WO2024036583A1 - Thermoplastic polyester, preparation method therefor and use thereof - Google Patents

Abstract

A thermoplastic polyester, a preparation method therefor and a use thereof. The thermoplastic polyester is prepared from diol and dicarboxylic acid by means of an esterification reaction and a copolycondensation reaction, the diol being a mixture of tricyclodecanedimethanol and another aliphatic diol. The thermoplastic polyester has the properties of high molecular weight, high toughness, high heat resistance and high transparency, and the raw material cost is low.

Description

Thermoplastic polyester and its preparation methods and applications Technical field

The invention relates to the field of polymer materials, and in particular to a thermoplastic polyester and its preparation method and application.

Background technique

Thermoplastic polyester materials usually refer to linear polyester materials obtained through esterification and polycondensation processes using dibasic acids and glycols. Common thermoplastic polyesters include polyethylene terephthalate resin (PET) and poly(p-ethylene glycol). Butylene phthalate (PBT) has a large output and a wide range of uses. It is mostly used as high-performance films and fibers. However, traditional thermoplastic polyester has the following problems: (1) The material is semi-crystalline, and during the injection molding process, the existence of crystallization effect results in low transparency of the injection molded parts; (2) The material has low heat resistance and does not function well at high temperatures. At 70℃, the parts are easily deformed by heat, making it difficult to meet the application requirements of food containers or structural parts.

Traditional technology discloses a polyethylene terephthalate-1,4-cyclohexane dimethanol (PETG) copolyester and its preparation method. Although the transparency is modified, the PETG material has poor resistance to It has low thermal properties, and its glass transition temperature is usually around 80°C. When the use temperature is close to 70°C, its structure is prone to thermal deformation, thus limiting its application in areas that require high temperature resistance.

There is also a traditional technology that discloses a preparation method that uses the third monomer 1,4-cyclohexanedimethanol (CHDM), terephthalic acid (TPA) and isosorbide (ISB) to copolymerize, which can obtain heat-resistant Transparent copolyester material, but the reactivity of isosorbide is low, it is difficult to increase the molecular weight, and side reactions are prone to occur at high temperatures, resulting in the final prepared copolyester material being prone to yellowing, insufficient material toughness, and poor processing performance.

Bisphenol A-based polycarbonate (PC) is a common polymer material with high transparency and good heat resistance. It has excellent transparency, dimensional stability, heat resistance and toughness. However, it will It releases bisphenol A (BPA) and is prohibited from being used in food contact products such as baby bottles. At the same time, the chemical resistance of PC materials is relatively poor, limiting its application.

The American company Eastman has developed a highly sterically hindered glycol monomer: 2,2,4,4-tetramethyl-1,3-cyclobutanediol (CBDO), and a combination of CBDO and 1,4-cyclobutanediol. A copolyester material prepared by co-condensation of hexane dimethanol (CHDM) and dimethyl terephthalate. The copolyester material has high transparency, with a visible light transmittance greater than 90%; good heat resistance, with a glass transition temperature higher than 100°C; high toughness, good chemical resistance, and does not contain or release BPA. As a safe, Highly transparent and high-temperature-resistant polymer materials have been widely used in baby bottles, water cups, kitchen appliances, e-cigarette oil tank materials and other fields. However, CBDO monomer is only produced by a very small number of chemical companies, and it is difficult to control the processing process. Currently, only Eastman has the capability of mass production and processing.

Contents of the invention

According to various embodiments of the present application, a thermoplastic polyester is provided, which thermoplastic polyester has high transparency, high heat resistance, high toughness and high molecular weight at the same time.

This application is implemented through the following technical solutions.

A thermoplastic polyester prepared from raw materials through esterification reaction and cocondensation polymerization reaction;

The raw materials include diols and dicarboxylic acids;

The glycol is a mixture of tricyclodecane dimethanol and other aliphatic glycols.

In one embodiment, the other aliphatic glycol is selected from the group consisting of ethylene glycol, 1,2-propanediol, 1,3-propanediol, n-butanediol, n-pentyl glycol, neopentyl glycol, 1, One or more of 3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol.

In one of the embodiments, in the glycol, the molar percentage of the tricyclodecanedimethanol is about 5% to about 60%, and the molar percentage of the other aliphatic glycols is about 40% to about 95%.

In one embodiment, the dicarboxylic acid is selected from one or more of terephthalic acid, 2,6-naphthalenedicarboxylic acid, isophthalic acid and furandicarboxylic acid.

In one embodiment, the molar ratio of the diol to the dicarboxylic acid is about 1.05:1 to about 2:1.

In one embodiment, the thermoplastic polyester includes one or more of structural unit A and structural unit B;

The structural unit A is

The structural unit B is

In one embodiment, the thermoplastic polyester meets one or more of the following conditions:

(1) The intrinsic viscosity is about 0.5dL/g to about 0.9dL/g;

(2) The glass transition temperature is about 90°C to about 150°C.

This application also provides an application of the thermoplastic polyester as described above in catering containers, kitchen appliances, optical base films or electronic cigarette oil storage devices.

The present application also provides a method for preparing thermoplastic polyester as described above, including the following steps:

Mix the raw materials with the first catalyst to perform an esterification reaction to prepare ester;

The ester, the phosphorus stabilizer and the second catalyst are mixed to perform a copolycondensation reaction.

In one embodiment, the conditions for the esterification reaction include: a temperature of about 160°C to about 265°C, a pressure of about 1 to about 3 atmospheres, and a time of about 120 min to about 300 min.

In one embodiment, the cocondensation polymerization reaction conditions include: a temperature of about 250°C to about 300°C, and a time of about 90 min to about 300 min.

In one embodiment, the second catalyst is selected from one or more of titanium-containing compounds, aluminum-containing compounds, tin-containing compounds and germanium-containing compounds.

The details of one or more embodiments of the application are set forth in the accompanying drawings and the description below. Other features, objects and advantages of the application will become apparent from the description, drawings and claims.

Detailed ways

In order to facilitate understanding of the present application, the present application will be described more fully below with reference to relevant embodiments. The preferred embodiments of the present application are given in the examples. However, the present application may be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that a thorough and comprehensive understanding of the disclosure of this application will be provided.

In addition, the terms “first” and “second” are used for descriptive purposes only and cannot be understood as indicating or implying relative importance or implicitly indicating the quantity of indicated technical features. Therefore, features defined as "first" and "second" may explicitly or implicitly include at least one of these features. In the description of the application, "plurality" means at least two, such as two, three, etc., unless otherwise expressly and specifically limited. In the description of this application, "several" means at least one, such as one, two, etc., unless otherwise expressly and specifically limited.

When a numerical range is disclosed herein, such range is deemed to be continuous and includes the minimum and maximum values of the range, and every value between such minimum and maximum values. Further, when a range refers to an integer, every integer between the minimum value and the maximum value of the range is included. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges can be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.

Unless otherwise specified, all percentages, fractions, and ratios are based on the total mass of the compositions herein. Unless otherwise specified, all qualities regarding listed ingredients are given to the active level and therefore they do not include solvents or by-products that may be included in commercially available materials. The term "mass percentage content" herein can be expressed by the symbol "%". Unless otherwise stated, all molecular weights herein are weight average molecular weights expressed in Daltons. Unless otherwise stated, all formulations and testing in this article occurred at 25°C. As used herein, "includes," "includes," "contains," "contains," "having," or other variations thereof are intended to encompass non-closed inclusions and no distinction is made between these terms. The term "comprising" means that other steps and ingredients may be added that do not affect the final result. The compositions and methods/processes of the present application comprise, consist of, and consist essentially of the essential elements and limitations described herein, as well as any additional or optional ingredients, components, steps, or limitations described herein. No distinction is made herein between the terms "efficacy", "performance", "effect" and "efficacy".

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the technical field to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing specific embodiments only and is not intended to limit the application.

This application provides a thermoplastic polyester, which is prepared from raw materials through esterification reaction and co-condensation polymerization reaction;

Raw materials include diols and dicarboxylic acids;

The glycol is a mixture of tricyclodecane dimethanol and other aliphatic glycols.

Tricyclodecane dimethanol (TCD-DM) is a special alicyclic diol. It is synthesized by hydroformylation of dicyclopentadiene to synthesize tricyclodecane dimethanol, which is further catalytically hydrogenated to synthesize tricyclodecane dimethanol. Cyclodecanedimethanol (TCD-DM) has now achieved industrial mass production. Due to the lower raw material cost of dicyclopentadiene, the monomer cost of TCD-DM has potential advantages.

In this application, tricyclodecanedimethanol is compounded with another aliphatic diol as the mixed diol raw material in the copolyester, so that the mixed diol has the characteristics of greater rigidity and spatial non-planar structure, and is consistent with After the esterification reaction and polycondensation reaction of dicarboxylic acid, the copolyester can have excellent visible light transmittance and improve the transparency of thermoplastic polyester; at the same time, the mixture of tricyclodecanedimethanol and aliphatic diol can further improve the transparency of the thermoplastic polyester. The heat resistance of thermoplastic polyester is reflected in the significant increase in the glass transition temperature and heat deformation temperature of thermoplastic polyester. The heat deformation temperature of the thermoplastic polyester provided in this application can reach 80°C to 110°C, and the conformation of the alicyclic ring The transformation in turn provides the copolyester with better toughness. In addition, the mixed glycol compounded with tricyclodecanedimethanol and aliphatic glycol has high reactivity and can reduce steric hindrance to a certain extent, thereby effectively promoting its ester with dicarboxylic acid. Chemicalization or transesterification reaction can further obtain high molecular weight thermoplastic polyester, and finally realize the thermoplastic polyester to achieve the properties of high molecular weight, high toughness, high heat resistance and high transparency.

Furthermore, tricyclodecanedimethanol has achieved industrial mass production, and its synthetic raw material dicyclopentadiene has a low cost. Therefore, the thermoplastic polyester of the present application also has a cost advantage.

In one embodiment, the other aliphatic glycol is selected from the group consisting of ethylene glycol, 1,2-propanediol, 1,3-propanediol, n-butanediol, n-pentyl glycol, neopentyl glycol, 1,3-propanediol, One or more of cyclohexanedimethanol and 1,4-cyclohexanedimethanol.

Dihydric alcohols containing aliphatic cyclic structures are special dihydroxy compounds. The unique cyclic structure can improve the heat resistance, weather resistance, hardness and other properties of polymer materials. They are odorless and have low toxicity. Among them, 1,4-cyclohexanedimethanol is an alicyclic diol containing a six-membered ring and an important monomer for the synthesis of various high-performance polyester materials such as PCT, PETG, and PCTG. However, it is difficult to increase the molecular weight of copolyesters traditionally prepared using 1,4-cyclohexanedimethanol as the glycol, and side reactions are prone to occur at high temperatures, resulting in the final prepared copolyester material being prone to yellowing in color, insufficient material toughness, and Processing performance is poor.

In one embodiment, among the glycols, the molar percentage of tricyclodecanedimethanol ranges from about 5% to about 60%, and the molar percentage of other aliphatic glycols ranges from about 40% to about 95%.

In one embodiment, the dicarboxylic acid is selected from one or more of terephthalic acid, 2,6-naphthalenedicarboxylic acid, isophthalic acid and furandicarboxylic acid.

In one embodiment, the molar ratio of glycol to dicarboxylic acid is about 1.05:1 to about 2:1.

It can be understood that in this application, the molar ratio of glycol to dicarboxylic acid includes but is not limited to 1.05:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6: 1. 1.7:1, 1.8:1, 1.9:1, 2:1.

In one embodiment, the thermoplastic polyester includes one or more of structural unit A and structural unit B;

Structural unit A is

Structural unit B is

In one embodiment, the thermoplastic polyester has an intrinsic viscosity of about 0.5 dL/g to about 0.9 dL/g.

It can be understood that in this application, the intrinsic viscosity of thermoplastic polyester includes but is not limited to 0.5dL/g, 0.6dL/g, 0.7dL/g, 0.8dL/g, and 0.9dL/g.

In one embodiment, the thermoplastic polyester has a glass transition temperature of about 90°C to about 150°C.

The glass transition temperature (Tg) of the thermoplastic polyester resin of the present application can be adjusted within a wide range. By increasing the TCDDM chain link content, a copolyester with a higher Tg can be produced, and by adjusting the proportion of glycol , adjust mechanical properties and heat resistance. In addition, the thermoplastic polyester resin of the present application has a glass transition temperature similar to or higher than traditional copolyesters (>100°C), and also has higher Young's modulus, tensile strength, impact toughness, and mechanical properties. Better performance.

This application also provides an application of the above-mentioned thermoplastic polyester in catering containers, kitchen appliances, optical base films or electronic cigarette oil storage devices.

It can be understood that in this application, catering containers include but are not limited to baby bottles and water cups; kitchen appliances include but are not limited to mixing cups and juicers.

This application also provides a method for preparing the above-mentioned thermoplastic polyester, which includes the following steps:

Mix the raw materials and the first catalyst to perform an esterification reaction to prepare ester;

Mix the ester and phosphorus stabilizers with the second catalyst to perform a cocondensation reaction.

In another embodiment, the preparation method of the above-mentioned thermoplastic polyester includes the following steps:

The raw materials are mixed with the first catalyst to cause an esterification reaction between at least one hydroxyl group in the diol and at least one carboxyl group in the dicarboxylic acid to prepare an ester.

In another embodiment, the preparation method of the above-mentioned thermoplastic polyester includes the following steps:

The ester, the phosphorus stabilizer and the second catalyst are mixed to cause at least one hydroxyl group in the ester and at least one carboxyl group in the ester to undergo a cocondensation reaction.

In one embodiment, the conditions for the esterification reaction include: a temperature of about 160°C to about 265°C, a pressure of about 1 to about 3 atmospheres, and a time of about 120 min to about 300 min.

In one embodiment, the cocondensation polymerization reaction conditions include: a temperature of about 250°C to about 300°C, and a time of about 90 min to about 300 min.

In one embodiment, the cocondensation polymerization reaction is performed under reduced pressure.

In another embodiment, the vacuum degree of the cocondensation polymerization reaction is gradually reduced to about 20 Pa to about 100 Pa.

In one embodiment, the first catalyst is selected from dibutyltin oxide.

In one embodiment, the second catalyst is selected from one or more of titanium-containing oxides, aluminum-containing oxides, tin-containing oxides and germanium-containing oxides.

In another embodiment, the second catalyst is selected from one or more of antimony trioxide, dibutyltin oxide, n-butyl titanate, and isopropyl titanate.

In one embodiment, the phosphorus stabilizer is selected from one or more of trimethyl phosphate, triphenyl phosphate, triethyl phosphite, trilauryl phosphite, and triisoctyl phosphite.

In another embodiment, the preparation method of the above-mentioned thermoplastic polyester includes the following steps:

Mix the raw materials and perform an esterification reaction at a temperature of 160°C to 265°C, a pressure of 1 to 3 atmospheres, and a time of 120min to 300min to prepare ester;

Mix the ester and phosphorus stabilizers with the catalyst, and perform a cocondensation polymerization reaction at a temperature of 250°C to 300°C, a time of 90min to 240min, and reduced pressure; where the catalyst is selected from titanium-containing compounds, aluminum-containing compounds, and compounds containing One or more of tin compounds and germanium-containing compounds.

In another embodiment, the preparation method of the above-mentioned thermoplastic polyester includes the following steps:

In the reactor, mix the diol and dicarboxylic acid at a molar ratio of (1.05~2):1, stir the material composed of the diol and dicarboxylic acid, and react at 160°C~265°C Under temperature and reaction pressure of 1 to 3 atmospheres, the esterification reaction is completed after 120 to 240 minutes; a phosphorus stabilizer is added to the slurry, or after the esterification is completed or before the polycondensation; then a second catalyst is added to the reactor , react at a temperature of 250°C to 300°C and under reduced pressure for 90min to 240min to obtain the modified copolyester.

The thermoplastic polyester of the present application and its preparation method will be further described in detail below with reference to specific examples. The raw materials used in the following examples are all commercially available products unless otherwise specified.

The intrinsic viscosity, glass transition temperature, tensile properties and transparency of the copolyester materials prepared in the examples were tested, specifically including the following analysis methods:

Intrinsic viscosity: The intrinsic viscosity (IV) of the copolyester sample was measured using a Hangzhou Zhongwang automatic viscometer. The test temperature was 25°C and the solvent was phenol/tetrachloroethane (mass ratio w/w=3/2);

Thermal properties: The DSC equipment of the American TA Company was used to measure the glass transition temperature of the sample, using a temperature program of primary heating-cooling-second heating. The test temperature range was room temperature to 250°C, and the temperature rising and cooling rate was 10°C/min. Isothermal time 3min;

Tensile properties: An injection molding machine was used to prepare dumbbell-shaped specimens with a width of 4 mm and a thickness of 2 mm, and were measured after being placed at room temperature for 1 week. According to the ASTM D638 standard, a universal material testing machine was used to conduct tensile testing at 25°C and a tensile rate of 10mm/min. Test 5 specimens for each sample, and take the average value as the test result.

Example 1

This embodiment provides a method for preparing thermoplastic polyester, specifically as follows:

Add terephthalic acid, tricyclodecane dimethanol TCDDM, ethylene glycol, and 1,4-cyclohexanedimethanol into the reactor according to the molar ratio of 1:0.20:0.6:0.3, and gradually raise the temperature to 180°C for esterification. React for 3.0 hours, then add 0.8‰ polycondensation catalyst antimony trioxide and 1.0‰ stabilizer trimethyl phosphate, gradually raise the temperature to 230°C, gradually reduce the vacuum to 50 Pa, and react for 3 hours to obtain a copolyester material.

The physical property test results of the copolyester material in this example are as follows:

The copolyester has an intrinsic viscosity of 0.78dL/g and a glass transition temperature of 106°C. Cutting off at 700nm, the visible light transmittance is 91%, the tensile strength is 55MPa, and the elongation at break is >200%.

Example 2

This embodiment provides a method for preparing thermoplastic polyester, specifically as follows:

(1) Add 2 mol of terephthalic acid, 1 mol of tricyclodecanedimethanol, 0.2 mol of neopentyl glycol, 0.5 mol of 1,4-cyclohexanedimethanol, and 0.8 mol of ethylene glycol into the _N atmosphere reactor. Catalyst 0.40g dibutyltin oxide, stabilizer triphenyl phosphate 0.30g, mix evenly, and then pressurize with nitrogen to a pressure of 2.0kg/cm ² , react at 200°C for 1h, and 210°C for 2h to obtain a transesterification product;

(2) The transesterification product is polycondensed for 2 hours under the conditions of 260~270℃ and absolute pressure ≤200Pa to obtain copolyester material.

The physical property test results of the copolyester material in this example are as follows:

The copolyester has an intrinsic viscosity of 0.63dL/g and a glass transition temperature of 115°C. Cutting off at 700nm, the visible light transmittance is 90%, the tensile strength is 62MPa, and the elongation at break is 110%.

Example 3

This embodiment provides a method for preparing thermoplastic polyester, specifically as follows:

Add terephthalic acid, 1,4-cyclohexanedimethanol, ethylene glycol, and tricyclodecanedimethanol into the reactor in a molar ratio of 1:0.4:0.8:0.2, and then add terephthalic acid in a molar amount of 1 ‰ of dibutyltin oxide, under nitrogen protection conditions, gradually raise the temperature to 185°C for esterification, react for 3 hours, and then add terephthalic acid molar amount of 0.6‰ of catalyst antimony trioxide and 1.0‰ of stabilizer triphosphate. Phenyl ester, gradually raise the temperature to 270°C, gradually reduce the vacuum degree to 30Pa, and react for 3.0 hours to obtain copolyester.

The intrinsic viscosity, glass transition temperature, tensile properties and transparency of the copolyester material prepared in this example were tested.

The copolyester has an intrinsic viscosity of 0.72dL/g, a glass transition temperature of 120°C, a cutoff of 700nm, a visible light transmittance of 89%, and a spline elongation at break of 140%.

Example 4

This embodiment provides a method for preparing thermoplastic polyester, specifically as follows:

Terephthalic acid, ethylene glycol, and tricyclodecanedimethanol were added into the reactor at a molar ratio of 1:0.8:0.5, and then dibutyltin oxide with a molar amount of terephthalic acid of 1‰ was added, and the mixture was heated under nitrogen protection conditions. , gradually raise the temperature to 185°C for esterification, react for 3 hours, then add the catalyst antimony trioxide with a molar amount of 0.6‰ of terephthalic acid, and the stabilizer triphenyl phosphate of 1.0‰, gradually raise the temperature to 270°C, and gradually increase the vacuum degree. Lowered to 30Pa, reacted for 3.0h, and obtained copolyester.

The intrinsic viscosity, glass transition temperature, tensile properties and transparency of the copolyester material prepared in this example were tested.

The copolyester has an intrinsic viscosity of 0.66dL/g, a glass transition temperature of 102°C, a cutoff of 700nm, a visible light transmittance of 89%, and a spline elongation at break of 60%.

Example 5

This embodiment provides a method for preparing thermoplastic polyester, specifically as follows:

(1) Add 2 mol of furandicarboxylic acid, 1 mol of tricyclodecane dimethanol, 0.5 mol of 1,4-cyclohexanedimethanol, 0.8 mol of ethylene glycol, and 0.40 g of dibutyltin oxide catalyst to a reactor in an _N2 atmosphere to stabilize Add 0.30g of triphenyl phosphate as an agent, mix evenly, and then pressurize with nitrogen to a pressure of 2.0kg/ ^cm2 , react at 200°C for 1h, and 210°C for 2h to obtain the transesterification product;

(2) The transesterification product is polycondensed for 2 hours under the conditions of 260~270℃ and absolute pressure ≤200Pa to obtain copolyester material.

The physical property test results of the copolyester material in this example are as follows:

The copolyester has an intrinsic viscosity of 0.65dL/g and a glass transition temperature of 120°C. Cutting off at 700nm, the visible light transmittance is 90%, the tensile strength is 48MPa, and the elongation at break is 80%.

Comparative example 1

This embodiment provides a method for preparing thermoplastic polyester, specifically as follows:

(1) Add 2 mol of terephthalic acid, 1 mol of tricyclodecanedimethanol, 0.8 mol of ethylene glycol, 0.35 g of dibutyltin oxide as catalyst, and 0.25 g of stabilizer triphenyl phosphate into the reactor, mix evenly, and then use nitrogen Pressurize to a pressure of 2.0kg/ ^cm2 , react at 200°C for 1 hour, and react at 210°C for 2 hours to obtain the transesterification product;

(2) The transesterification product is polycondensed for 2 hours under the conditions of 260~270℃ and absolute pressure ≤200Pa to obtain copolyester material.

The physical property test results of the copolyester material of this comparative example are as follows:

The copolyester has an intrinsic viscosity of 0.63dL/g and a glass transition temperature of 120°C. Cutting off at 700nm, the visible light transmittance is 86%, the tensile strength is 44MPa, and the elongation at break is 10%.

Comparative example 2

This embodiment provides a method for preparing thermoplastic polyester, specifically as follows:

(1) Add 2 mol of terephthalic acid, 1 mol of 1,4-cyclohexanedimethanol, 1.6 mol of ethylene glycol, 0.40 g of dibutyltin oxide as catalyst, and 0.30 g of stabilizer triphenyl phosphate into the reactor, mix evenly, and Then pressurize with nitrogen to a pressure of 2.0kg/ ^cm2 , react at 200°C for 1h, and 210°C for 2h to obtain the transesterification product;

(2) The transesterification product is polycondensed for 2 hours under the conditions of 260~270℃ and absolute pressure ≤200Pa to obtain copolyester material.

The physical property test results of the copolyester material of this comparative example are as follows:

The copolyester has an intrinsic viscosity of 0.68dL/g and a glass transition temperature of 84°C. Cutting off at 700nm, the visible light transmittance is 89%, the tensile strength is 42MPa, and the elongation at break is 100%.

The technical features of the above-described embodiments can be combined in any way. To simplify the description, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, All should be considered to be within the scope of this manual.

The above-mentioned embodiments only express several implementation modes of the present application to facilitate a specific and detailed understanding of the technical solutions of the present application, but should not be construed as limiting the scope of patent protection. It should be noted that, for those of ordinary skill in the art, several modifications and improvements can be made without departing from the concept of the present application, and these all fall within the protection scope of the present application. It should be understood that technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited testing based on the technical solutions provided in this application are within the protection scope of the claims appended to this application. Therefore, the protection scope of the patent of this application shall be subject to the contents of the appended claims, and the description may be used to interpret the contents of the claims.

Claims (12)

A thermoplastic polyester, which is characterized in that it is prepared from raw materials through esterification reaction and cocondensation reaction; The raw materials include diols and dicarboxylic acids; The glycol is a mixture of tricyclodecane dimethanol and other aliphatic glycols. The thermoplastic polyester according to claim 1, characterized in that the other aliphatic diols are selected from the group consisting of ethylene glycol, 1,2-propanediol, 1,3-propanediol, n-butanediol, and n-pentanediol. , one or more of neopentyl glycol, 1,3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol. The thermoplastic polyester according to any one of claims 1 to 2, characterized in that, in the glycol, the molar percentage of the tricyclodecane dimethanol is about 5% to about 60%, and the other fats The mole percent of the family diol ranges from about 40% to about 95%. The thermoplastic polyester according to any one of claims 1 to 3, characterized in that the dicarboxylic acid is selected from the group consisting of terephthalic acid, 2,6-naphthalenedicarboxylic acid, isophthalic acid and furandicarboxylic acid. of one or more. The thermoplastic polyester according to any one of claims 1 to 4, wherein the molar ratio of the diol to the dicarboxylic acid is about 1.05:1 to about 2:1. The thermoplastic polyester according to any one of claims 1 to 5, characterized in that the thermoplastic polyester includes one or more of structural unit A and structural unit B; The structural unit A is

The structural unit B is

The thermoplastic polyester according to any one of claims 1 to 6, characterized in that the thermoplastic polyester meets one or more of the following conditions: (1) The intrinsic viscosity is about 0.5dL/g to about 0.9dL/g; (2) The glass transition temperature is about 90°C to about 150°C. Application of the thermoplastic polyester according to any one of claims 1 to 7 in catering containers, kitchen appliances, optical base films or electronic cigarette oil storage devices. A method for preparing thermoplastic polyester according to any one of claims 1 to 7, characterized in that it includes the following steps: Mix the raw materials with the first catalyst to perform an esterification reaction to prepare ester; The ester, the phosphorus stabilizer and the second catalyst are mixed to perform a copolycondensation reaction. The method for preparing thermoplastic polyester according to claim 9, wherein the conditions for the esterification reaction include: a temperature of about 160°C to about 265°C, a pressure of about 1 to about 3 atmospheres, and a time of about 120 minutes to about 265°C. About 300 minutes. The method for preparing thermoplastic polyester according to any one of claims 9 to 10, wherein the conditions for the cocondensation polymerization reaction include: a temperature of about 250°C to about 300°C, and a time of about 90 min to about 300 min. The method for preparing thermoplastic polyester according to any one of claims 9 to 11, wherein the second catalyst is selected from one of titanium-containing compounds, aluminum-containing compounds, tin-containing compounds and germanium-containing compounds, or Various.