homogenize the sample. Next, the sample is mixed with acetone (solvent) to prepare a solution with a concentration of 1% by weight.

In some embodiments of the present invention, the polyester composition further comprises a third component. When characterizing the polyester composition by GC, the third component bleeds with retention times ranging from 36.99 minutes to 37.55 minutes. That is, the chromatographic wave peaks (peak values) of the third component are 36.99 minutes, 37.00 minutes, 37.01 minutes, 37.02 minutes, 37.03 minutes, 37.04 minutes, 37.04 minutes, and 37.04 minutes. 05 min, 37.06 min, 37.07 min, 37.08 min, 37.09 min, 37.10 min, 37.11 min, 37.12 min, 37.13 min, 37.14 min, 37.14 min. 15 minutes, 37.16 minutes, 37.17 minutes, 37.18 minutes, 37.19 minutes, 37.20 minutes, 37.21 minutes, 37.22 minutes, 37.23 minutes, 37.24 minutes, 37.24 minutes. 25 min, 37.26 min, 37.27 min, 37.28 min, 37.29 min, 37.30 min, 37.31 min, 37.32 min, 37.33 min, 37.34 min, 37.34 min. 35 minutes, 37.36 minutes, 37.37 minutes, 37.38 minutes, 37.39 minutes, 37.40 minutes, 37.41 minutes, 37.42 minutes, 37.43 minutes, 37.44 minutes, 37.44 minutes. 45 minutes, 37.46 minutes, 37.47 minutes, 37.48 minutes, 37.49 minutes, 37.50 minutes, 37.51 minutes, 37.52 minutes, 37.53 minutes, 37.54 minutes or 37.54 minutes. 55 minutes, or can fall within the range between these two stated values. In addition, the third component is indicated by the corresponding retention time chromatographic peaks of the GC spectrum, and the third component is 8.0% to 10% of the total area of the chromatographic peaks of the polyester composition. It has a chromatographic peak area in the range of 0.0%. Further, when characterizing the polyester composition by GC-MS, the third component is eluted with retention times ranging from 29.001 minutes to 29.100 minutes. the fragment pattern of the third component is selected from the group consisting of: containing one or more signals of m/z Preferably, the fragment pattern of the third component comprises signals at m/z of 41, 55, 56, 69, 111, 127, 129, 141, 201 and 215. The methods of GC analysis and GC-MS analysis are the same as those described above.

1.1.1. First Component In order to give the polyester composition of the present invention good storage stability and heat resistance, and to give the thermoplastic polymer suitable properties such as tensile strength, elongation, and 100% tensile stress, polyester The amount of the first component in the composition is controlled within a specific range. Thus, as noted above, when characterizing the polyester compositions of the present invention by the GC analysis described above, the retention time of the chromatographic peak in the GC spectrum is shown by the total area of the chromatographic peak of the polyester composition. The first component is in the range of 1.5% to 7.0%, for example 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5.0%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, 6.0%, 6.1%, 6.2%, 6.3%, 6.4%, 6.5%, 6.6%, 6.7%, 6.8% or 6.9%, or between these two stated values with a chromatographic peak area percentage within the range of . Compared to the other components, the structure of the first component has poor heat resistance. If the amount of the first component is higher than the above range, the thermoplastic polymer using the polyester composition may have a low residual elongation after heat aging. In addition, if the amount of the first component is lower than the above range, the structure of the first component will be soft and the thermoplastic polymer using the polyester composition will not be effectively plasticized, resulting in an excessively high 100% Tensile stress.

In some embodiments of the present invention, the first component can be a compound of formula (I) below.

Ｒ_１は、好ましくは以下の基である。

＊は、結合位置を示す。式（Ｉ）で示される化合物は、アジピン酸を２－メチル－１，３－プロパンジオール、エチレングリコール又は１，３－プロパンジオールと反応させることで得ることができる。 In formula (I), R ₁ is the following group.

R ₁ is preferably the following groups.

* indicates the binding position. Compounds of formula (I) can be obtained by reacting adipic acid with 2-methyl-1,3-propanediol, ethylene glycol or 1,3-propanediol.

1.1.2. Second component In order to provide the polyester composition of the present invention with good storage stability and heat resistance, and to the thermoplastic polymer using the polyester composition, suitable properties such as tensile strength, elongation, 100% tensile stress, etc. To impart properties, the amount of the second component in the polyester composition is controlled within a specific range. Thus, as noted above, when characterizing the polyester composition of the present invention by the GC analysis described above, the retention time of the chromatographic peak in the GC spectrum is shown by the total area of the chromatographic peak of the polyester composition. The second component is in the range of 3.5% to 7.5%, for example 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5.0%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, 6.0%, 6.1%, 6.2%, 6.3%, 6.4%, 6.5%, 6.6%, 6.7%, 6.8%, 6.9%, 7.0%, 7.1%, Chromatographic peak area percent within 7.2%, 7.3% or 7.4%, or a range between these two stated values. The structure of the second component has branching useful for improving migration resistance of the polyester composition. If the amount of the second component is lower than the above range, the migration resistance of the polyester composition is poor. If the amount of the second component is higher than the above range, precipitation of crystals will occur and the migration resistance of the polyester composition will be low.

In some embodiments of the present invention, the second component can be a compound of formula (II) below.

Ｒ_２は、好ましくは以下の基である。

＊は、結合位置を示す。式（ＩＩ）で示される化合物は、アジピン酸をネオペンチルグリコール又は１，４－ブタンジオールと反応させることで得ることができる。 In formula (II), R ₂ is the following group.

R ₂ is preferably the following groups.

* indicates the binding position. Compounds of formula (II) can be obtained by reacting adipic acid with neopentyl glycol or 1,4-butanediol.

1.1.3. Third Component In some embodiments of the present invention, the polyester composition of the present invention further comprises a third component. To provide the polyester composition of the present invention with good shelf life and heat resistance, and to impart suitable properties such as tensile strength, elongation, and 100% tensile stress to thermoplastic polymers using the polyester composition. Therefore, the amount of the third component in the polyester composition is controlled within a specific range. Thus, as noted above, when characterizing the polyester composition of the present invention by the GC analysis described above, the retention time of the chromatographic peak in the GC spectrum is shown by the total area of the chromatographic peak of the polyester composition. The third component is in the range of 8.0% to 10.0%, such as 8.1%, 8.2%, 8.3%, 8.4%, 8.5%, 8.6%, 8.7%, 8.8%, 8.9%, 9.0%, 9.1%, 9.2%, 9.3%, 9.4%, 9.5%, 9.6%, Chromatographic peak area percent within 9.7%, 9.8% or 9.9%, or a range between these two stated values.

In some embodiments of the present invention, the third component is a compound of formula (III) below.

Ｒ_４は、以下の基である。

＊は、結合位置を示す。式（ＩＩＩ）で示される化合物は、アジピン酸をネオペンチルグリコール及び２－メチル－１，３－プロパンジオールと反応させることで得ることができる。 In formula (III), R ₃ is the following group.

R ₄ is the following group.

* indicates the binding position. Compounds of formula (III) can be obtained by reacting adipic acid with neopentyl glycol and 2-methyl-1,3-propanediol.

1.2. Preparation of Polyester Composition The polyester composition of the present invention can be obtained by subjecting one or more aliphatic diacids and one or more aliphatic diols to an esterification polymerization reaction. Examples of aliphatic diacids include, but are not limited to, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, undecanoic acid and decanoic acid. The above aliphatic diacids can be used alone or in combination of two or more. Examples of aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2 ,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-ethyl-2-butyl-1,3-propanediol and 2,2,4-trimethyl-1, Including but not limited to 5-propanediol. The above aliphatic diols can be used alone or in combination of two or more. In some embodiments of the present invention, the esterification polymerization reaction is carried out by reacting adipic acid with neopentyl glycol and 2-methyl-1,3-propanediol.

In addition, the esterification polymerization reaction is usually terminated by adding a mixed terminating agent. Mixed reaction terminators include, but are not limited to, aliphatic monocarboxylic acids and aliphatic saturated monohydric alcohols. Examples of aliphatic monocarboxylic acids include n-butanoic acid, isobutanoic acid, n-pentanoic acid, isopentanoic acid, n-hexanoic acid, isohexanoic acid, n-heptanoic acid, isoheptanoic acid, n-octanoic acid, isooctanoic acid, Including, but not limited to, 2-ethylhexanoic acid, n-nonanoic acid, n-decanoic acid, lauric acid, myristic acid, palmitic acid and stearic acid. The above aliphatic monocarboxylic acids may be used alone or in combination of two or more. Examples of aliphatic saturated monohydric alcohols include n-pentyl alcohol, isopentyl alcohol, n-hexyl alcohol, isohexyl alcohol, n-octyl alcohol, isooctyl alcohol, 2-ethylhexanol, 2,2-dimethylpentanol. , n-nonyl alcohol, isononyl alcohol, n-decyl alcohol, isodecyl alcohol, 2,2,4-trimethylpentanol and lauryl alcohol. The above aliphatic saturated monohydric alcohols may be used alone or in combination of two or more. In some embodiments of the present invention, mixtures of lauric acid and 2-ethylhexanoic acid are used.

The polyester compositions of the present invention can be prepared in the absence of catalyst. However, catalysts can also be used to reduce the reaction time. Examples of catalysts that can be used to prepare the polyester compositions of the present invention include sulfuric acid, phosphoric acid, p-toluenesulfonic acid, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin oxide, tetraisopropyl titanate, tetra Including but not limited to butyl titanate, tetraisooctyl titanate and titanium.

In some embodiments of the invention, the polyester composition of the invention is prepared as follows. First, the reactants are added to the reaction vessel, nitrogen is introduced, and the atmospheric esterification reaction is carried out at 140° C. to 200° C. under the condition of stirring the reactants to initiate the dehydration reaction. Subsequently, a catalyst is added, and an atmospheric esterification reaction is carried out at 210° C. to 230° C. under a nitrogen atmosphere. Thereafter, the pressure is reduced to 460 torr to 200 torr and the reduced pressure esterification reaction is carried out at 210°C to 240°C. The esterification reaction is terminated when the acid value of the reaction intermediate is lower than 5 mgKOH/g. The pressure is then reduced to 0 torr and the reduced pressure polycondensation reaction is carried out at 210-230°C. The polycondensation reaction is terminated when the hydroxyl value of the reaction product is between 1.0 mgKOH/g and 15.0 mgKOH/g. Finally, the product is cooled and filtered to obtain the polyester composition.

In the polyester composition, by controlling the amount ratio of raw materials to be added, the esterification temperature, the esterification time and the polycondensation time to achieve the ideal amount of each component, the first component, the second component and the second component The amounts of the three components can be adjusted.

1.3. Properties of the Polyester Compositions In some embodiments of the present invention, the polyester compositions of the present invention have the following properties. However, the present invention is not limited to the following properties, and those skilled in the art can adjust the properties of the polyester composition as needed.ポリエステル組成物は、２０００ｃｐｓ～４０００ｃｐｓの範囲内、例えば、２０５０ｃｐｓ、２１００ｃｐｓ、２１５０ｃｐｓ、２２００ｃｐｓ、２２５０ｃｐｓ、２３００ｃｐｓ、２３５０ｃｐｓ、２４００ｃｐｓ、２４５０ｃｐｓ、２５００ｃｐｓ、２５５０ｃｐｓ、２６００ｃｐｓ、２６５０ｃｐｓ、２７００ｃｐｓ、２７５０ｃｐｓ、２８００ｃｐｓ、２８５０ｃｐｓ、２９００ｃｐｓ、 ２９５０ｃｐｓ、３０００ｃｐｓ、３０５０ｃｐｓ、３１００ｃｐｓ、３１５０ｃｐｓ、３２００ｃｐｓ、３２５０ｃｐｓ、３３００ｃｐｓ、３３５０ｃｐｓ、３４００ｃｐｓ、３４５０ｃｐｓ、３５００ｃｐｓ、３５５０ｃｐｓ、３６００ｃｐｓ、３６５０ｃｐｓ、３７００ｃｐｓ、３７５０ｃｐｓ、３８００ｃｐｓ、３８５０ｃｐｓ、３９００ｃｐｓ若しくは３９５０ｃｐｓ、又はこれら記載された２つの値It has a viscosity at 25°C in the range between The polyester composition is in the range of 0.1 mg KOH/g to 0.7 mg KOH/g, such as 0.15 mg KOH/g, 0.2 mg KOH/g, 0.25 mg KOH/g, 0.3 mg KOH/g, 0.35 mg KOH/g. g, 0.4 mg KOH/g, 0.45 mg KOH/g, 0.5 mg KOH/g, 0.55 mg KOH/g, 0.6 mg KOH/g or 0.65 mg KOH/g, or any range between these two stated values It has an acid value within The polyester composition is in the range of 5.0 mg KOH/g to 15.0 mg KOH/g, such as 5.5 mg KOH/g, 6.0 mg KOH/g, 6.5 mg KOH/g, 7.0 mg KOH/g, 7.5 mg KOH/g. g, 8.0 mg KOH/g, 8.5 mg KOH/g, 9.0 mg KOH/g, 9.5 mg KOH/g, 10.0 mg KOH/g, 10.5 mg KOH/g, 11.0 mg KOH/g, 11.5 mg KOH/g, 12.0 mg KOH/g, 12.5 mg KOH/g, 13.0 mg KOH/g, 13.5 mg KOH/g, 14.0 mg KOH/g or 14.5 mg KOH/g, or any range between these two stated values It has a hydroxyl value.

2. Thermoplastic Polymeric Materials The polyester composition of the present invention can be used as a plasticizer for thermoplastic polymers. Accordingly, the present invention also provides a thermoplastic polymeric material comprising a plasticizer and a thermoplastic polymer that can contain the polyester composition of the present invention. Alternatively, the plasticizer can consist essentially of the polyester composition of the present invention, or the plasticizer consists of the polyester composition of the present invention. Examples of said thermoplastic polymers include homopolymers of vinyl chloride and copolymers of vinyl chloride such as vinyl chloride-vinyl acetate copolymer, vinyl chloride-dichloroethylene copolymer, vinyl chloride-methyl methacrylate copolymer, etc. Not limited. The thermoplastic polymeric materials of the present invention have good tensile strength, elongation, 100% tensile stress, etc., and are therefore useful in a variety of processing applications.

In the thermoplastic polymer material of the present invention, the amount of the polyester composition can be 10 parts by weight to 120 parts by weight with respect to 100 parts by weight of the thermoplastic polymer, such as 11 parts by weight, 12 parts by weight. parts, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, 26 parts by weight, 27 parts by weight, 28 parts by weight, 29 parts by weight, 30 parts by weight, 31 parts by weight, 32 parts by weight, 33 parts by weight, 34 parts by weight, 35 parts by weight, 36 parts by weight, 37 parts by weight parts, 38 parts by weight, 39 parts by weight, 40 parts by weight, 41 parts by weight, 42 parts by weight, 43 parts by weight, 44 parts by weight, 45 parts by weight, 46 parts by weight, 47 parts by weight, 48 parts by weight, 49 parts by weight, 50 parts by weight, 51 parts by weight, 52 parts by weight, 53 parts by weight, 54 parts by weight, 55 parts by weight, 56 parts by weight, 57 parts by weight, 58 parts by weight, 59 parts by weight, 60 parts by weight, 61 parts by weight, 62 parts by weight parts, 63 parts by weight, 64 parts by weight, 65 parts by weight, 66 parts by weight, 67 parts by weight, 68 parts by weight, 69 parts by weight, 70 parts by weight, 71 parts by weight, 72 parts by weight, 73 parts by weight, 74 parts by weight, 75 parts by weight, 76 parts by weight, 77 parts by weight, 78 parts by weight, 79 parts by weight, 80 parts by weight, 81 parts by weight, 82 parts by weight, 83 parts by weight, 84 parts by weight, 85 parts by weight, 86 parts by weight, 87 parts by weight parts, 88 parts by weight, 89 parts by weight, 90 parts by weight, 91 parts by weight, 92 parts by weight, 93 parts by weight, 94 parts by weight, 95 parts by weight, 96 parts by weight, 97 parts by weight, 98 parts by weight, 99 parts by weight, 100 parts by weight, 101 parts by weight, 102 parts by weight, 103 parts by weight, 104 parts by weight, 105 parts by weight, 106 parts by weight, 107 parts by weight, 108 parts by weight, 109 parts by weight, 110 parts by weight, 111 parts by weight, 112 parts by weight 113 parts by weight, 114 parts by weight, 115 parts by weight, 116 parts by weight, 117 parts by weight, 118 parts by weight, or 119 parts by weight, or any range between these two recited values.

The thermoplastic polymeric material of the present invention may optionally contain other additives to optimally improve the processability of the thermoplastic polymeric material during processing or to impart specific properties to the final product. can include Additives include, but are not limited to, stabilizers, fillers, dyes, pigments, antioxidants, flame retardants, foaming agents and antistatic agents.

In some embodiments of the invention, the thermoplastic polymeric material further comprises a stabilizer. Examples of stabilizers include, but are not limited to, epoxidized soybean oil, calcium/zinc stabilizers, barium/zinc stabilizers, and lead size stabilizers. In the thermoplastic polymeric material of the present invention, the amount of the stabilizer can be 0 to 10 parts by weight with respect to 100 parts by weight of the thermoplastic polymer, such as 0.1 parts by weight, 0 .2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, 0.9 parts by weight, 1 part by weight , 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, or 9 parts by weight, or any range between these two recited values. can.

3. Example
3.1. Test method [GC spectrum analysis]
A sample of the polyester composition is heated in an oven at 70° C. for 1 hour to homogenize the sample. The sample is then mixed with acetone (solvent) to prepare a 5% by weight solution to complete the pretreatment of the sample to be tested.

The pretreated sample is loaded onto a SGE BPI capillary column of 60 m length, 530 μm internal diameter and 3 μm film thickness. Subsequently, the sample is analyzed using a gas chromatograph mass spectrometer (model: QP 2020, Shimadzu Corporation). GC analysis was performed under the following conditions: 100% dimethylpolysiloxane stationary phase, nitrogen carrier gas at a flow rate of 12 ml/min, 50° C. for 5 minutes, heating from 50° C. to 300° C. at a rate of 10° C./min. , 300°C for 40 minutes in a series of temperature steps, an inlet temperature of 340°C, a sample injection volume of 1 μl of the polyester composition, and the use of a flame ionization detector operated at 340°C.

[GC-MS analysis]
A sample of the polyester composition is heated in an oven at 70° C. for 1 hour to homogenize the sample. The sample is then mixed with acetone (solvent) to prepare a 5% by weight solution to complete the pretreatment of the sample to be tested.

The pretreated sample is loaded into a ZB-1 capillary column with a length of 30 m, internal diameter of 250 μm and film thickness of 0.25 μm. Subsequently, the sample is analyzed using a gas chromatograph mass spectrometer (model: QP 2020, Shimadzu Corporation). Using 100% dimethylpolysiloxane as stationary phase, using helium as carrier gas at a flow rate of 1.8 ml/min, heating at 50°C for 5 minutes from 50°C to 330°C at a rate of 10°C/min, 330 A continuous temperature step of 27 minutes is performed at °C. GC-MS analysis was then performed under the following conditions: inlet temperature 340°C, electron energy 70 eV (electron volts), ion source temperature 250°C, use of a quadrupole mass filter, interface temperature 340°C, 29.0 m/z~ A mass scan range of 900 m/z and a solvent delay time of 1.5 minutes are performed.

[Acid value analysis]
First, a KOH solution is prepared as follows. Weigh 0.7 g of KOH, dissolve in a small amount of distilled water, and then dilute to 1000 ml with neutral ethanol to obtain a KOH solution. Weigh 0.4 g of reagent grade potassium hydrogen phthalate (KHP) and add to a 250 ml conical flask. Add 100 ml of distilled water to dissolve KHP to obtain a KHP solution. Two drops of phenolphthalein indicator are then added to the KHP solution and the KHP solution is subsequently titrated with the KOH solution to calculate the normality N of the KOH solution.

Next, 10 g of the sample to be tested is weighed and added to a 250 ml conical flask, to which 100 ml of neutral 2-propanol solution and 3-4 drops of phenolphthalein indicator are added. Shake the flask and heat slightly to ensure complete dissolution of the sample. The sample is titrated with the KOH solution until the solution becomes reddish and the reddish color is maintained for 30 seconds to the end point of the titration. The acid number of the sample is calculated according to formula (1) below.

[Hydroxyl value analysis]
First, an acetylating reagent is made as follows. 10 ml of acetic anhydride is drawn through a straw and added to a 100 ml flask, 50 ml of pyridine is added to the flask and the resulting mixture is stirred to obtain the acetylating reagent.

A KOH solution is then prepared according to the following method. Weigh 0.7 g of KOH, dissolve in a small amount of distilled water, and then dilute to 1000 ml with neutral ethanol to obtain a KOH solution. Weigh 0.4 g of reagent grade potassium hydrogen phthalate (KHP) and add to a 250 ml conical flask. Add 100 ml of distilled water to dissolve KHP to obtain a KHP solution. Two drops of phenolphthalein indicator are then added to the KHP solution and the KHP solution is subsequently titrated with the KOH solution. Record the KOH titer (ie, blank titer) and calculate the normality N of the KOH solution.

10 g of the sample to be tested is then weighed and added to a stoppered conical flask, to which 10 ml of acetylating reagent is added. An air cooler is placed on top of the flask, and the flask is shaken and heated with steam (98±2° C.). After completion of the reaction, the flask is cooled to room temperature, 25 ml of n-butanol is added to the flask, and the flask is vigorously shaken. Then add 2-3 drops of phenolphthalein indicator. The sample is titrated with the KOH solution until the solution becomes reddish and the reddish color is maintained for 30 seconds to the end point of the titration. Record the KOH titer (ie, test titer) and calculate the hydroxyl number of the sample according to equation (2) below.

[Viscosity analysis]
The sample to be tested is added to a volumetric cylinder with a height of 180 mm and a diameter of 50 mm. The volumetric cylinder is then placed in a constant temperature water bath at 25±1°C. Samples are tested using a Brookfield Viscometer model LV with suitable shaft and rotational speeds.

First, the hot press is preheated at 170°C for 5 minutes. The thermoplastic polymeric material is then hot-pressed at 170° C. and a pressure of 50 kg/cm ³ for 5 minutes to obtain a test piece with a length of 20 cm, a width of 20 cm and a thickness of 1 mm. The specimen is then cooled to room temperature under a pressure of 60 kg/cm ³ . Subsequently, using JIS-6301-3 model die-cut mold, the test pieces are cut into dumbbell-shaped test pieces. Dumbbell specimens are tested to obtain initial tensile strength, initial elongation and initial 100% tensile stress using a universal testing machine (model: 3366, Instron) according to ASTM D638.

[Volatilization analysis]
First, the hot press is preheated at 170°C for 5 minutes. The thermoplastic polymeric material is then hot-pressed at 170° C. and a pressure of 50 kg/cm ³ for 5 minutes to obtain a test piece with a length of 20 cm, a width of 20 cm and a thickness of 1 mm. The specimen is then cooled to room temperature under a pressure of 60 kg/cm ³ . Measure the weight of the specimen. The specimen is then placed at 136° C. for 168 hours, subjected to heat aging, and the weight of the specimen after heat aging is determined. The volatilization rate of the specimen is calculated according to Equation (3) below.

[Analysis of tensile strength after heat aging, elongation after heat aging, and 100% tensile stress after heat aging]
First, the hot press is preheated at 170°C for 5 minutes. The thermoplastic polymeric material is then hot-pressed at 170° C. and a pressure of 50 kg/cm ³ for 5 minutes to obtain a test piece with a length of 20 cm, a width of 20 cm and a thickness of 1 mm. Subsequently, using JIS-6301-3 model die-cut mold, the test pieces are cut into dumbbell-shaped test pieces. Dumbbell-shaped specimens are placed at 136° C. for 168 hours and subjected to heat aging. Heat aged specimens are tested according to ASTM D638 using a universal testing machine 3366 to obtain heat aged tensile strength, heat aged elongation and 100% heat aged tensile stress. The percentage of residual tensile strength (hereinafter referred to as “residual tensile percentage”) can be obtained by dividing the tensile strength after heat aging by the initial tensile strength. The residual percentage of elongation (hereinafter referred to as "residual elongation") can be obtained by dividing the elongation after heat aging by the initial elongation.

[Migration resistance test]
A thermoplastic polymeric material is pressed into a test piece 38 mm long, 6 mm wide and 1 mm thick. Each specimen was placed between two acrylonitrile-butadiene-styrene resin plates (Model: TAIRILAC AG15E1, FORMOSA CHEMICALS & FIBRE CORPORATION) and two high impact polystyrene resin ramps (Model: TAIREX HP8250, FORMOSA CHEMICALS & FIBRE CORPORATION). ) to generate a laminate. The laminate is clamped using sandwich clamps, a 1 kg counterweight is placed on top of the laminate, and the laminate is placed in an oven at 70° C. for 72 hours. After that, the resin plate is observed to confirm whether or not the polyester composition migrates from the test piece made of the thermoplastic polymer material to the resin plate and causes etching. Visually inspect the surface of the resin plate for damage. Evaluation criteria are as follows. The number "1" indicates that no trace is observed on the surface. The number "2" represents that a shadow pressed against the surface is observed. The number "3" indicates that obvious depressions are observed on the surface. The number "4" indicates that obvious bulges and dents are observed on the surface. The number "5" represents significant damage and stickiness observed on the surface. The smaller the number, the better the migration resistance.

3.2. Preparation and Characterization of Polyester Compositions
3.2.1. Preparation of polyester composition [Synthesis Example 1]
In a 3 L round bottom flask equipped with stirrer, thermometer, distillation tube and concentration meter, 1000 g adipic acid, 240.53 g neopentyl glycol, 485.63 g 2-methyl-1,3-propanediol, 155. 95 g of 2-ethylhexanol and 274.02 g of lauric acid were added. An atmospheric esterification reaction was carried out at 150° C. under the conditions of introducing nitrogen and stirring the reactants to initiate the dehydration reaction. Subsequently, 0.22 g of tetraisopropyl titanate was added as a catalyst, and normal pressure esterification was carried out at 220° C. under nitrogen atmosphere. After that, the pressure was lowered to 460 torr to 200 torr and the vacuum esterification reaction was carried out at 210°C. The esterification reaction was run for a total of 298 minutes. The acid value, which marks the end of esterification, is 4.79 mg KOH/g. The pressure was then lowered to 0 Torr and the vacuum polycondensation reaction was carried out at 230° C. for 397 minutes. The reaction product was then cooled to 105° C. and 0.05 wt % (relative to the total weight of the product) of diatomaceous earth (model: HYFLO) was added. Subsequently, the product was filtered using a frame filter to obtain a polyester composition of Synthesis Example 1.

[Synthesis Example 2]
In a 3 L round bottom flask equipped with stirrer, thermometer, distillation tube and concentration meter, 1000 g adipic acid, 320.70 g neopentyl glycol, 416.25 g 2-methyl-1,3-propanediol, 155. 95 g of 2-ethylhexanol and 274.02 g of lauric acid were added. An atmospheric esterification reaction was carried out at 150° C. under the conditions of introducing nitrogen and stirring the reactants to initiate the dehydration reaction. Subsequently, 0.22 g of tetraisopropyl titanate was added as a catalyst, and normal pressure esterification was carried out at 220° C. under nitrogen atmosphere. After that, the pressure was lowered to 460 torr to 200 torr and the vacuum esterification reaction was carried out at 220°C. The esterification reaction was run for a total of 318 minutes. The acid value, which marks the end of esterification, is 4.69 mg KOH/g. The pressure was then reduced to 0 Torr and the vacuum polycondensation reaction was carried out at 220° C. for 465 minutes. The reaction product was then cooled to 105° C. and 0.05 wt % (relative to the total weight of the product) of diatomaceous earth (model: HYFLO) was added. Subsequently, the product was filtered using a frame filter to obtain a polyester composition of Synthesis Example 2.

[Synthesis Example 3]
Into a 3 L round bottom flask equipped with stirrer, thermometer, distillation tube and concentration meter, 1000 g adipic acid, 400.88 g neopentyl glycol, 346.88 g 2-methyl-1,3-propanediol, 155. 95 g of 2-ethylhexanol and 274.02 g of lauric acid were added. An atmospheric esterification reaction was carried out at 150° C. under the conditions of introducing nitrogen and stirring the reactants to initiate the dehydration reaction. Subsequently, 0.22 g of tetraisopropyl titanate was added as a catalyst, and normal pressure esterification was carried out at 220° C. under nitrogen atmosphere. After that, the pressure was lowered to 460 torr to 200 torr and the vacuum esterification reaction was carried out at 210°C. The esterification reaction was run for a total of 310 minutes. The acid value, which marks the end of esterification, is 4.87 mg KOH/g. The pressure was then lowered to 0 Torr and the vacuum polycondensation reaction was carried out at 220° C. for 450 minutes. The reaction product was then cooled to 105° C. and 0.05 wt % (relative to the total weight of the product) of diatomaceous earth (model: HYFLO) was added. Subsequently, the product was filtered using a frame filter to obtain a polyester composition of Synthesis Example 3.

[Synthesis Example 4]
In a 3 L round bottom flask equipped with stirrer, thermometer, distillation tube and concentration meter, 1000 g adipic acid, 481.05 g neopentyl glycol, 277.50 g 2-methyl-1,3-propanediol, 155. 95 g of 2-ethylhexanol and 274.02 g of lauric acid were added. An atmospheric esterification reaction was carried out at 150° C. under the conditions of introducing nitrogen and stirring the reactants to initiate the dehydration reaction. Subsequently, 0.22 g of tetraisopropyl titanate was added as a catalyst, and normal pressure esterification was carried out at 230° C. under nitrogen atmosphere. After that, the pressure was lowered to 460 torr to 200 torr and the vacuum esterification reaction was carried out at 220°C. The esterification reaction was run for a total of 271 minutes. The acid value, which marks the end of esterification, is 3.9 mg KOH/g. The pressure was then reduced to 0 Torr and the vacuum polycondensation reaction was carried out at 210° C. for 510 minutes. The reaction product was then cooled to 105° C. and 0.05 wt % (relative to the total weight of the product) of diatomaceous earth (model: HYFLO) was added. Subsequently, the product was filtered using a frame filter to obtain a polyester composition of Synthesis Example 4.

[Synthesis Example 5]
In a 3 L round bottom flask equipped with stirrer, thermometer, distillation tube and concentration meter, 1000 g adipic acid, 481.05 g neopentyl glycol, 277.50 g 2-methyl-1,3-propanediol, 155. 95 g of 2-ethylhexanol and 274.02 g of lauric acid were added. An atmospheric esterification reaction was carried out at 150° C. under the conditions of introducing nitrogen and stirring the reactants to initiate the dehydration reaction. Subsequently, 0.22 g of tetraisopropyl titanate was added as a catalyst, and atmospheric pressure esterification was carried out at 220° C. under a nitrogen atmosphere. After that, the pressure was lowered to 460 torr to 200 torr and the vacuum esterification reaction was carried out at 235°C. The esterification reaction was run for a total of 235 minutes. The acid value, which marks the end of esterification, is 2.4 mg KOH/g. The pressure was then reduced to 0 Torr and the vacuum polycondensation reaction was carried out at 225° C. for 413 minutes. The reaction product was then cooled to 105° C. and 0.05 wt % (relative to the total weight of the product) of diatomaceous earth (model: HYFLO) was added. Subsequently, the product was filtered using a frame filter to obtain a polyester composition of Synthesis Example 5.

[Comparative Synthesis Example 1]
In a 3 L round bottom flask equipped with stirrer, thermometer, distillation tube and concentration meter, 1000 g adipic acid, 160.35 g neopentyl glycol, 555.00 g 2-methyl-1,3-propanediol, 155. 95 g of 2-ethylhexanol and 274.02 g of lauric acid were added. An atmospheric esterification reaction was carried out at 150° C. under the conditions of introducing nitrogen and stirring the reactants to initiate the dehydration reaction. Subsequently, 0.21 g of tetraisopropyl titanate was added as a catalyst, and atmospheric pressure esterification was carried out at 220° C. under nitrogen atmosphere. After that, the pressure was lowered to 460 torr to 200 torr and the vacuum esterification reaction was carried out at 230°C. The esterification reaction was run for a total of 325 minutes. The acid value, which marks the end of esterification, is 3.21 mg KOH/g. The pressure was then reduced to 0 Torr and the vacuum polycondensation reaction was carried out at 210° C. for 524 minutes. The reaction product was then cooled to 105° C. and 0.05 wt % (relative to the total weight of the product) of diatomaceous earth (model: HYFLO) was added. Subsequently, the product was filtered using a frame filter to obtain a polyester composition of Comparative Synthesis Example 1.

[Comparative Synthesis Example 2]
In a 3 L round bottom flask equipped with stirrer, thermometer, distillation tube and concentration meter, 1000 g adipic acid, 561.23 g neopentyl glycol, 208.13 g 2-methyl-1,3-propanediol, 155. 95 g of 2-ethylhexanol and 274.02 g of lauric acid were added. An atmospheric esterification reaction was carried out at 150° C. under the conditions of introducing nitrogen and stirring the reactants to initiate the dehydration reaction. Subsequently, 0.22 g of tetraisopropyl titanate was added as a catalyst, and normal pressure esterification was carried out at 220° C. under nitrogen atmosphere. After that, the pressure was lowered to 460 torr to 200 torr and the vacuum esterification reaction was carried out at 220°C. The esterification reaction was run for a total of 310 minutes. The acid value, which marks the end of esterification, is 4.70 mg KOH/g. The pressure was then reduced to 0 torr and the vacuum polycondensation reaction was carried out at 220° C. for 492 minutes. The reaction product was then cooled to 105° C. and 0.05 wt % (relative to the total weight of the product) of diatomaceous earth (model: HYFLO) was added. Subsequently, the product was filtered using a frame filter to obtain a polyester composition of Comparative Synthesis Example 2.

[Comparative Synthesis Example 3]
Into a 3 L round bottom flask equipped with a stirrer, thermometer, distillation tube and concentration meter were added 1000 g adipic acid, 641.41 g neopentyl glycol, 138.75 g 2-methyl-1,3-propanediol, 155. 95 g of 2-ethylhexanol and 274.02 g of lauric acid were added. An atmospheric esterification reaction was carried out at 150° C. under the conditions of introducing nitrogen and stirring the reactants to initiate the dehydration reaction. Subsequently, 0.22 g of tetraisopropyl titanate was added as a catalyst, and normal pressure esterification was carried out at 220° C. under nitrogen atmosphere. After that, the pressure was lowered to 460 torr to 200 torr and the vacuum esterification reaction was carried out at 225°C. The esterification reaction was run for a total of 271 minutes. The acid value, which marks the end of esterification, is 4.98 mg KOH/g. The pressure was then lowered to 0 torr and the vacuum polycondensation reaction was carried out at 230° C. for 300 minutes. The reaction product was then cooled to 105° C. and 0.05 wt % (relative to the total weight of the product) of diatomaceous earth (model: HYFLO) was added. Subsequently, the product was filtered using a frame filter to obtain a polyester composition of Comparative Synthesis Example 3.

3.2.2. Characterization of Polyester Compositions The polyester compositions of Synthesis Examples 1-5 and Comparative Synthesis Examples 1-3 were analyzed for properties including GC spectrum, GC-MS spectrum, acid value, hydroxyl value and viscosity according to the test methods described above. It was measured. The areas of the chromatographic peaks of the first, second and third components were calculated. Table 1 shows the results.

3.3. Preparation and Characterization of Thermoplastic Polymer Materials
3.2.2. Preparation of thermoplastic polymer material [Example 1]
100 parts by weight of polyvinyl chloride (model: S-70, Formosa Plastics Group), 50 parts by weight of the polyester composition of Synthesis Example 1, 2 parts by weight of epoxidized soybean oil (model: B-22, Chang Chun Petrochemical), and 2.5 parts by weight of a calcium/zinc-based stabilizer (model: Mark 37W, Chang Chiang Chemical) was added to a Laboratory Mill (model: MT22615, YITZUNG Precision Machinery) and milled at 172°C for 7 minutes to perform A thermoplastic polymeric material of Example 1 was obtained.

[Example 2]
100 parts by weight of polyvinyl chloride S-70, 50 parts by weight of the polyester composition of Synthesis Example 2, 2 parts by weight of epoxidized soybean oil B-22, and 2.5 parts by weight of the calcium/zinc stabilizer Mark 37W. , Laboratory Mill MT22615 and milled at 172°C for 7 minutes to obtain the thermoplastic polymeric material of Example 2.

[Example 3]
100 parts by weight of polyvinyl chloride S-70, 50 parts by weight of the polyester composition of Synthesis Example 3, 2 parts by weight of epoxidized soybean oil B-22, and 2.5 parts by weight of the calcium/zinc stabilizer Mark 37W. , Laboratory Mill MT22615 and milled at 172°C for 7 minutes to obtain the thermoplastic polymeric material of Example 3.

[Example 4]
100 parts by weight of polyvinyl chloride S-70, 50 parts by weight of the polyester composition of Synthesis Example 4, 2 parts by weight of epoxidized soybean oil B-22, and 2.5 parts by weight of the calcium/zinc stabilizer Mark 37W. , Laboratory Mill MT22615 and milled at 172°C for 7 minutes to obtain the thermoplastic polymeric material of Example 4.

[Example 5]
100 parts by weight of polyvinyl chloride S-70, 50 parts by weight of the polyester composition of Synthesis Example 5, 2 parts by weight of epoxidized soybean oil B-22, and 2.5 parts by weight of the calcium/zinc stabilizer Mark 37W. , Laboratory Mill MT22615 and milled at 172°C for 7 minutes to obtain the thermoplastic polymeric material of Example 5.

[Comparative Example 1]
100 parts by weight of polyvinyl chloride S-70, 50 parts by weight of the polyester composition of Comparative Synthesis Example 1, 2 parts by weight of epoxidized soybean oil B-22, and 2.5 parts by weight of the calcium/zinc stabilizer Mark 37W. was added to a Laboratory Mill MT22615 and milled at 172° C. for 7 minutes to obtain a thermoplastic polymeric material of Comparative Example 1.

[Comparative Example 2]
100 parts by weight of polyvinyl chloride S-70, 50 parts by weight of the polyester composition of Comparative Synthesis Example 2, 2 parts by weight of epoxidized soybean oil B-22, and 2.5 parts by weight of the calcium/zinc stabilizer Mark 37W. was added to a Laboratory Mill MT22615 and milled at 172° C. for 7 minutes to obtain a thermoplastic polymeric material of Comparative Example 2.

[Comparative Example 3]
100 parts by weight of polyvinyl chloride S-70, 50 parts by weight of the polyester composition of Comparative Synthesis Example 3, 2 parts by weight of epoxidized soybean oil B-22, and 2.5 parts by weight of the calcium/zinc stabilizer Mark 37W. was added to a Laboratory Mill MT22615 and milled at 172° C. for 7 minutes to obtain a thermoplastic polymeric material of Comparative Example 3.

3.3.2. Characterization of thermoplastic polymeric materials (I)
Initial Tensile Strength, Initial Elongation, Initial 100% Tensile Stress, Volatility After Heat Aging, Residual Tensile, Residual Elongation of Thermoplastic Polymer Materials of Examples 1-5 and Comparative Examples 1-3 and 100% tensile stress were measured according to the test methods described above. Table 2 shows the results.

As shown in Table 2, thermoplastic polymeric materials using the polyester composition of the present invention as a plasticizer exhibited good initial tensile strength, initial elongation and initial 100% tensile stress, and good of residual tensile modulus, residual elongation and 100% tensile stress at the same time. In contrast, as shown in Table 2, a thermoplastic polymeric material that does not use the polyester composition of the present invention as a plasticizer exhibits good initial tensile strength, initial elongation and initial 100% tensile stress, It does not have good heat aged residual tensile modulus, residual elongation and 100% tensile stress at the same time. Specifically, as shown in Comparative Example 1, if the area percent of the chromatographic peak of the first component is higher than the specified range, the thermoplastic polymeric material has reduced residual elongation after heat aging. As shown in Comparative Examples 2 and 3, if the area percent of the chromatographic peak of the first component is lower than the specified range, the thermoplastic polymer of the thermoplastic polymer material is not effectively plasticized and the initial degraded of 100% tensile stress.

3.3.3. Characterization of thermoplastic polymeric materials (II)
The migration resistance of the thermoplastic polymeric materials of Examples 2-5 and Comparative Examples 1 and 3 was determined according to the test method described above. Table 3 shows the results.

As shown in Table 3, the thermoplastic polymer material using the polyester composition of the present invention as a plasticizer has good migration resistance, that is, the polyester composition migrates and etches the surface of the resin plate. unlikely to cause damage. On the other hand, as shown in Table 3, thermoplastic polymeric materials that do not use the polyester composition of the present invention as a plasticizer cannot have good migration resistance. Specifically, as shown in Comparative Examples 1 and 3, if the area percent of the chromatographic peak of the second component in the polyester composition used as the plasticizer is outside the specified range, the polyester composition exhibits reduced resistance. It has migratory properties, and clear depressions can be observed on the surface of the resin slope.

The above examples are used to explain the principles and effects of the present invention and to demonstrate its inventive features, and are not used to limit the scope of the present invention. A person skilled in the art can make various modifications and replacements based on the disclosures and suggestions of the described invention. Therefore, the scope of protection of the present invention is defined in the appended claims.

In some embodiments of the present invention, the polyester composition further comprises a second component. When characterizing the polyester composition by GC, the second component was eluted with a retention time in the range of 37.56 minutes to 38.29 minutes, with the second component indicated by a chromatographic peak at said retention time in the GC spectrum. has a chromatographic peak area ranging from 3.5% to 7.5 % relative to the total chromatographic peak area of the polyester composition.

In some embodiments of the present invention, in the GC-MS described above, the polyester composition is loaded into a ZB-1 capillary column of 30 m length, 250 μm inner diameter and 0.25 μm film thickness, under the following conditions: 100% Stationary phase of dimethylpolysiloxane, carrier gas of helium at a flow rate of 1.8 ml/min, 5 min at 50° C., ramping from 50° C. to 330° C. at a rate of 10° C./min, continuous at 330° C. for 27 min. , inlet temperature 350 °C, electron energy 70 eV (electron volts), ion source temperature 250 °C, use of a quadrupole mass filter, interface temperature 340 °C, mass scan range from 29.0 m/z to 900 m/z. , and a solvent delay time of 1.5 minutes.

The GC-MS analysis described above is performed as follows. First, the polyester composition is loaded into a ZB-1 capillary column with a length of 30 m, an internal diameter of 250 μm and a film thickness of 0.25 μm. GC analysis was then performed under the following conditions: stationary phase of 100% dimethylpolysiloxane, carrier gas of helium at a flow rate of 1.8 ml/min at 50°C for 5 minutes, from 50°C to 330°C at a rate of 10°C/min. 330° C. for 27 minutes in a series of temperature steps, inlet temperature 350 ° C., electron energy 70 eV (electron volts), ion source temperature 250° C., use of quadrupole mass filter, interface temperature 340° C., A mass scan range of 29.0 m/z to 900 m/z and a solvent delay time of 1.5 minutes are performed.

[GC-MS analysis]
A sample of the polyester composition is heated in an oven at 70° C. for 1 hour to homogenize the sample. The sample is then mixed with acetone (solvent) to prepare a 1 % by weight solution to complete the pretreatment of the sample to be tested.

The pretreated sample is loaded into a ZB-1 capillary column with a length of 30 m, internal diameter of 250 μm and film thickness of 0.25 μm. Subsequently, the sample is analyzed using a gas chromatograph mass spectrometer (model: QP 2020, Shimadzu Corporation). Using 100% dimethylpolysiloxane as stationary phase, using helium as carrier gas at a flow rate of 1.8 ml/min, heating at 50°C for 5 minutes from 50°C to 330°C at a rate of 10°C/min, 330 A continuous temperature step of 27 minutes is performed at °C. GC-MS analysis was then performed under the following conditions: inlet temperature 350°C , electron energy 70 eV (electron volts), ion source temperature 250°C, use of a quadrupole mass filter, interface temperature 340°C, 29.0 m/z~ A mass scan range of 900 m/z and a solvent delay time of 1.5 minutes are performed.

10 g of the sample to be tested is then weighed and added to a stoppered conical flask, to which 10 ml of acetylating reagent is added. Place an air cooler on top of the flask, shake the flask, and heat with steam (98±2° C.) for 1 hour . After completion of the reaction, the flask is cooled to room temperature, 25 ml of n-butanol is added to the flask, and the flask is vigorously shaken. Then add 2-3 drops of phenolphthalein indicator. The sample is titrated with the KOH solution until the solution becomes reddish and the reddish color is maintained for 30 seconds to the end point of the titration. Record the KOH titer (ie, test titer) and calculate the hydroxyl number of the sample according to equation (2) below.

[Initial Tensile Strength, Initial Elongation and Initial 100% Tensile Stress Analysis]
First, the hot press is preheated at 170°C for 5 minutes. The thermoplastic polymeric material is then hot-pressed at 170° C. and a pressure of 50 kg/cm ³ for 5 minutes to obtain a test piece with a length of 20 cm, a width of 20 cm and a thickness of 1 mm. The specimen is then cooled to room temperature under a pressure of 60 kg/cm ³ . Subsequently, using JIS-6301-3 model die-cut mold, the test pieces are cut into dumbbell-shaped test pieces. Dumbbell specimens are tested to obtain initial tensile strength, initial elongation and initial 100% tensile stress using a universal testing machine (model: 3366, Instron) according to ASTM D638.

3.2. Preparation and Characterization of Polyester Compositions
3.2.1. Preparation of polyester composition [Synthesis Example 1]
In a 3 L round bottom flask equipped with stirrer, thermometer, distillation tube and concentration meter, 1000 g adipic acid, 240.53 g neopentyl glycol, 485.63 g 2-methyl-1,3-propanediol, 155. 95 g of 2-ethylhexanol and 274.02 g of lauric acid were added. An atmospheric esterification reaction was carried out at 150° C. under the conditions of introducing nitrogen and stirring the reactants to initiate the dehydration reaction. Subsequently, 0.22 g of tetraisopropyl titanate was added as a catalyst, and normal pressure esterification was carried out at 220° C. under nitrogen atmosphere. Thereafter, the pressure was lowered from 460 Torr to 200 Torr and the vacuum esterification reaction was carried out at 210°C. The esterification reaction was run for a total of 298 minutes. The acid value, which marks the end of esterification, is 4.79 mg KOH/g. The pressure was then lowered to 0 Torr and the vacuum polycondensation reaction was carried out at 230° C. for 397 minutes. The reaction product was then cooled to 105° C. and 0.05 wt % (relative to the total weight of the product) of diatomaceous earth (model: HYFLO) was added. Subsequently, the product was filtered using a frame filter to obtain a polyester composition of Synthesis Example 1.

[Synthesis Example 2]
In a 3 L round bottom flask equipped with stirrer, thermometer, distillation tube and concentration meter, 1000 g adipic acid, 320.70 g neopentyl glycol, 416.25 g 2-methyl-1,3-propanediol, 155. 95 g of 2-ethylhexanol and 274.02 g of lauric acid were added. An atmospheric esterification reaction was carried out at 150° C. under the conditions of introducing nitrogen and stirring the reactants to initiate the dehydration reaction. Subsequently, 0.22 g of tetraisopropyl titanate was added as a catalyst, and normal pressure esterification was carried out at 220° C. under nitrogen atmosphere. Thereafter, the pressure was lowered from 460 Torr to 200 Torr and the vacuum esterification reaction was carried out at 220°C. The esterification reaction was run for a total of 318 minutes. The acid value, which marks the end of esterification, is 4.69 mg KOH/g. The pressure was then reduced to 0 Torr and the vacuum polycondensation reaction was carried out at 220° C. for 465 minutes. The reaction product was then cooled to 105° C. and 0.05 wt % (relative to the total weight of the product) of diatomaceous earth (model: HYFLO) was added. Subsequently, the product was filtered using a frame filter to obtain a polyester composition of Synthesis Example 2.

[Synthesis Example 3]
Into a 3 L round bottom flask equipped with stirrer, thermometer, distillation tube and concentration meter, 1000 g adipic acid, 400.88 g neopentyl glycol, 346.88 g 2-methyl-1,3-propanediol, 155. 95 g of 2-ethylhexanol and 274.02 g of lauric acid were added. An atmospheric esterification reaction was carried out at 150° C. under the conditions of introducing nitrogen and stirring the reactants to initiate the dehydration reaction. Subsequently, 0.22 g of tetraisopropyl titanate was added as a catalyst, and normal pressure esterification was carried out at 220° C. under nitrogen atmosphere. Thereafter, the pressure was lowered from 460 Torr to 200 Torr and the vacuum esterification reaction was carried out at 210°C. The esterification reaction was run for a total of 310 minutes. The acid value, which marks the end of esterification, is 4.87 mg KOH/g. The pressure was then lowered to 0 Torr and the vacuum polycondensation reaction was carried out at 220° C. for 450 minutes. The reaction product was then cooled to 105° C. and 0.05 wt % (relative to the total weight of the product) of diatomaceous earth (model: HYFLO) was added. Subsequently, the product was filtered using a frame filter to obtain a polyester composition of Synthesis Example 3.

[Synthesis Example 4]
In a 3 L round bottom flask equipped with stirrer, thermometer, distillation tube and concentration meter, 1000 g adipic acid, 481.05 g neopentyl glycol, 277.50 g 2-methyl-1,3-propanediol, 155. 95 g of 2-ethylhexanol and 274.02 g of lauric acid were added. An atmospheric esterification reaction was carried out at 150° C. under the conditions of introducing nitrogen and stirring the reactants to initiate the dehydration reaction. Subsequently, 0.22 g of tetraisopropyl titanate was added as a catalyst, and normal pressure esterification was carried out at 230° C. under nitrogen atmosphere. Thereafter, the pressure was lowered from 460 Torr to 200 Torr and the vacuum esterification reaction was carried out at 220°C. The esterification reaction was run for a total of 271 minutes. The acid value, which marks the end of esterification, is 3.9 mg KOH/g. The pressure was then reduced to 0 Torr and the vacuum polycondensation reaction was carried out at 210° C. for 510 minutes. The reaction product was then cooled to 105° C. and 0.05 wt % (relative to the total weight of the product) of diatomaceous earth (model: HYFLO) was added. Subsequently, the product was filtered using a frame filter to obtain a polyester composition of Synthesis Example 4.

[Synthesis Example 5]
In a 3 L round bottom flask equipped with stirrer, thermometer, distillation tube and concentration meter, 1000 g adipic acid, 481.05 g neopentyl glycol, 277.50 g 2-methyl-1,3-propanediol, 155. 95 g of 2-ethylhexanol and 274.02 g of lauric acid were added. An atmospheric esterification reaction was carried out at 150° C. under the conditions of introducing nitrogen and stirring the reactants to initiate the dehydration reaction. Subsequently, 0.22 g of tetraisopropyl titanate was added as a catalyst, and normal pressure esterification was carried out at 220° C. under nitrogen atmosphere. After that, the pressure was lowered from 460 Torr to 200 Torr and the vacuum esterification reaction was carried out at 235°C. The esterification reaction was run for a total of 235 minutes. The acid value, which marks the end of esterification, is 2.4 mg KOH/g. The pressure was then reduced to 0 Torr and the vacuum polycondensation reaction was carried out at 225° C. for 413 minutes. The reaction product was then cooled to 105° C. and 0.05 wt % (relative to the total weight of the product) of diatomaceous earth (model: HYFLO) was added. Subsequently, the product was filtered using a frame filter to obtain a polyester composition of Synthesis Example 5.

[Comparative Synthesis Example 1]
In a 3 L round bottom flask equipped with stirrer, thermometer, distillation tube and concentration meter, 1000 g adipic acid, 160.35 g neopentyl glycol, 555.00 g 2-methyl-1,3-propanediol, 155. 95 g of 2-ethylhexanol and 274.02 g of lauric acid were added. An atmospheric esterification reaction was carried out at 150° C. under the conditions of introducing nitrogen and stirring the reactants to initiate the dehydration reaction. Subsequently, 0.21 g of tetraisopropyl titanate was added as a catalyst, and atmospheric pressure esterification was carried out at 220° C. under nitrogen atmosphere. After that, the pressure was lowered from 460 torr to 200 torr and the vacuum esterification reaction was carried out at 230°C. The esterification reaction was run for a total of 325 minutes. The acid value, which marks the end of esterification, is 3.21 mg KOH/g. The pressure was then reduced to 0 Torr and the vacuum polycondensation reaction was carried out at 210° C. for 524 minutes. The reaction product was then cooled to 105° C. and 0.05 wt % (relative to the total weight of the product) of diatomaceous earth (model: HYFLO) was added. Subsequently, the product was filtered using a frame filter to obtain a polyester composition of Comparative Synthesis Example 1.

[Comparative Synthesis Example 2]
In a 3 L round bottom flask equipped with stirrer, thermometer, distillation tube and concentration meter, 1000 g adipic acid, 561.23 g neopentyl glycol, 208.13 g 2-methyl-1,3-propanediol, 155. 95 g of 2-ethylhexanol and 274.02 g of lauric acid were added. An atmospheric esterification reaction was carried out at 150° C. under the conditions of introducing nitrogen and stirring the reactants to initiate the dehydration reaction. Subsequently, 0.22 g of tetraisopropyl titanate was added as a catalyst, and normal pressure esterification was carried out at 220° C. under nitrogen atmosphere. Thereafter, the pressure was lowered from 460 Torr to 200 Torr and the vacuum esterification reaction was carried out at 220°C. The esterification reaction was run for a total of 310 minutes. The acid value, which marks the end of esterification, is 4.70 mg KOH/g. The pressure was then reduced to 0 torr and the vacuum polycondensation reaction was carried out at 220° C. for 492 minutes. The reaction product was then cooled to 105° C. and 0.05 wt % (relative to the total weight of the product) of diatomaceous earth (model: HYFLO) was added. Subsequently, the product was filtered using a frame filter to obtain a polyester composition of Comparative Synthesis Example 2.

[Comparative Synthesis Example 3]
Into a 3 L round bottom flask equipped with a stirrer, thermometer, distillation tube and concentration meter were added 1000 g adipic acid, 641.41 g neopentyl glycol, 138.75 g 2-methyl-1,3-propanediol, 155. 95 g of 2-ethylhexanol and 274.02 g of lauric acid were added. An atmospheric esterification reaction was carried out at 150° C. under the conditions of introducing nitrogen and stirring the reactants to initiate the dehydration reaction. Subsequently, 0.22 g of tetraisopropyl titanate was added as a catalyst, and normal pressure esterification was carried out at 220° C. under nitrogen atmosphere. After that, the pressure was lowered from 460 torr to 200 torr and the vacuum esterification reaction was carried out at 225°C. The esterification reaction was run for a total of 271 minutes. The acid value, which marks the end of esterification, is 4.98 mg KOH/g. The pressure was then lowered to 0 torr and the vacuum polycondensation reaction was carried out at 230° C. for 300 minutes. The reaction product was then cooled to 105° C. and 0.05 wt % (relative to the total weight of the product) of diatomaceous earth (model: HYFLO) was added. Subsequently, the product was filtered using a frame filter to obtain a polyester composition of Comparative Synthesis Example 3.

Claims (20)

A polyester composition comprising a polyester and a first component,
When characterizing the polyester composition by gas chromatography (GC), the first component was eluted with a retention time in the range of 36.38 minutes to 36.98 minutes, and at the chromatographic peak at said retention time in the GC spectrum, A polyester composition wherein the indicated first component has a chromatographic peak area ranging from 1.5% to 7.0% relative to the total chromatographic peak area of the polyester composition. The polyester composition of claim 1, further comprising a second component,
When characterizing the polyester composition by GC, the second component was eluted with a retention time in the range of 37.56 minutes to 38.29 minutes and the second component indicated by the chromatographic peak at said retention time in the GC spectrum. has a chromatographic peak area ranging from 3.5% to 7.7% relative to the total chromatographic peak area of the polyester composition. The polyester composition according to claim 1 or 2,
In gas chromatography (GC), the polyester composition was loaded into a SGE BPI capillary column of length 60 m, internal diameter 530 μm and film thickness 3 μm under the following conditions: stationary phase of 100% dimethylpolysiloxane, flow rate 12 ml/min. Nitrogen carrier gas, 50° C. for 5 minutes, temperature ramp from 50° C. to 300° C. at a rate of 10° C./minute, continuous stepwise temperature at 300° C. for 40 minutes, inlet temperature 340° C., polyester composition A polyester composition characterized by the use of a sample injection volume of 1 μl and a flame ionization detector operated at 340°C. The polyester composition according to any one of claims 1 to 3,
When characterizing the polyester composition by Gas Chromatography-Mass Spectrometry (GC-MS), the first component was eluted with retention times ranging from 28.900 minutes to 29.000 minutes and the fragmentation pattern of the first component was mass/charge number selected from the group consisting of 29, 41, 42, 43, 55, 56, 83, 84, 101, 111, 114, 127, 129, 141, 154, 156, 183, 201, 273 and 400 A polyester composition comprising one or more signals of (m/z). 5. The polyester composition of claim 4, wherein the fragment pattern of the first component comprises signals at m/z of 41, 55, 56, 83, 111, 114, 127, 129, 141 and 201. A polyester composition according to claim 2,
When characterizing the polyester composition by GC-MS, the second component was eluted with retention times ranging from 29.101 minutes to 29.200 minutes and the fragmentation pattern of the second component was 29,41,43,55,56 , 69, 83, 101, 111, 127, 129, 141, 147, 155, 168, 197, 215, 216, 343 and 428. thing. 7. The polyester composition of claim 6, wherein the fragment pattern of the second component comprises signals at m/z of 41, 55, 56, 69, 83, 111, 129, 141, 155 and 215. The polyester composition according to any one of claims 4 to 7,
In the GC-MS, the polyester composition was loaded into a ZB-1 capillary column of length 30 m, internal diameter 250 μm and film thickness 0.25 μm under the following conditions: stationary phase of 100% dimethylpolysiloxane, flow rate 1.8 ml/ml. helium carrier gas at 50° C. for 5 min, ramp from 50° C. to 330° C. at a rate of 10° C./min, continuous temperature stepping at 330° C. for 27 min, inlet temperature 340° C., electron energy Characterized by 70 eV (electron volts), ion source temperature of 250° C., use of quadrupole mass filter, interface temperature of 340° C., mass scan range from 29.0 m/z to 900 m/z, and solvent delay time of 1.5 min. polyester composition. The polyester composition according to any one of claims 1 to 8, wherein the first component is a compound represented by formula (I) below.

[In the formula, R ₁ is the following group.

* indicates the binding position. ] The polyester composition according to any one of claims 2 to 8, wherein the second component is a compound represented by formula (II) below.

[In the formula, R ₂ is the following group.

* indicates the binding position. ] A polyester composition according to any one of claims 1 to 10, wherein the polyester is a polyadipate. A polyester composition according to any preceding claim, wherein the polyester composition has a viscosity in the range of 2000cps to 4000cps at 25°C. A polyester composition according to any preceding claim, wherein the polyester composition has an acid value in the range of 0.1 mg KOH/g to 0.7 mg KOH/g. The polyester composition according to any one of claims 1 to 13, wherein the polyester composition has a hydroxyl value in the range of 5.0 mg KOH/g to 15.0 mg KOH/g. Further comprising a third component, the polyester composition according to any one of claims 1 to 14,
When characterizing the polyester composition by gas chromatography (GC), the third component was eluted with a retention time in the range of 36.99 minutes to 37.55 minutes, with a chromatographic peak at said retention time in the GC spectrum. A polyester composition wherein the indicated third component has a chromatographic peak area ranging from 8.0% to 10.0% relative to the total chromatographic peak area of the polyester composition. 16. The polyester composition according to claim 15, wherein the third component is a compound represented by formula (III) below.

[In the formula, R ₃ is the following group.

R ₄ is the following group.

* indicates the binding position. ] A polyester composition according to claim 15 or 16,
When characterizing the polyester composition by GC-MS, the third component was eluted with retention times ranging from 29.001 minutes to 29.100 minutes, and the fragmentation pattern of the third component was 29, 41, 55, 56, 69 , 83, 101, 111, 114, 127, 129, 141, 155, 183, 201, 215, 287, 319 and 414. 18. The polyester composition of claim 17, wherein the fragment pattern of the third component comprises signals at m/z of 41, 55, 56, 69, 111, 127, 129, 141, 201 and 215. A thermoplastic polymeric material comprising a plasticizer comprising the polyester composition of any of claims 1-18 and a thermoplastic polymer. 20. Thermoplastic polymeric material according to claim 19, wherein the thermoplastic polymer is a homopolymer of vinyl chloride or a copolymer of vinyl chloride.

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