TWI817105B - Polyester composition and method for preparing the same, product and application - Google Patents

Abstract

The instant disclosure relates to a polyester composition and method for preparing the same, as well as products comprising the polyester composition and applications thereof. The polyester composition comprises aliphatic polyester, titanium and zirconium, wherein the weight ratio of titanium/zirconium is greater than 0.05. The polyester composition of the present invention has a specific titanium/zirconium weight ratio range, can reduce the process time, and can obtain a biodegradable composition with a lower acid value.

Description

Polyester compositions and preparation methods, products and applications thereof

The present invention relates to a polyester composition and a preparation method of the polyester composition, as well as products containing the polyester composition and applications thereof. In particular, the polyester composition has a specific titanium/zirconium weight ratio.

Poly(butylene succinate) (PBS) is mainly obtained from the melt polymerization reaction of succinic acid and butylene glycol. It can be decomposed into carbon dioxide and water by microorganisms in the soil, and is biodegradable (hereinafter referred to in this article Also known as biodegradation) characteristics.

The inventor found that the current polymerization of polybutylene succinate using tetrabutyl titanate (TBT) alone as a catalyst cannot obtain the target viscosity and low acid value finished product in a short time.

In view of the fact that conventional polyester finished products cannot achieve the expected viscosity, have high acid values, and require long polymerization reaction times, there is a continuous need in this field for biodegradable compositions that reduce process times and obtain lower acid values.

The invention relates to a polyester composition comprising aliphatic polyester, titanium and zirconium, wherein the weight ratio of titanium/zirconium is greater than 0.05. In some preferred embodiments, the polyester composition is a biodegradable composition. In other aspects of the invention, a method for preparing the polyester composition as described above is provided.

According to at least one embodiment, the aliphatic polyester is produced by esterification polymerization of C2~12 aliphatic dicarboxylic acid and C2~12 aliphatic diol.

According to at least one embodiment, the C2~12 aliphatic dicarboxylic acid is selected from malonic acid, oxalic acid, succinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, Adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid (brassylic acid), tetradecanedioic acid, 3, 3-Dimethylglutaric acid, fumaric acid, 2,2-dimethylglutaric acid, suberic acid, fatty acid dimer, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexane A group consisting of alkanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, diglycolic acid, itaconic acid and maleic acid.

According to at least one embodiment, the C2~12 aliphatic diol is selected from the group consisting of ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,4-dimethyl-2-ethylhexane-1,3-diol, 2,2-dimethyl-1,3- Propylene glycol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 2,2,4-trimethyl-1,6-hexane Diol, cyclopentanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol and 2,2 , a group composed of 4,4-tetramethyl-1,3-cyclobutanediol.

According to at least one embodiment, the titanium content is 15 to 130 ppm. In some preferred embodiments, the titanium series is derived from a titanium series compound, and the titanium series compound is Ti(OR) ₄ , wherein R is a C1 to C6 alkyl group.

According to at least one embodiment, the zirconium content is 2 to 250 ppm. In some preferred embodiments, the zirconium series is derived from a zirconium series compound, and the zirconium series compound is selected from the group consisting of zirconium oxide, zirconium hydroxide, zirconium octoate, zirconium carbonate, alkaline earth zirconate salts, and rare earth zirconate salts. A group composed of salt and zircon.

Additionally, according to at least one embodiment, the polyester composition has an acid value less than 20 meqKOH/g. In some cases, the polyester composition has a colorimetric (YI) less than 55. In some preferred embodiments, the polyester composition has a color less than 30. In some cases, the polyester composition has a melt index (MI) of about 1 to 30. In some preferred embodiments, the polyester composition has a melt index (MI) of 1 to 15.

According to at least one embodiment, the preparation method of the polyester composition includes: (1) esterifying a C2~12 aliphatic dicarboxylic acid and a C2~12 aliphatic diol; and (2) using zirconium The polyester compound and the titanium compound are used as catalysts to perform a precondensation polymerization reaction to obtain the polyester composition; wherein the weight ratio of titanium/zirconium in the catalyst is greater than 0.05.

Additionally/or alternatively, the present invention also relates to an article comprising the polyester composition as described above. On the other hand, the present invention provides an application of a polyester composition, which is to apply the aforementioned products to the packaging field, disposable utensil field, agricultural field and/or medical field.

The inventor believes that by controlling the range of the weight ratio of titanium and zirconium in the polyester composition, for example, making the weight ratio of titanium/zirconium greater than 0.05, the processing time of the polyester composition can be effectively reduced, and a lower acid value can be obtained The raw decomposition composition.

The present invention provides a polyester composition, preferably a biodegradable composition. Specifically, the polyester composition contains aliphatic polyester, titanium and zirconium, wherein the weight ratio of titanium/zirconium is preferably is greater than 0.05. In a preferred embodiment, the polyester composition includes aliphatic polyester, titanium and zirconium, wherein the weight ratio of titanium/zirconium is greater than 0.05, the titanium element content is 15-130 ppm, and the zirconium element content is 2- 250ppm. In addition/or, the present invention also provides a method for preparing a polyester composition. For the aforementioned titanium/zirconium weight ratio, for example, but not limited to: greater than 0.05, greater than 0.10, greater than 0.15, greater than 0.20, greater than 0.25, greater than 0.30, greater than 0.35, greater than 0.40, greater than 0.45, greater than 0.50, greater than 0.55, greater than 0.60, Greater than 0.65, greater than 0.70, greater than 0.75, greater than 0.80, greater than 0.85, greater than 0.90, greater than 0.95, greater than 1, greater than 2, greater than 3, greater than 4, greater than 5, greater than 10, greater than 15, greater than 20, greater than 25 or greater than 30 .

In some cases, the aliphatic polyester is formed by esterification polymerization of C2~12 aliphatic dicarboxylic acid and C2~12 aliphatic diol, wherein the C2~12 aliphatic dicarboxylic acid can be selected from the group consisting of: Malonic acid, oxalic acid, succinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid Acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, 3,3-dimethylglutaric acid, fumaric acid, 2,2-di Methylglutaric acid, suberic acid, fatty acid dimer, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, diethanol acid, itaconic acid and maleic acid.

In some cases, the aliphatic polyester is formed by esterification polymerization of C2~12 aliphatic dicarboxylic acid and C2~12 aliphatic diol, wherein the C2~12 aliphatic diol can be selected from Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2, 4-Dimethyl-2-ethylhexane-1,3-diol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-Ethyl-2-isobutyl-1,3-propanediol, 2,2,4-trimethyl-1,6-hexanediol, cyclopentanediol, 1,4-cyclohexanediol, 1 ,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol and 2,2,4,4-tetramethyl-1,3-cyclobutanediol The group formed.

In a preferred embodiment, the aliphatic polyester is produced by esterification polymerization of succinic acid and butylene glycol. In another preferred embodiment, the aliphatic polyester is produced by esterification polymerization of succinic acid, adipic acid and butylene glycol. In another preferred embodiment, the aliphatic polyester is produced by esterification polymerization of adipic acid and butanediol.

The term "Titanium (Ti)" referred to herein is based on the titanium atomic content, which can be obtained by analyzing the titanium atomic content with an inductively coupled plasma atomic emission spectrometer (ICP-OES), for example. The titanium series is derived from a titanium series compound, and the titanium series compound is Ti(OR) ₄ , in which R is a C1 to C6 alkyl group. In a preferred embodiment, the titanium compound is tetrabutyl titanate. The titanium content is preferably 15~130 ppm, such as but not limited to: 15~130 ppm, 15~115 ppm, 15~100 ppm, 15~85 ppm, 15~70 ppm, 15~55 ppm, 15~40 ppm , 15~25 ppm, 20~130 ppm, 20~115 ppm, 20~100 ppm, 20~85 ppm, 20~70 ppm, 20~55 ppm, 20~40 ppm, 20~25 ppm, 30~130 ppm , 30~115 ppm, 30~100 ppm, 30~85 ppm, 30~70 ppm, 30~55 ppm, 40~130 ppm, 40~115 ppm, 40~100 ppm, 40~85 ppm, 40~70 ppm , 40~55 ppm, 50~130 ppm, 50~115 ppm, 50~100 ppm, 50~85 ppm, 50~70 ppm, 60~130 ppm, 60~115 ppm, 60~100 ppm, 60~85 ppm , 60~70 ppm, 70~130 ppm, 70~115 ppm, 70~100 ppm, 70~85 ppm, 80~130 ppm, 80~115 ppm, 80~100 ppm, 90~130 ppm, 90~115 ppm , 90~100 ppm, 100~130 ppm or 100~115 ppm.

"Zirconium (Zr)" as referred to herein is measured in terms of zirconium atomic content, which can be obtained, for example, by analyzing the zirconium atomic content with an inductively coupled plasma atomic emission spectrometer. The zirconium series is derived from a zirconium series compound, and the zirconium series compound is selected from the group consisting of zirconium oxide, zirconium hydroxide, zirconium octoate, zirconium carbonate, alkaline earth zirconate salts, rare earth zirconate salts and zircon (zircon). The group formed. In some embodiments, the zirconium system is derived from a zirconium series compound, and the zirconium series compound is selected from the group consisting of zirconium oxide, zirconium hydroxide, zirconium octoate, zirconium carbonate, alkaline earth zirconate salts, and rare earth zirconate salts. and one of the groups composed of zircons. In another embodiment, the zirconium system is derived from a zirconium series compound, and the zirconium series compound is selected from the group consisting of zirconium oxide, zirconium hydroxide, zirconium octoate, zirconium carbonate, alkaline earth zirconate salts, and rare earth zirconate salts. and more than two types of groups composed of zircons. In a preferred embodiment, the zirconium-based compound is zirconium octoate. The zirconium content is preferably 2~250 ppm, such as but not limited to: 2~250 ppm, 2~230 ppm, 2~210 ppm, 2~190 ppm, 2~170 ppm, 2~150 ppm, 2~130 ppm , 2~110 ppm, 2~90 ppm, 2~70 ppm, 2~50 ppm, 2~30 ppm, 2~10 ppm, 5~250 ppm, 5~230 ppm, 5~210 ppm, 5~190 ppm , 5~170 ppm, 5~150 ppm, 5~130 ppm, 5~110 ppm, 5~90 ppm, 5~70 ppm, 5~50 ppm, 5~30 ppm, 5~10 ppm, 10~250 ppm , 10~230 ppm, 10~210 ppm, 10~190 ppm, 10~170 ppm, 10~150 ppm, 10~130 ppm, 10~110 ppm, 10~90 ppm, 10~70 ppm, 10~50 ppm , 10~30 ppm, 30~250 ppm, 30~230 ppm, 30~210 ppm, 30~190 ppm, 30~170 ppm, 30~150 ppm, 30~130 ppm, 30~110 ppm, 30~90 ppm , 30~70 ppm, 30~50 ppm, 50~250 ppm, 50~230 ppm, 50~210 ppm, 50~190 ppm, 50~170 ppm, 50~150 ppm, 50~130 ppm, 50~110 ppm , 50~90 ppm, 50~70 ppm, 70~250 ppm, 70~230 ppm, 70~210 ppm, 70~190 ppm, 70~170 ppm, 70~150 ppm, 70~130 ppm, 70~110 ppm , 70~90 ppm, 90~250 ppm, 90~230 ppm, 90~210 ppm, 90~190 ppm, 90~170 ppm, 90~150 ppm, 90~130 ppm, 90~110 ppm, 110~250 ppm , 110~230 ppm, 110~210 ppm, 110~190 ppm, 110~170 ppm, 110~150 ppm, 110~130 ppm, 130~250 ppm, 130~230 ppm, 130~210 ppm, 130~190 ppm , 130~170 ppm, 130~150 ppm, 150~250 ppm, 150~230 ppm, 150~210 ppm, 150~190 ppm, 150~170 ppm, 170~250 ppm, 170~230 ppm, 170~210 ppm , 170~190 ppm, 190~250 ppm, 190~230 ppm, 190~210 ppm, 210~250 ppm, 210~230 ppm or 230~250 ppm.

The polyester composition preferably has a lower acid value. The acid value of the polyester composition can be evaluated by an acid value test. In some cases, the aforementioned polyester composition has an acid value, and the acid value is preferably less than 20 meqKOH/g, which can be, for example: 19 meqKOH/g, 18 meqKOH/g, 17 meqKOH/g, 16 meqKOH/g , 15 meqKOH/g, 14 meqKOH/g, 13 meqKOH/g, 12 meqKOH/g, 11 meqKOH/g, 10 meqKOH/g, 9 meqKOH/g, 8 meqKOH/g, 7 meqKOH/g, 6 meqKOH/g , 5 meqKOH/g, 4 meqKOH/g, 3 meqKOH/g, 2 meqKOH/g or 1 meqKOH/g.

The polyester composition preferably has a lower color (YI). The color of the polyester composition can be evaluated by colorimetry testing. In some cases, the aforementioned polyester composition has a chromaticity, and the chromaticity is preferably less than 55, which can be, for example: less than 55, less than 50, less than 45, less than 40, less than 35, less than 30, less than 25, less than 20 , less than 15, less than 10, less than 5 or less than 3. In a preferred embodiment, the polyester composition has a color less than 30.

The polyester composition preferably has a desired viscosity. The viscosity of the polyester composition can be evaluated by melt index (MI) testing. Generally speaking, the larger the melt index, the better the fluidity; otherwise, the worse the fluidity. In some cases, the aforementioned polyester composition has a melt index, and the melt index is preferably about 1 to 30, which can be, for example: 1 to 30, 1 to 25, 1 to 20, 1 to 15, 1 to 10, 1~5, 2~30, 2~25, 2~20, 2~15, 2~10, 2~5, 3~30, 3~25, 3~20, 3~15, 3~10, 3~ 5, 4~30, 4~25, 4~20, 4~15, 4~10, 5~30, 5~25, 5~20, 5~15, 5~10, 10~30, 10~25, 10~20 or 10~15. In a preferred embodiment, the polyester composition has a melt index of 1 to 15.

The preparation method of the aforementioned polyester composition, in a preferred embodiment, includes the following steps: (1) esterifying the C2~12 aliphatic dicarboxylic acid and the C2~12 aliphatic diol; and (2) using the zirconium-based compound and the titanium-based compound as a catalyst to perform a precondensation polymerization reaction to obtain the polyester composition; wherein the weight ratio of titanium/zirconium in the catalyst is greater than 0.05. Suitable methods and equipment for preparing the aforementioned polyester compositions may include methods and equipment readily understood by those of ordinary skill in the art.

On the other hand, the present invention provides a polyester composition, which is made by comprising the following steps: (1) esterifying the C2~12 aliphatic dicarboxylic acid and the C2~12 aliphatic diol ; and (2) using the zirconium-based compound and the titanium-based compound as a catalyst to perform a precondensation polymerization reaction to obtain the polyester composition; wherein the weight ratio of titanium/zirconium in the polyester composition is greater than 0.05, and The titanium element content is 15-130ppm, and the zirconium element content is 2-250ppm.

In addition/or alternatively, the preparation method of the polyester composition may also include the following steps in some cases: (3) adding a chain extender (or chain extender) to perform a chain extension reaction. According to the method of the present invention, a predetermined degree of polymerization can be achieved without using a chain extender, but those skilled in the art can also use a chain extender as needed. The aforementioned chain extender may be a diisocyanate compound, a carbonate compound or a dioxazoline compound, and is preferably a diisocyanate compound.

The aforementioned diisocyanate compounds include, but are not limited to, toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, diphenylmethane 4,4'- and 2,4'-diisocyanate, and naphthalene 1,5-diisocyanate. , xylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, isophorone diisocyanate and methylene di(4-isocyanatocyclohexane) diisocyanate. Preferred is hexamethylene diisocyanate.

The aforementioned carbonate compounds include, but are not limited to: diphenyl carbonate, xylene carbonate, Di(chlorophenyl carbonate), m-creyl carbonate, dinaphthyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, ethylene carbonate, dipyl carbonate, dicyclohexyl carbonate. In addition, carbonate compounds derived from hydroxyl compounds of the same type or different types such as phenols and alcohols can also be used.

The aforementioned dioxazoline compounds include, but are not limited to: 2,2′-bis(2-oxazoline), bis(2-oxazolinyl)methane, 1,2-bis(2-oxazolinyl)ethane alkane, 1,3-bis(2-oxazolinyl)propane or 1,4-bis(2-oxazolinyl)butane, especially 1,4-bis(2-oxazolinyl)benzene, 1,2-bis(2-oxazolinyl)benzene or 1,3-bis(2-oxazolinyl)benzene. Other examples are: 2,2'-bis(2-oxazoline), 2,2'-bis(4-methyl-2-oxazoline), 2,2'-bis(4,4'-bis Methyl-2-oxazoline), 2,2'-bis(4-ethyl-2-oxazoline), 2,2'-bis(4,4'-diethyl-2-oxazoline) ), 2,2′-bis(4-propyl-2-oxazoline), 2,2′-bis(4-butyl-2-oxazoline), 2,2′-bis(4-hexyl -2-oxazoline), 2,2′-bis(4-phenyl-2-oxazoline), 2,2′-bis(4-cyclohexyl-2-oxazoline), 2,2′ -Bis(4-phenylmethyl-2-oxazoline), 2,2′-p-phenylene bis(4-methyl-2-oxazoline), 2,2′-p-phenylene Bis(4,4'-dimethyl-2-oxazoline), 2,2'-m-phenylene bis(4-methyl-2-oxazoline), 2,2'-m-phenylene Phenylbis(4,4′-dimethyl-2-oxazoline), 2,2′-hexamethylenebis(2-oxazoline), 2,2′-octamethylenebis(2 -oxazoline), 2,2′-decamethylene bis(2-oxazoline), 2,2′-ethylene bis(4-methyl-2-oxazoline), 2,2′ -Tetramethylene bis(4,4'-dimethyl-2-oxazoline), 2,2'-9,9'-diphenoxyethane bis(2-oxazoline), 2, 2'-cyclohexylene bis(2-oxazoline) and 2,2'-diphenylene(2-oxazoline).

In another aspect, the present invention provides an article comprising the polyester composition as described above. In addition, the present invention also provides an application of the polyester composition, which is to apply the aforementioned products to the packaging field, disposable equipment field, agricultural field and/or medical field, etc.

The aforementioned applications refer to the application of products containing the polyester composition in the field of packaging (for example: packaging films, bags, boxes, cosmetic and pharmaceutical bottles, electronic devices, etc.), the field of disposable appliances (for example: disposable Catering utensils, disposable medical supplies, etc.), agricultural fields (such as agricultural films, pesticide-grade fertilizer slow-release materials, etc.) and medical fields (such as biomedical polymer materials).

Although not limited to any particular theory, the inventors believe that as long as the precondensation polymerization reaction is controlled so that the weight ratio of titanium and zirconium in the catalyst is within the desired range and/or the weight ratio of titanium and zirconium in the resulting polyester composition is within the desired range. Within the range, the process time can be reduced (for example: <600 minutes), and the obtained polyester composition is not only a biodegradable composition, but also has a lower acid value and/or expected viscosity and/or lower Chroma. Example

The following non-limiting examples of aspects of the invention are provided primarily to illustrate the aspects of the invention and the benefits achieved therewith.

Non-limiting methods of preparing polyester compositions are provided below. Fourteen non-limiting example polyester compositions (Examples 1-14) and three comparative example polyester compositions (Comparative Examples 1-3) were prepared according to methods similar to those disclosed below. However, the specific methods for preparing Examples 1-14 and Comparative Examples 1-3 will generally differ from the methods disclosed below in one or more aspects. Polyester preparation process

Esterification reaction: perform esterification reaction between aliphatic dibasic acid (for example: succinic acid) and aliphatic dihydric alcohol (for example: butylene glycol) at a temperature of 180-220°C, a pressure of 50-100 kPa, reaction 2 -3 hours.

Precondensation polymerization reaction: transfer the esterified product of step (1) to the precondensation kettle for reaction. The reaction temperature of the precondensation kettle is 200-260°C, the reaction time is 4.5-6 hours, and the pressure is less than 0.1 kPa. During the precondensation polymerization reaction, an appropriate amount of catalyst is added to carry out the catalytic reaction. Such catalysts are zirconium-based compounds and titanium-based compounds.

Chain extension reaction (this is an optional step): After the precondensation polymerization reaction, hexamethylene diisocyanate (HDI) is added to the prepolymer at 180-220°C. Stir evenly and leave for 0.5-1 hour.

Collection of finished products: Finally, after the granulation process, the melt index of the aliphatic polyester (for example: PBS) obtained is about 1-30. Example 1

Step (1): Put the following raw materials into a reaction kettle equipped with a stirring device, a nitrogen inlet, a heating device, a temperature detector and a decompression exhaust port: aliphatic dibasic acid (for example: 50 parts by weight of succinic acid) and Aliphatic glycol (for example: 49.8 parts by weight of butanediol) is decompressed and deoxygenated, and nitrogen is used to restore atmospheric pressure. Repeat the operation three times to fill the system with nitrogen.

Step (2): Next, heat the system to 180-220°C under nitrogen and stirring at 68 rpm, and react at this temperature for 2 hours to perform a dehydration reaction.

Step (3): Transfer the esterified product of step (2) to the condensation kettle for reaction. The reaction temperature of the condensation kettle is 200-260°C, the reaction time is 485 minutes, and the pressure is less than 0.1 kPa. As the viscosity climbs, the speed of the stirring device decreases to 68 rpm, 52 rpm, 32 rpm. During the polycondensation reaction, an appropriate amount of catalyst is added to carry out the catalytic reaction. These catalysts are zirconium compounds (Zr atomic content: 250ppm) and titanium compounds (Ti atomic content: 16.5ppm).

Step (4): Pull out the polyester in strip form from the bottom of the reaction kettle at 200-260°C, immerse it in water at 10°C, and use a granulating device to granulate to obtain the final granular polyester. The polyester The melt index is approximately 1.19. Example 2

Using a similar process to Example 1, Example 2 was prepared. However, when preparing step (3) of Example 2, the reaction temperature of the condensation tank is 200-260°C, the reaction time is 330 minutes, and the pressure is less than 0.1 kPa. As the viscosity climbs, the rotation speed of the stirring device decreases to 68 rpm, 52 rpm, 32 rpm, and 32 rpm. rpm. During the polycondensation reaction, an appropriate amount of catalyst is added to catalyze the reaction. Such catalysts are zirconium-based compounds (Zr atomic content: 225ppm) and titanium-based compounds (Ti atomic content: 40ppm). The polyester has a melt index of approximately 1.75. Example 3

Using a similar process to Example 1, Example 3 was prepared. However, when preparing step (3) of Example 3, the reaction temperature of the condensation tank is 200-260°C, the reaction time is 305 minutes, and the pressure is less than 0.1 kPa. As the viscosity climbs, the rotation speed of the stirring device decreases to 68 rpm, 52 rpm, 32 rpm, and 32 rpm. rpm. During the polycondensation reaction, an appropriate amount of catalyst is added to catalyze the reaction. Such catalysts are zirconium-based compounds (Zr atomic content: 225ppm) and titanium-based compounds (Ti atomic content: 70ppm). The polyester has a melt index of approximately 1.53. Example 4

Using a similar process to Example 1, Example 4 was prepared. However, when preparing step (3) of Example 4, the reaction temperature of the condensation tank is 200-260°C, the reaction time is 320 minutes, and the pressure is less than 0.1 kPa. As the viscosity climbs, the rotation speed of the stirring device decreases to 68 rpm, 52 rpm, 32 rpm, and 32 rpm. rpm. During the polycondensation reaction, an appropriate amount of catalyst is added to catalyze the reaction. Such catalysts are zirconium-based compounds (Zr atomic content: 120ppm) and titanium-based compounds (Ti atomic content: 40ppm). The polyester has a melt index of approximately 2.21. Example 5

Using a similar process to Example 1, Example 5 was prepared. However, when preparing step (3) of Example 5, the reaction temperature of the condensation tank is 200-260°C, the reaction time is 300 minutes, and the pressure is less than 0.1 kPa. As the viscosity climbs, the rotating speed of the stirring device decreases to 68 rpm, 52 rpm, 32 rpm, and 32 rpm. rpm. During the polycondensation reaction, an appropriate amount of catalyst is added to catalyze the reaction. Such catalysts are zirconium-based compounds (Zr atomic content: 120ppm) and titanium-based compounds (Ti atomic content: 70ppm). The polyester has a melt index of approximately 3.1. Example 6

Using a similar process to Example 1, Example 6 was prepared. However, when preparing step (3) of Example 6, the reaction temperature of the condensation tank is 200-260°C, the reaction time is 480 minutes, and the pressure is less than 0.1 kPa. As the viscosity climbs, the rotation speed of the stirring device decreases to 68 rpm, 52 rpm, 32 rpm, and 32 rpm. rpm. During the polycondensation reaction, an appropriate amount of catalyst is added to catalyze the reaction. Such catalysts are zirconium-based compounds (Zr atomic content: 120ppm) and titanium-based compounds (Ti atomic content: 25ppm). The polyester has a melt index of approximately 1.5. Example 7

Using a similar process to Example 1, Example 7 was prepared. However, when preparing step (3) of Example 7, the reaction temperature of the condensation tank was 200-260°C, the reaction time was 540 minutes, and the pressure was less than 0.1 kPa. As the viscosity climbed, the rotating speed of the stirring device decreased to 68 rpm, 52 rpm, and 32 rpm. rpm. During the polycondensation reaction, an appropriate amount of catalyst is added to catalyze the reaction. Such catalysts are zirconium-based compounds (Zr atomic content: 50ppm) and titanium-based compounds (Ti atomic content: 25ppm). The polyester has a melt index of approximately 4.54. Example 8

Using a similar process to Example 1, Example 8 was prepared. However, when preparing step (3) of Example 8, the reaction temperature of the condensation tank was 200-260°C, the reaction time was 305 minutes, and the pressure was less than 0.1 kPa. As the viscosity climbed, the rotating speed of the stirring device dropped to 68 rpm, 52 rpm, 32 rpm rpm. During the polycondensation reaction, an appropriate amount of catalyst is added to catalyze the reaction. Such catalysts are zirconium-based compounds (Zr atomic content: 100ppm) and titanium-based compounds (Ti atomic content: 100ppm). The polyester has a melt index of approximately 2.87. Example 9

Using a similar process to Example 1, Example 9 was prepared. However, when preparing step (3) of Example 9, the reaction temperature of the condensation tank is 200-260°C, the reaction time is 320 minutes, and the pressure is less than 0.1 kPa. As the viscosity climbs, the rotation speed of the stirring device decreases to 68 rpm, 52 rpm, 32 rpm, and 32 rpm. rpm. During the polycondensation reaction, an appropriate amount of catalyst is added to catalyze the reaction. Such catalysts are zirconium-based compounds (Zr atomic content: 50ppm) and titanium-based compounds (Ti atomic content: 100ppm). The polyester has a melt index of approximately 4.82. Example 10

Using a similar process to Example 1, Example 10 was prepared. However, when preparing step (3) of Example 10, the reaction temperature of the condensation tank was 200-260°C, the reaction time was 365 minutes, and the pressure was less than 0.1 kPa. As the viscosity climbed, the rotating speed of the stirring device decreased to 68 rpm, 52 rpm, 32 rpm, and 32 rpm. rpm. During the polycondensation reaction, an appropriate amount of catalyst is added to catalyze the reaction. Such catalysts are zirconium-based compounds (Zr atomic content: 20ppm) and titanium-based compounds (Ti atomic content: 100ppm). The polyester has a melt index of approximately 3.59. Example 11

Using a similar process to Example 1, Example 11 was prepared. However, when preparing step (3) of Example 11, the reaction temperature of the condensation tank was 200-260°C, the reaction time was 470 minutes, and the pressure was less than 0.1 kPa. As the viscosity climbed, the rotating speed of the stirring device decreased to 68 rpm, 52 rpm, and 32 rpm. rpm. During the polycondensation reaction, an appropriate amount of catalyst is added to catalyze the reaction. Such catalysts are zirconium-based compounds (Zr atomic content: 10ppm) and titanium-based compounds (Ti atomic content: 100ppm). The polyester has a melt index of approximately 4.31. Example 12

Using a similar process to Example 1, Example 12 was prepared. However, when preparing step (3) of Example 12, the reaction temperature of the condensation tank was 200-260°C, the reaction time was 345 minutes, and the pressure was less than 0.1 kPa. As the viscosity climbed, the rotating speed of the stirring device decreased to 68 rpm, 52 rpm, 32 rpm, and 32 rpm. rpm. During the polycondensation reaction, an appropriate amount of catalyst is added to catalyze the reaction. Such catalysts are zirconium-based compounds (Zr atomic content: 5ppm) and titanium-based compounds (Ti atomic content: 125ppm). The polyester has a melt index of approximately 4.85. Example 13

Using a similar process to Example 1, Example 13 was prepared. However, when preparing step (3) of Example 13, the reaction temperature of the condensation tank was 200-260°C, the reaction time was 315 minutes, and the pressure was less than 0.1 kPa. As the viscosity climbed, the rotating speed of the stirring device decreased to 68 rpm, 52 rpm, 32 rpm, and 32 rpm. rpm. During the polycondensation reaction, an appropriate amount of catalyst is added to catalyze the reaction. Such catalysts are zirconium-based compounds (Zr atomic content: 2ppm) and titanium-based compounds (Ti atomic content: 90ppm). The polyester has a melt index of approximately 4.39. Example 14

Step (1): Put the following raw materials into a reaction kettle equipped with a stirring device, a nitrogen inlet, a heating device, a temperature detector and a decompression exhaust port: aliphatic dibasic acid (for example: 55.36 parts by weight of adipic acid) With an aliphatic glycol (for example: 44.37 parts by weight of butanediol), perform decompression and oxygen removal, and use nitrogen to restore atmospheric pressure. Repeat the operation three times to fill the system with nitrogen.

Step (2): Next, heat the system to 180-220°C under nitrogen and stirring at 68 rpm, and react at this temperature for 2 hours to perform a dehydration reaction.

Step (3): Transfer the esterified product of step (2) to the condensation kettle for reaction. The reaction temperature of the condensation kettle is 200-260°C, the reaction time is 475 minutes, and the pressure is less than 0.1 kPa. As the viscosity climbs, the rotation speed of the stirring device is reduced to 68 rpm, 52 rpm, 32 rpm. During the polycondensation reaction, an appropriate amount of catalyst is added to catalyze the reaction. Such catalysts are zirconium compounds (Zr atomic content: 100 ppm) and titanium compounds (Ti atomic content: 100 ppm).

Step (4): Pull out the polyester in strip form from the bottom of the reaction kettle at 200-260°C, immerse it in water at 10°C, and use a granulating device to granulate to obtain the final granular polyester. The polyester The melt index is approximately 14.2. Comparative example 1

Step (1): Put the following raw materials into a reaction kettle equipped with a stirring device, a nitrogen inlet, a heating device, a temperature detector and a decompression exhaust port: aliphatic dibasic acid (for example: 50 parts by weight of succinic acid) and Aliphatic glycol (for example: 49.8 parts by weight of butanediol) is decompressed and deoxygenated, and nitrogen is used to restore atmospheric pressure. Repeat the operation three times to fill the system with nitrogen.

Step (2): Next, heat the system to 180-220°C under nitrogen and stirring at 68 rpm, and react at this temperature for 2 hours to perform a dehydration reaction.

Step (3): Transfer the esterified product of step (2) to the condensation kettle for reaction. The reaction temperature of the condensation kettle is 200-260°C, the reaction time is 540 minutes, and the pressure is less than 0.1 kPa. As the viscosity climbs, the rotation speed of the stirring device is reduced to 68 rpm, 52 rpm, 32 rpm. During the polycondensation reaction, an appropriate amount of catalyst is added to catalyze the reaction. This type of catalyst is a zirconium-based compound (Zr atomic content: 300 ppm).

Step (4): Pull out the polyester in strip form from the bottom of the reaction kettle at 200-260°C, immerse it in water at 10°C, and use a granulating device to granulate to obtain the final granular polyester. The polyester The melt index is approximately 4.45. Comparative example 2

Step (1): Put the following raw materials into a reaction kettle equipped with a stirring device, a nitrogen inlet, a heating device, a temperature detector and a decompression exhaust port: aliphatic dibasic acid (for example: 50 parts by weight of succinic acid) and Aliphatic glycol (for example: 49.8 parts by weight of butanediol) is decompressed and deoxygenated, and nitrogen is used to restore atmospheric pressure. Repeat the operation three times to fill the system with nitrogen.

Step (2): Next, heat the system to 180-220°C under nitrogen and stirring at 68 rpm, and react at this temperature for 2 hours to perform a dehydration reaction.

Step (3): Transfer the esterification product of step (2) to the condensation kettle for reaction. The reaction temperature of the condensation kettle is 200-260°C, the reaction time is 600 minutes, the pressure is less than 0.1 kPa, and the rotation speed of the stirring device is reduced to 68 rpm. During the polycondensation reaction, an appropriate amount of catalyst is added to carry out the catalytic reaction. This type of catalyst is a titanium-based compound (Ti atom content: 100ppm). High viscosity finished product cannot be obtained within 600 minutes.

Step (4): Discharge from the bottom of the reaction kettle at 200-260°C, and immerse in 10°C water to cool down to obtain a sample. Comparative example 3

Step (1): Put the following raw materials into a reaction kettle equipped with a stirring device, a nitrogen inlet, a heating device, a temperature detector and a decompression exhaust port: aliphatic dibasic acid (for example: 50 parts by weight of succinic acid) and Aliphatic glycol (for example: 49.8 parts by weight of butanediol) is decompressed and deoxygenated, and nitrogen is used to restore atmospheric pressure. Repeat the operation three times to fill the system with nitrogen.

Step (2): Next, heat the system to 180-220°C under nitrogen and stirring at 68 rpm, and react at this temperature for 2 hours to perform a dehydration reaction.

Step (3): Transfer the esterification product of step (2) to the condensation kettle for reaction. The reaction temperature of the condensation kettle is 200-260°C, the reaction time is 600 minutes, the pressure is less than 0.1 kPa, and the rotation speed of the stirring device is reduced to 68 rpm. During the polycondensation reaction, an appropriate amount of catalyst is added to catalyze the reaction. Such catalysts are zirconium compounds (Zr atomic content: 250 ppm) and titanium compounds (Ti atomic content: 5 ppm). High viscosity finished product cannot be obtained within 600 minutes.

Step (4): Discharge from the bottom of the reaction kettle at 200-260°C, and immerse in 10°C water to cool down to obtain a sample. result

Examples 1-14 and Comparative Examples 1-3 were evaluated to determine the properties of these polyester compositions. As described above, Examples 2-14 and Comparative Examples 1-3 were prepared according to a method similar to that described in Example 1 above. However, the prepared polyester compositions are different in terms of process reaction time, type of C2~12 aliphatic dicarboxylic acid, zirconium atom content, titanium atom content and titanium/zirconium weight ratio.

Further analysis of the polyester composition was conducted to evaluate the melt index, acid value, color, zirconium atom content, titanium atom content and titanium/zirconium weight ratio. Table 1 provides the process conditions and some physical property detection data of Examples 1-14 and Comparative Examples 1-3.

Table 1 Example 1 2 3 4 5 6 7 8 9 Process conditions Alkyd-to-acid ratio 1.05:1 ~ 1.8:1 Types of diacids succinic acid Zr(ppm) 250 225 225 120 120 120 50 100 50 Ti (ppm) 16.5 40 70 40 70 25 25 100 100 Ti/Zr weight ratio 0.066 0.178 0.311 0.333 0.583 0.208 0.5 1 2 Processing time (min) 485 330 305 320 300 480 540 305 320 Temperature( ^° C) 200~260 Physical property testing MI 1.19 1.75 1.53 2.21 3.1 1.50 4.54 2.87 4.82 AV (meqKOH/g) 7.95 12.84 16.04 12.3 17.76 12.27 10.29 11.35 8.69 YI 22.73 3.78 3.49 4.58 3.99 6.19 10.07 31.48 27.27 Zr (ICP) (ppm) 247.3 228.7 193.3 123 118.2 142.6 50.9 87.2 43.0 Ti (ICP) (ppm) 17.2 46.3 59.1 45.6 62.1 24.6 25.4 98.0 91.9 Ti/Zr weight ratio 0.0696 0.202 0.306 0.371 0.525 0.173 0.499 1.124 2.137

Table 1 (continued) Example Comparative example 10 11 12 13 14 1 2 3 Process conditions Alkyd-to-acid ratio 1.05:1 ~ 1.8:1 Types of diacids succinic acid Adipic acid succinic acid Zr(ppm) 20 10 5 2 100 300 0 250 Ti (ppm) 100 100 125 90 100 0 100 5 Ti/Zr weight ratio 5 10 25 45 1 - - 0.02 Processing time (min) 365 470 345 315 475 540 >600 >600 Temperature( ^° C) 200~260 Physical property testing MI 3.59 4.31 4.85 4.39 14.2 4.45 X X AV (meqKOH/g) 6.55 8.43 6.54 6.72 10.21 20.55 X X YI 50.75 45.85 48.41 49.94 24.25 4.61 X X Zr (ICP) (ppm) 18.2 8.8 6.1 2.82 98.7 305.4 - 252.7 Ti (ICP) (ppm) 101.4 100.1 129.3 92.47 100.2 - 87.2 7.21 Ti/Zr weight ratio 5.571 11.375 21.196 32.79 1.015 - - 0.029

In order to evaluate the melt index (MI) of Examples 1-14 and Comparative Examples 1-3, a melt index test was performed and the instructions are as follows: 1. The instrument and its brand: Melt Index Analyzer, model LMI5000. 2. Sample preparation method: Place the sample in a hot air circulation oven (80 ± 2℃* 4hrs) to ensure that no moisture adheres to the sample to be tested. 3. Test standard: based on ISO 1133-1:2011(E). 4. Test conditions: temperature (190 ± 2℃) and total load (including compression rod) weight 2.16kg. 5. Test process: Place 4~8 g of the baked sample to be tested into a 190°C heating tube. After preheating, add weights and start the melt index test of the sample to be tested. Time the sampling scale for 10 minutes. Each sample is tested twice and the average value is calculated.

The acid value (AV) of Examples 1-14 and Comparative Examples 1-3 was evaluated using the acid value test. The description is as follows: 1. The instrument and its brand: METROHM 725 DOSIMAT. 2. Sample preparation method: Place about 0.4-0.6 g of the sample to be tested in a pre-dried 100 c.c. sample bottle, add 30-50 ml o-cresol; place the sample bottle on a heating stirrer, and heat at 110 ± 5°C Stir until completely dissolved, about 30 minutes; cool the solution to room temperature and prepare for titration. 3. Test conditions: Use 0.03N KOH to perform potentiometric titration on the sample to be tested. 4. Test process: Add 3 ml 0.01N KCl into the liquid to be tested and stir for about 1 minute. Confirm the titrant concentration, blank value and titration parameters and set them in the instrument. Then immerse the electrode into the liquid to be tested and press to start titration. . Titrator results are expressed in meqKOH/g.

The colorimetric (YI) of Examples 1-14 and Comparative Examples 1-3 were evaluated using the colorimetric test. The description is as follows: 1. The instrument and its brand: NIPPON DENSHOKU 300a, ZE-2000. 2. Sample preparation method: Take about 20-40 g of sample powder/particles to be tested and put them into a square quartz colorimetric cell (Quartz Cell) or use a prepared suitable color plate. 3. Test process: Select the ''EZMQC'' analysis software to calibrate the white plate and standard color plate first, place the sample at the test port of the reflected light test area, perform the test after fixation, and repeat three times until the test is completed. Average and record the readings (L*, a*, b*, YI) in the window.

For the titanium and zirconium contents in Examples 1-14 and Comparative Examples 1-3, the atomic contents of titanium and zirconium were analyzed, and the description is as follows: 1. Instrument and its brand: Inductively coupled plasma atomic emission spectrometer (ICP-OES), model CEM-MARS 6. 2. Sample preparation method: Weigh 0.2 g of the biodegradation composition, add 9 mL nitric acid/3 mL hydrochloric acid, seal it in a microwave digestion bottle, raise the temperature from room temperature to 210°C for 30 minutes, and maintain the temperature for microwave digestion for 30 minutes. After cooling to 60°C, add ultrapure water to dilute to 30 mL, and filter using filter paper with a pore size of 11um and a thickness of 0.18mm. 3. Testing process: Configure standard solutions for detecting elements zirconium and titanium, and establish element calibration lines; test the samples to be tested after microwave digestion through ICP-OES.

The results show that Examples 1-14 have a titanium/zirconium weight ratio greater than 0.05, the process times of Examples 1-14 are all less than 600 minutes, and the acid values are all less than 20 meqKOH/g. It shows that no matter how the diacid type, titanium content, and zirconium content change, as long as the titanium/zirconium weight ratio in the polyester composition is greater than 0.05, the desired effect can be achieved.

In comparison, Comparative Example 1 only contains zirconium but not titanium. Although the process time is less than 600 minutes, the acid value is as high as 20.55 meqKOH/g. Comparative Example 2 only contains titanium but not zirconium. The process time exceeds 600 minutes and the expected high viscosity finished product cannot be obtained. Although Comparative Example 3 contains titanium and zirconium, the weight ratio of titanium/zirconium is not greater than 0.05, the process time exceeds 600 minutes, and the target viscosity finished product cannot be obtained.

In addition, the polyester compositions of Examples 1 to 14 also have desired viscosity (melt index 1 to 30) and excellent color (less than 55).

In summary, although not limited to any particular theory, the inventor believes that as long as the precondensation polymerization reaction is controlled so that the weight ratio of titanium and zirconium in the catalyst is within the desired range and/or the titanium and zirconium in the resulting polyester composition are When the zirconium weight ratio is within the desired range, the process time can be reduced (for example: <600 minutes), and the resulting polyester composition is not only a biodegradable composition, but also has a lower acid value and/or expected viscosity. and/or lower chroma.

All ranges provided herein are intended to include each specific range within the given range and every combination of subranges between the given ranges. Furthermore, unless otherwise indicated, all ranges provided herein include the endpoints of the ranges. Thus, the range 1-5 specifically includes 1, 2, 3, 4, and 5, as well as subranges such as 2-5, 3-5, 2-3, 2-4, 1-4, and the like.

All publications and patent applications cited in this specification are hereby incorporated by reference, and each individual publication or patent application is expressly and individually indicated to be incorporated by reference for any and all purposes. In the event of any inconsistency between this document and any publication or patent application incorporated by reference, this document shall control.

The terms "includes," "has," and "includes" are used herein in an open, non-limiting sense. The terms "a" and "the" shall be understood to cover both the plural and the singular. The term "one or more" means "at least one" and thus may include a single feature or a mixture/combination of features.

Except in the Operating Examples or where otherwise indicated, all numbers expressing quantities of ingredients and/or reaction conditions may in all cases be modified by the term "about" meaning within ±5% of the indicated number. . As used herein, the terms "substantially free" or "substantially free" mean less than about 2% of a specified characteristic. All elements or features affirmatively set forth herein are negligibly excluded from the scope of the claim.

without.

without.

without.

without.

Claims (17)

A polyester composition comprising aliphatic polyester, titanium and zirconium, wherein the titanium content is 15~130ppm, the zirconium content is 2~250ppm, the titanium/zirconium weight ratio is greater than 0.05, and the polyester composition does not contain Tetraalkyl ammonium hydroxide, and has an acid value less than 20meqKOH/g. The polyester composition as claimed in claim 1, wherein the aliphatic polyester is produced by esterification polymerization of C2~12 aliphatic dicarboxylic acid and C2~12 aliphatic diol. The polyester composition as claimed in claim 2, wherein the C2~12 aliphatic dicarboxylic acid is selected from malonic acid, oxalic acid, succinic acid, glutaric acid, 2-methylglutaric acid, 3 -Methyl glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, 3,3-dimethylglutaric acid, Fumaric acid, 2,2-dimethylglutaric acid, fatty acid dimer, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid A group consisting of carboxylic acid, diglycolic acid, itaconic acid and maleic acid. The polyester composition as claimed in claim 2, wherein the C2~12 aliphatic diol is selected from the group consisting of ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1 ,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,4-dimethyl-2-ethylhexane-1,3-diol, 2,2-diol Methyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 2,2,4-trimethyl -1,6-hexanediol, cyclopentanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol A group consisting of alkanedimethanol and 2,2,4,4-tetramethyl-1,3-cyclobutanediol. The polyester composition of claim 1, wherein the titanium series is derived from a titanium series compound, and the titanium series compound is Ti(OR) ₄ , wherein R is a C1 to C6 alkyl group. The polyester composition of claim 1, wherein the zirconium is derived from a zirconium-based compound, and the zirconium-based compound is selected from the group consisting of zirconium oxide, zirconium hydroxide, zirconium octoate, zirconium carbonate, and zirconium acid alkaline earth salts , a group composed of zirconate rare earth salts and zircon. The polyester composition according to any one of claims 1 to 6, which is a biodegradable composition. The polyester composition according to any one of claims 1 to 6, which has a chromaticity (YI) less than 55. The polyester composition according to any one of claims 1 to 6, which has a chromaticity less than 30. The polyester composition according to any one of claims 1 to 6, which has a melt index (MI) of 1 to 30. The polyester composition according to claim 10, which has a melt index (MI) of 1 to 15. A method for preparing the polyester composition as described in claim 1, comprising: (1) esterifying a C2~12 aliphatic dicarboxylic acid with a C2~12 aliphatic dihydric alcohol; and (2) A zirconium-based compound and a titanium-based compound are used as a catalyst to perform a precondensation polymerization reaction to obtain the polyester composition; wherein the weight ratio of titanium/zirconium in the catalyst is greater than 0.05. Such as the preparation method of claim 12, wherein the C2~12 aliphatic dicarboxylic acid is selected from the group consisting of malonic acid, oxalic acid, succinic acid, glutaric acid, 2-methylglutaric acid, and 3-methylglutaric acid. Diacid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, 3,3-dimethylglutaric acid, fumaric acid, 2,2-dimethylglutaric acid, fatty acid dimer, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, dicarboxylic acid A group consisting of glycolic acid, itaconic acid and maleic acid. Such as the preparation method of claim 12, wherein the C2~12 aliphatic diol is selected from ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol Diol, 1,5-pentanediol, 1,6-hexanediol, 2,4-dimethyl-2-ethylhexane-1,3-diol, 2,2-dimethyl-1 ,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 2,2,4-trimethyl-1, 6-hexanediol, cyclopentanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol and A group consisting of 2,2,4,4-tetramethyl-1,3-cyclobutanediol. Such as the preparation method of claim 12, wherein the titanium compound is Ti(OR) ₄ , wherein R is a C1~C6 alkyl group. Such as the preparation method of claim 12, wherein the zirconium-based compound is selected from the group consisting of zirconium oxide, zirconium hydroxide, zirconium octoate, zirconium carbonate, zirconate alkaline earth salts, zirconate rare earth salts and zircon (zircon) group. An application of a polyester composition, which is to apply the polyester composition as described in any one of claims 1 to 11 to the packaging field, disposable equipment field, agricultural field and/or medical field.