Bio-based polyester with high glass transition temperature and high mechanical strength as well as preparation method and application of bio-based polyester

Abstract

The invention discloses bio-based polyester with high glass transition temperature and high mechanical strength as well as a preparation method and application of the bio-based polyester. The structure of the bio-based polyester with the high glass transition temperature and the high mechanical strength is as shown in a formula (1): # imgabs0 #, x is an integer of 5-70, y is an integer of 0-100, z is an integer of 30-100, and R is dihydric alcohol residues with the carbon atom number of 2-8. The glass transition temperature of the bio-based polyester with high glass transition temperature and high mechanical strength is 69.6 DEG C to 174.6 DEG C, the tensile strength of the bio-based polyester with high glass transition temperature and high mechanical strength is 62 MPa to 134 MPa, and the tensile modulus of the bio-based polyester with high glass transition temperature and high mechanical strength is 2134 MPa to 3102 MPa. The preparation method disclosed by the invention is simple, and the obtained polyester has high glass transition temperature, high tensile strength and thermal stability and can be widely applied to the fields of fire-fighting equipment, baby milk bottles, water cups, kitchen electric products, packaging inner films, device supports, optical base films, decorative materials, automobile accessories and the like.

Description

Technical Field

[0001] The present invention relates to a bio - based polyester, and specifically to a bio - based polyester with a high glass transition temperature and high mechanical strength, its preparation method and application, belonging to the technical field of polymer materials. Background Art

[0002] Heat - resistant polymers have wide applications in fields such as packaging, electronic products, and automobiles. However, most of them are synthesized in polar aprotic solvents, with high prices and complex processes. How to effectively synthesize heat - resistant polymers also faces at least three important challenges: solvent - free, cost reduction and pollution, a high glass temperature above 130 °C, and continuously available renewable monomer resources. Traditional polyesters can be prepared by melt polycondensation, but it is difficult to reach a glass transition temperature of 130 °C, and it is also difficult to improve the mechanical properties. Moreover, most of them are traditional petroleum - based polymer materials. Therefore, there is an urgent need to develop a bio - based polyester with both a high glass transition temperature and excellent mechanical properties to fill the gap in this field. Summary of the Invention

[0003] The main purpose of the present invention is to provide a bio - based polyester with a high glass transition temperature and excellent mechanical properties and its preparation method, aiming to overcome the problems that the monomer raw materials of existing polyesters are non - renewable resources, and the glass transition temperature is relatively low and the mechanical strength is insufficient.

[0004] Another purpose of the present invention is to provide the application of the bio - based polyester with a high glass transition temperature and high mechanical strength.

[0005] To achieve the foregoing invention purposes, the technical solutions adopted by the present invention include:

[0006] The embodiment of the present invention provides a bio - based polyester with a high glass transition temperature and high mechanical strength, and its structural formula is shown as the following formula (1):

[0007]

[0008] Wherein, x is an integer from 5 to 70, y is an integer from 0 to 100, z is an integer from 30 to 100, and R is a diol residue with 2 to 8 carbon atoms.

[0009] In some embodiments, the glass transition temperature of the bio - based polyester with a high glass transition temperature and high mechanical strength is 69.6 °C to 174.6 °C, the tensile strength is 62 MPa to 134 MPa, and the tensile modulus is 2134 MPa to 3102 MPa.

[0010] The embodiment of the present invention also provides a preparation method of a bio - based polyester with a high glass transition temperature and high mechanical strength, which includes:

[0011] Subject a first mixed reaction system comprising a dihydroxyethoxylated polybiphenyl aromatic hydrocarbon, a dibasic acid and / or a dibasic acid esterified product, a diol, and an esterification or transesterification catalyst to an esterification reaction to obtain a first intermediate product;

[0012] Under vacuum conditions, subject the intermediate product to a pre-polycondensation reaction to obtain a second intermediate product;

[0013] Under vacuum conditions, subject the second intermediate product to a polycondensation reaction to obtain a bio-based polyester with a high glass transition temperature and high mechanical strength;

[0014] Wherein, the dihydroxyethoxylated polybiphenyl aromatic hydrocarbon has the following structure of formula (2):

[0015]

[0016] The dibasic acid includes furandicarboxylic acid, and the diol includes a cyclic diol and / or an aliphatic diol.

[0017] An embodiment of the present invention also provides a bio-based polyester with a high glass transition temperature and high mechanical strength prepared by the foregoing preparation method.

[0018] An embodiment of the present invention also provides the application of the bio-based polyester with a high glass transition temperature and high mechanical strength in the preparation of fire-fighting equipment, baby bottles, water cups, kitchen electrical products, food packaging materials, hot-fill beverage bottles, optical base films, decorative materials or automotive parts.

[0019] Compared with the prior art, the present invention has at least the following beneficial effects:

[0020] 1) By using a dihydroxyethoxylated polybiphenyl aromatic hydrocarbon and an alicyclic rigid diol to synthesize a polyester, the present invention can utilize the characteristics that the structure of the dihydroxyethoxylated polybiphenyl aromatic hydrocarbon has multiple benzene rings, a very rigid structure, and highly active hydroxyethyl groups, enabling it to efficiently undergo an esterification or transesterification reaction with a dicarboxylic acid or an esterified product. On this basis, by copolymerizing with an alicyclic diol and utilizing the characteristics of the alicyclic diol having greater rigidity and a non-planar spatial structure than an aliphatic diol, the glass transition temperature, transparency, and impact resistance of the copolyester are improved, and finally a high-molecular-weight copolyester is prepared, greatly improving the comprehensive performance of the copolyester;

[0021] 2) The preparation method of the present invention is simple, controllable, easy to implement, and suitable for large-scale industrial production. Moreover, using 2,5-furandicarboxylic acid or its diester prepared from biomass as a raw material can promote the sustainable development of bio-based polymer materials. Description of the Drawings

[0022] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are only some embodiments recorded in the present invention. For those of ordinary skill in the art, without creative work, other drawings can be obtained based on these drawings.

[0023] Figure 1 1H-NMR spectrum of the poly(2,5-furandicarboxylic acid-bis(hydroxyethoxypolycyclic aromatic hydrocarbon)-ethylene glycol-1,4-cyclohexanedimethanol) copolymer of Example 4 of the present invention 1 1H-NMR spectrum;

[0024] Figure 2 DSC spectrum of the poly(2,5-furandicarboxylic acid-bis(hydroxyethoxypolycyclic aromatic hydrocarbon)-ethylene glycol-1,4-cyclohexanedimethanol) copolymer of Example 4 of the present invention. Detailed implementation manners

[0025] The bio-based 2,5-furandicarboxylic acid (FDCA) derived from renewable fructose or furfural has a rigid aromatic ring and highly reactive carboxyl groups, and is considered to be the most important bio-based aromatic monomer for synthesizing new polymers to replace petroleum-based terephthalic acid. 2,5-Furandicarboxylic acid has greater rigidity and polarity than terephthalic acid. Designing for the synthesis of bio-based polymer materials can effectively improve their heat resistance and mechanical properties. The present invention uses 2,5-furandicarboxylic acid or its ester / terephthalic acid or its ester and bis(hydroxyethoxypolycyclic aromatic hydrocarbon) and various cyclic diols and / or aliphatic diols to carry out copolymerization to prepare a copolyester with high molecular weight, high transparency, high heat resistance and excellent mechanical properties as shown in the structural formula of formula (1).

[0026] Through long-term research and a large number of practices, the inventors of this case have been able to propose the technical solution of the present invention. It is mainly prepared by copolymerizing an aromatic ring with excellent rigidity and highly active bis(hydroxyethoxypolycyclic aromatic hydrocarbon) with 2,5-furandicarboxylic acid or its ester / terephthalic acid or its ester and various cyclic diols and / or aliphatic diols to obtain a copolyester with a glass transition temperature of 69.9 °C to 174.6 °C, a tensile strength of 62 MPa to 134 MPa, and a tensile modulus of 2134 MPa to 3102 MPa. The present invention will be more fully understood by reading the following detailed implementation manners together with the accompanying drawings. The detailed embodiments of the present invention are disclosed herein; however, it should be understood that the disclosed embodiments are only exemplary of the present invention, and the present invention can be embodied in various forms. Therefore, the specific functional details disclosed herein should not be construed as restrictive, but only as the basis of the claims and as a representative basis for teaching those skilled in the art to adopt the present invention in any appropriate detailed embodiment in fact.

[0027] The following will further describe a class of bio - based polyesters with high glass transition temperature and high mechanical strength provided by the present invention and their preparation methods.

[0028] Specifically, as an aspect of the technical solution of the present invention, the structural formula of a bio - based polyester with high glass transition temperature and high mechanical strength is shown as the following formula (1):

[0029]

[0030] Among them, x is an integer from 5 to 70, y is an integer from 0 to 100, z is an integer from 30 to 100, and R is a residue of a diol with 2 to 8 carbon atoms.

[0031] In some embodiments, the diol includes cyclic diols and / or aliphatic diols, etc., and it can include any one or more of the following diols: such as ethylene glycol, 1,4 - cyclohexanedimethanol, propylene glycol, butanediol, 2,2,4,4 - tetramethyl - 1,3 - cyclobutanedimethanol, isosorbide, etc., or any combination of two or more of them, but not limited thereto.

[0032] Specifically, the diol can include any one of the following structures:

[0033]

[0034] In some embodiments, the glass transition temperature of the bio - based polyester with high glass transition temperature and high mechanical strength is 69.9 °C to 174.6 °C, the tensile strength is 62 MPa to 134 MPa, and the tensile modulus is 2134 MPa to 3102 MPa. It has excellent heat resistance and mechanical properties, and can meet the manufacturing requirements for fields such as packaging, electronic products, and automobiles.

[0035] As another aspect of the technical solution of the present invention, a preparation method of a bio - based polyester with high glass transition temperature and high mechanical strength includes:

[0036] Subjecting a first mixed reaction system containing bis - hydroxyethoxypolyphenyl aromatic hydrocarbon, dicarboxylic acid and / or dicarboxylic acid esterified product, diol, and an esterification or transesterification catalyst to an esterification reaction to obtain a first intermediate product;

[0037] Under vacuum conditions, subjecting the intermediate product to a pre - polycondensation reaction to obtain a second intermediate product;

[0038] Under vacuum conditions, subjecting the second intermediate product to a polycondensation reaction to obtain a bio - based polyester with high glass transition temperature and high mechanical strength.

[0039] In some embodiments, the bis - hydroxyethoxypolyphenyl aromatic hydrocarbon has the following structure of formula (2):

[0040]

[0041] In some embodiments, the dicarboxylic acid may be furandicarboxylic acid or terephthalic acid. Correspondingly, the dicarboxylic acid ester may be furandicarboxylic acid ester, terephthalic acid ester, etc.

[0042] Specifically, the dicarboxylic acid is 2,5-furandicarboxylic acid or terephthalic acid, and the ester is dimethyl 2,5-furandicarboxylate or dimethyl terephthalate. Since dimethyl 2,5-furandicarboxylate and dimethyl terephthalate have better reactivity, dimethyl 2,5-furandicarboxylate and dimethyl terephthalate are used. For example, the dicarboxylic acid or its ester may be any one of the following structures:

[0043]

[0044] In some embodiments, the diol includes a cyclic diol and / or an aliphatic diol. Specifically, the diol includes any one or a combination of two or more of bis(hydroxyethoxy) polyphenyl aromatic hydrocarbons, ethylene glycol, 1,4-cyclohexanedimethanol, propylene glycol, butanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanedimethanol, isosorbide, etc., but is not limited thereto. Further, the diol includes any one of the following structures:

[0045]

[0046] In some embodiments, the preparation method may specifically include: under a protective atmosphere, subjecting the first mixed reaction system to an esterification reaction at 180-200°C for 4-6 h to obtain a second mixed reaction system.

[0047] In some embodiments, the preparation method may specifically include: subjecting the second mixed reaction system containing the first intermediate product, a polycondensation catalyst, and a stabilizer to a pre-polycondensation reaction under vacuum conditions to obtain a pre-polycondensation product, i.e., a second intermediate product.

[0048] In some more specific embodiments, the preparation method includes: subjecting the second mixed reaction system to a pre-polycondensation reaction at a temperature of 200-240°C and a vacuum degree of 100 Pa-1000 Pa for 0.5-1 h to obtain a second intermediate product.

[0049] In some embodiments, the preparation method may specifically include: subjecting the second intermediate product to a polycondensation reaction at a vacuum degree of less than 20 Pa and a reaction temperature of 260°C-280°C for 2-4 h to obtain the high glass transition temperature and high mechanical strength bio-based polyester.

[0050] In some more preferred embodiments, the method for preparing the high glass transition temperature and high mechanical strength biobased polyester comprises the following steps:

[0051] Subject a first mixed reaction system comprising bis(hydroxyethoxy)polyphenyl aromatic hydrocarbon, a dibasic acid or its esterified product, a diol, and an esterification or transesterification catalyst to an esterification reaction to obtain a first intermediate product;

[0052] Subject a second mixed reaction system comprising the first intermediate product, a polycondensation catalyst, and a stabilizer to a pre-polycondensation reaction under vacuum conditions to obtain a pre-polycondensation product;

[0053] Subject the pre-polycondensation product to a polycondensation reaction under vacuum conditions to obtain the high glass transition temperature and high mechanical strength biobased polyester.

[0054] Among them, in some more specific embodiments, the method for preparing the high glass transition temperature and high mechanical strength polyester comprises:

[0055] (1) Under a protective atmosphere, subject the first mixed reaction system to an esterification reaction at 180 - 200 °C for 4 - 6 h to obtain a second mixed reaction system;

[0056] (2) Subject the second mixed reaction system to a pre-polycondensation reaction at a temperature of 200 - 240 °C and a vacuum degree of 100 Pa - 1000 Pa for 0.5 - 1 h to obtain a pre-polycondensation product;

[0057] (3) Subject the pre-polycondensation product to a polycondensation reaction at a vacuum degree of less than 20 Pa and a reaction temperature of 260 °C - 280 °C for 2 - 4 h to obtain the high glass transition temperature and high mechanical strength biobased polyester.

[0058] In some preferred embodiments, in step (1), the molar ratio of the bis(hydroxyethoxy)polyphenyl aromatic hydrocarbon to furandicarboxylic acid and / or its esterified product is 5 - 70:100.

[0059] In some preferred embodiments, in step (1), the molar ratio of the combination of the diol and the bis(hydroxyethoxy)polyphenyl aromatic hydrocarbon to furandicarboxylic acid and / or its esterified product is 1.6 - 2.1:1.

[0060] In some preferred embodiments, in step (1), the molar ratio of the diol to terephthalic acid and / or its esterified product is 1.6 - 2.1:1.

[0061] Furthermore, in step (1), the molar ratio of the esterification or transesterification catalyst to furandicarboxylic acid and / or its esterified product is 1.5 - 2:1000.

[0062] Further, in step (1), the molar ratio of the esterification or transesterification catalyst to terephthalic acid and / or terephthalic acid esterified product is 1.5 - 2:1000.

[0063] Further, in step (1), the esterification or transesterification catalyst includes a zinc-based catalyst, and particularly preferably includes anhydrous zinc acetate.

[0064] Further, in step (1), the molar ratio of the dibasic acid or its esterified product, the diol, and the esterification catalyst is 1:2.1:0.0015 - 0.002.

[0065] Further, when the dibasic acid esterified product is dimethyl furandicarboxylate and the diol is ethylene glycol and 1,4-cyclohexanedimethanol, the molar ratio of dimethyl furandicarboxylate, ethylene glycol, 1,4-cyclohexanedimethanol, and dihydroxyethoxylated polybiphenyl aromatic hydrocarbon is 1:1.1:(0.3 - 1):(0 - 0.7).

[0066] In the present invention, the first intermediate product formed after the reaction of the dibasic acid or its esterified product with the diol monomer is a mixture, including unreacted diol, esterification reaction catalyst, and the reaction products of the dibasic acid or its esterified product with each diol, etc. Considering the activity of the compounds, there will be partial reactions between the reaction products to form low-molecular-weight copolyesters.

[0067] If the polycondensation is directly carried out after the first-step reaction is completed, it will cause the unreacted diol monomer to not be condensed in time, increasing side reactions and broadening the molecular weight distribution of the copolyester. Therefore, in the present invention, the first intermediate product is first subjected to the pre-polycondensation reaction of step (2) to remove the unreacted diol monomer.

[0068] In some preferred embodiments, in step (2), the vacuum degree of the pre-polycondensation reaction is 100 Pa - 1000 Pa, the reaction temperature is 200 °C - 240 °C, and the reaction time is 0.5 hour - 1 hour, so that the unreacted diol monomer can be condensed in time and slowly removed, and the molecular weight of the first intermediate product can increase slowly to obtain the second intermediate product.

[0069] In some preferred embodiments, step (2) further includes adding a polycondensation catalyst to the first intermediate product, and the dosage of the polycondensation catalyst is 1‰ - 2‰ of the molar amount of the dibasic acid or its esterified product.

[0070] Further, in step (2), the molar ratio of the polycondensation catalyst to furandicarboxylic acid and / or furandicarboxylic acid esterified product is 1 - 2:1000.

[0071] Further, in step (2), the molar ratio of the polycondensation catalyst to terephthalic acid and / or terephthalic acid esterified product is 1 - 2:1000.

[0072] Further, the polycondensation catalyst includes an antimony-based catalyst, preferably including antimony trioxide, but not limited thereto.

[0073] In some preferred embodiments, step (2) further includes adding a stabilizer to the first intermediate product, and the dosage of the stabilizer is 0.5‰ to 1‰ of the molar amount of the dibasic acid or its esterified product.

[0074] Further, in step (2), the molar ratio of the stabilizer to furandicarboxylic acid and / or its esterified product is 0.5 - 1:1000.

[0075] Further, in step (2), the molar ratio of the stabilizer to terephthalic acid and / or its esterified product is 0.5 - 1:1000.

[0076] Further, the stabilizer can reduce the oxidative cleavage of ester bonds, aliphatic chains, carbon-carbon bonds, etc. under oxygen, preventing thermal decomposition. The stabilizer can be triphenyl phosphate, but not limited thereto.

[0077] In some preferred embodiments, step (2) further includes adding an antioxidant to the first intermediate product, and the dosage of the antioxidant is 0.5‰ to 1‰ of the molar amount of the dibasic acid or its esterified product.

[0078] Further, the molar ratio of the antioxidant to furandicarboxylic acid and / or its esterified product is 0.5 - 1:1000.

[0079] Further, the molar ratio of the antioxidant to terephthalic acid and / or its esterified product is 0.5 - 1:1000.

[0080] Further, the antioxidant can capture oxygen free radicals, eliminate trace oxygen, thereby reducing the occurrence of thermal decomposition reactions and oxidative side reactions. The antioxidant can be antioxidant - 1010, but not limited thereto.

[0081] In some preferred embodiments, in step (3), the vacuum degree of the polycondensation reaction is less than 20 Pa, the reaction temperature is 260°C to 280°C, and the reaction time is 2 hours to 4 hours. During the polycondensation reaction, the molecular weight of the second intermediate product gradually increases, and a bio-based polyester with a high glass transition temperature and high mechanical strength is obtained.

[0082] The reaction equation of the present invention is as follows:

[0083]

[0084] In the present invention, a polyester is synthesized by using dihydroxyethoxylated polyphenyl aromatic hydrocarbons and alicyclic rigid diols. The structure of dihydroxyethoxylated polyphenyl aromatic hydrocarbons has multiple benzene rings, with great rigidity, and the characteristics of highly active hydroxyethyl groups, enabling it to efficiently carry out esterification or transesterification reactions with furandicarboxylic acid or its esters. On this basis, by copolymerizing with alicyclic diols, taking advantage of the greater rigidity and spatial non-planar structure of alicyclic diols compared to aliphatic diols, the glass transition temperature, transparency, and impact resistance of the copolyester are improved. Finally, a high-molecular-weight copolyester is prepared, significantly enhancing the comprehensive performance of the furandicarboxylic acid-based copolyester.

[0085] In the preparation method of the present invention, through a pre-polycondensation reaction after esterification, unreacted diol monomers can be slowly removed, enabling the molecular weight of the first intermediate to increase slowly during polycondensation, thereby obtaining a high-molecular-weight, high glass transition temperature, and high mechanical strength bio-based polyester after the polycondensation reaction. This preparation method is simple, controllable, easy to implement, and suitable for large-scale industrial production. Moreover, using 2,5-furandicarboxylic acid or its diester prepared from biomass as raw materials can promote the sustainable development of bio-based polymeric materials.

[0086] As another aspect of the technical solution of the present invention, it also relates to a high glass transition temperature and high mechanical strength bio-based polyester prepared by the aforementioned preparation method.

[0087] As another aspect of the technical solution of the present invention, it also relates to the application of the aforementioned high glass transition temperature and high mechanical strength bio-based polyester in the fields of fire-fighting equipment, baby bottles, water cups, kitchen electrical products, food packaging materials, hot-fill beverage bottles, optical base films, decorative materials, or automotive parts, etc.

[0088] Hereinafter, the high glass transition temperature and high mechanical strength polyester and its preparation method will be further described through the following specific examples. Based on the following examples, the present invention can be better understood. However, those skilled in the art can easily understand that the specific material ratios, process conditions, and their results described in the examples are only used to illustrate the present invention and should not and will not limit the present invention described in detail in the claims.

[0089] Unless otherwise specified, various raw materials, reaction equipment, testing equipment, and testing methods used in the following examples are well-known in the art.

[0090] In the examples, nuclear magnetic resonance hydrogen spectrum 1 1H-NMR was measured on a Bruker 400AVANCEⅢSpectrometer type instrument at 400 MHz, and the solvent used was CDCl 3 .

[0091] In the examples, the molecular weights of all polymers were measured using an Agilent PL-GPC220. Two PLgel 5μm Mixed-D 300*7.5mm columns were connected in series. The mobile phase was chloroform, the test temperature was 40 °C, the sample dissolution solvent was o-chlorophenol:chloroform = 1:9 (v / v), the sample concentration was 1 mg / mL, the flow rate was 1 mL / min, and the standard sample was PS (3070 - 258000 g / mol).

[0092] In the examples, thermal analysis was performed using differential scanning calorimetry (Mettler Toledo DSC) at a heating rate of 10 °C / min in an N 2 atmosphere, and the temperature range was 50 - 275 °C. Thermal stability was tested using a Mettler Toledo TGA / DSC. Among them, 5 - 8 mg of the sample was heated in a ceramic furnace at a rate of 20 °C / min from 50 - 800 °C in an N 2 (flow rate of 50 ml / min) and air environment.

[0093] In the examples, the elongation at break, tensile strength, and tensile modulus of the copolymer were tested on an Instron 5567 tensile testing machine. The specimens used were dumbbell-shaped, with a specimen size of 1 mm × 2 mm (thickness × width). The test used a 1 kn load cell, and the tensile rate was 50 mm / min.

[0094] Example 1

[0095] 92.1 g of dimethyl 2,5-furandicarboxylate, 68.5 g of 1,4-cyclohexanedimethanol, 13.5 g of bis(hydroxyethoxy)polyphenyl aromatic hydrocarbon, and 34.1 g of ethylene glycol were added to a polymerization reactor, and then 0.2% of anhydrous zinc acetate based on the molar amount of dimethyl 2,5-furandicarboxylate was added. Under an inert atmosphere, an esterification reaction was carried out at 180 °C for 6 h to obtain a first intermediate product.

[0096] 0.1% of antimony trioxide, 0.5‰ of triphenyl phosphate, and 0.5‰ of antioxidant 1010 based on the molar amount of dimethyl 2,5-furandicarboxylate were added to the first intermediate product. The vacuum was 100 Pa - 1000 Pa, and pre-polycondensation was carried out at 240 °C for 1 h to obtain a second intermediate product.

[0097] Then the second intermediate product was reacted at 260 °C under a vacuum of less than 20 Pa for 4 h to obtain a furandicarboxylic acid copolyester.

[0098] After testing, the relative number-average molecular weight of this furandicarboxylic acid copolyester was 33800 g / mol, the relative weight-average molecular weight was 56000 g / mol, and the glass transition temperature was 89.8 °C.

[0099] In this copolyester of furandicarboxylic acid, the molar ratio of ethylene glycol structural unit: 1,4-cyclohexanedimethanol structural unit: dihydroxyethoxypolyphenyl aromatic hydrocarbon structural unit = 9:86:5.

[0100] The tensile strength of this copolyester of furandicarboxylic acid is 66 MPa, the tensile modulus is 2480 MPa, and the elongation at break is 113%.

[0101] Example 2

[0102] 92.1 g of dimethyl furandicarboxylate, 64.9 g of 1,4-cyclohexanedimethanol, 26.9 g of dihydroxyethoxypolyphenyl aromatic hydrocarbon and 34.1 g of ethylene glycol were added to a polymerization reactor, and then 0.2% of anhydrous zinc acetate based on the molar amount of dimethyl furandicarboxylate was added. Under an inert atmosphere, an esterification reaction was carried out at 180 °C for 6 h to obtain a first intermediate product.

[0103] 0.1% of antimony trioxide, 0.5‰ of triphenyl phosphate and 0.5‰ of antioxidant 1010 based on the molar amount of dimethyl furandicarboxylate were added to the first intermediate product. The vacuum was 100 Pa to 1000 Pa, and pre-polycondensation was carried out at 240 °C for 1 h to obtain a second intermediate product.

[0104] Then the second intermediate product was reacted at 260 °C under a vacuum of less than 20 Pa for 4 h to obtain a copolyester of furandicarboxylic acid.

[0105] After testing, the relative number-average molecular weight of this copolyester of furandicarboxylic acid is 31900 g / mol, the relative weight-average molecular weight is 55000 g / mol, and the glass transition temperature is 99.1 °C.

[0106] In this copolyester of furandicarboxylic acid, the molar ratio of ethylene glycol structural unit: 1,4-cyclohexanedimethanol structural unit: dihydroxyethoxypolyphenyl aromatic hydrocarbon structural unit = 10:80:10.

[0107] The tensile strength of this copolyester of furandicarboxylic acid is 80 MPa, the tensile modulus is 2525 MPa, and the elongation at break is 48%.

[0108] Example 3

[0109] 92.1 g of dimethyl furandicarboxylate, 57.5 g of 1,4-cyclohexanedimethanol, 53.8 g of dihydroxyethoxypolyphenyl aromatic hydrocarbon and 31.0 g of ethylene glycol were added to a polymerization reactor, and then 0.2% of anhydrous zinc acetate based on the molar amount of dimethyl furandicarboxylate was added. Under an inert atmosphere, an esterification reaction was carried out at 180 °C for 5 h to obtain a first intermediate product.

[0110] Add 0.1% of antimony trioxide, 0.5‰ of triphenyl phosphate and 0.5‰ of antioxidant 1010 based on the molar amount of dimethyl 2,5-furandicarboxylate to the first intermediate product. Under a vacuum of 100 Pa to 1000 Pa, pre-polycondense at 230 °C for 1 h to obtain the second intermediate product.

[0111] Then react the second intermediate product at 270 °C under a vacuum of less than 20 Pa for 4 h to obtain the furandicarboxylic acid copolyester.

[0112] Upon detection, the relative number-average molecular weight of the furandicarboxylic acid copolyester is 35700 g / mol, and the relative weight-average molecular weight is 58800 g / mol. As Figure 2 shown, the glass transition temperature of the furandicarboxylic acid copolyester is 113.7 °C.

[0113] As Figure 1 shown, in the furandicarboxylic acid copolyester, the molar ratio of ethylene glycol structural unit: 1,4-cyclohexanedimethanol structural unit: bis(hydroxyethoxy)polyphenyl aromatic hydrocarbon structural unit = 9:71:20.

[0114] The tensile strength of the furandicarboxylic acid copolyester is 96 MPa, the tensile modulus is 2734 MPa, and the elongation at break is 27%.

[0115] Example 4

[0116] Add 92.1 g of dimethyl 2,5-furandicarboxylate, 50.1 g of 1,4-cyclohexanedimethanol, 80.7 g of bis(hydroxyethoxy)polyphenyl aromatic hydrocarbon and 27.9 g of ethylene glycol to the polymerization reactor, and then add 0.2% of anhydrous zinc acetate based on the molar amount of dimethyl 2,5-furandicarboxylate. Under an inert atmosphere, carry out an esterification reaction at 190 °C for 5 h to obtain the first intermediate product.

[0117] Add 0.1% of antimony trioxide, 0.5‰ of triphenyl phosphate and 0.5‰ of antioxidant 1010 based on the molar amount of dimethyl 2,5-furandicarboxylate to the first intermediate product. Under a vacuum of 100 Pa to 1000 Pa, pre-polycondense at 220 °C for 1 h to obtain the second intermediate product.

[0118] Then react the second intermediate product at 270 °C under a vacuum of less than 20 Pa for 3 h to obtain the furandicarboxylic acid copolyester.

[0119] Upon detection, the relative number-average molecular weight of the furandicarboxylic acid copolyester is 35700 g / mol, the relative weight-average molecular weight is 58800 g / mol, and the glass transition temperature is 131.1 °C.

[0120] In this copolyester of furandicarboxylic acid, the molar ratio of ethylene glycol structural unit: 1,4-cyclohexanedimethanol structural unit: bis(hydroxyethoxy)polyphenyl aromatic hydrocarbon structural unit = 8:62:30.

[0121] The tensile strength of this copolyester of furandicarboxylic acid is 106 MPa, the tensile modulus is 2885 MPa, and the elongation at break is 12%.

[0122] Example 5

[0123] 92.1 g of dimethyl furandicarboxylate, 39.7 g of 1,4-cyclohexanedimethanol, 107.7 g of bis(hydroxyethoxy)polyphenyl aromatic hydrocarbon, and 26.4 g of ethylene glycol were added to a polymerization reactor, and then 0.2% of anhydrous zinc acetate based on the molar amount of dimethyl furandicarboxylate was added. Under an inert atmosphere, an esterification reaction was carried out at 190 °C for 5 h to obtain a first intermediate product.

[0124] 0.1% of antimony trioxide, 0.5‰ of triphenyl phosphate, and 0.5‰ of antioxidant 1010 based on the molar amount of dimethyl furandicarboxylate were added to the first intermediate product. With a vacuum degree of 100 Pa - 1000 Pa, a pre-polycondensation was carried out at 230 °C for 0.5 h to obtain a second intermediate product.

[0125] Then the second intermediate product was reacted at 270 °C under a vacuum degree below 20 Pa for 3 h to obtain the copolyester of furandicarboxylic acid.

[0126] After testing, the relative number-average molecular weight of this copolyester of furandicarboxylic acid is 28500 g / mol, the relative weight-average molecular weight is 49000 g / mol, and the glass transition temperature is 141.2 °C.

[0127] In this copolyester of furandicarboxylic acid, the molar ratio of ethylene glycol structural unit: 1,4-cyclohexanedimethanol structural unit: bis(hydroxyethoxy)polyphenyl aromatic hydrocarbon structural unit = 7:53:40.

[0128] The tensile strength of this copolyester of furandicarboxylic acid is 121 MPa, the tensile modulus is 2914 MPa, and the elongation at break is 6%.

[0129] Example 6

[0130] 92.1 g of dimethyl furandicarboxylate, 32.4 g of 1,4-cyclohexanedimethanol, 134.6 g of bis(hydroxyethoxy)polyphenyl aromatic hydrocarbon, and 26.4 g of ethylene glycol were added to a polymerization reactor, and then 0.2% of anhydrous zinc acetate based on the molar amount of dimethyl furandicarboxylate was added. Under an inert atmosphere, an esterification reaction was carried out at 190 °C for 4 h to obtain a first intermediate product.

[0131] Add 0.1% antimony trioxide, 0.5‰ triphenyl phosphate and 0.5‰ antioxidant 1010 based on the molar amount of dimethyl 2,5-furandicarboxylate to the first intermediate product. With a vacuum degree of 100 Pa - 1000 Pa, pre-polycondense at 220 °C for 1 h to obtain the second intermediate product.

[0132] Then react the second intermediate product at 280 °C under a vacuum degree of less than 20 Pa for 3 h to obtain the furandicarboxylic acid copolyester.

[0133] After testing, the relative number-average molecular weight of this furandicarboxylic acid copolyester is 26500 g / mol, the relative weight-average molecular weight is 44600 g / mol, and the glass transition temperature is 153.4 °C.

[0134] In this furandicarboxylic acid copolyester, the molar ratio of ethylene glycol structural unit: 1,4-cyclohexanedimethanol structural unit: dihydroxyethoxypolyphenyl aromatic hydrocarbon structural unit = 7:43:50.

[0135] The tensile strength of this furandicarboxylic acid copolyester is 121 MPa, the tensile modulus is 2972 MPa, and the elongation at break is 6%.

[0136] Example 7

[0137] Add 92.1 g of dimethyl 2,5-furandicarboxylate, 25.2 g of 1,4-cyclohexanedimethanol, 161.5 g of dihydroxyethoxypolyphenyl aromatic hydrocarbon and 23.3 g of ethylene glycol to the polymerization reactor, and then add 0.2% anhydrous zinc acetate based on the molar amount of dimethyl 2,5-furandicarboxylate. Under an inert atmosphere, carry out the esterification reaction at 200 °C for 4 h to obtain the first intermediate product.

[0138] Add 0.1% antimony trioxide, 0.5‰ triphenyl phosphate and 0.5‰ antioxidant 1010 based on the molar amount of dimethyl 2,5-furandicarboxylate to the first intermediate product. With a vacuum degree of 100 Pa - 1000 Pa, pre-polycondense at 210 °C for 0.5 h to obtain the second intermediate product.

[0139] Then react the second intermediate product at 280 °C under a vacuum degree of less than 20 Pa for 3 h to obtain the furandicarboxylic acid copolyester.

[0140] After testing, the relative number-average molecular weight of this furandicarboxylic acid copolyester is 24600 g / mol, the relative weight-average molecular weight is 41600 g / mol, and the glass transition temperature is 164.2 °C.

[0141] In this furandicarboxylic acid copolyester, the molar ratio of ethylene glycol structural unit: 1,4-cyclohexanedimethanol structural unit: dihydroxyethoxypolyphenyl aromatic hydrocarbon structural unit = 5:35:60.

[0142] The tensile strength of the furandicarboxylic acid copolyester is 134 MPa, the tensile modulus is 3029 MPa, and the elongation at break is 6%.

[0143] Example 8

[0144] 92.1 g of dimethyl 2,5-furandicarboxylate, 18.1 g of 1,4-cyclohexanedimethanol, 188.4 g of dihydroxyethoxypolyaryl hydrocarbon, and 20.2 g of ethylene glycol were added to a polymerization reactor, and then 0.2% of anhydrous zinc acetate based on the molar amount of dimethyl 2,5-furandicarboxylate was added. Under an inert atmosphere, an esterification reaction was carried out at 200 °C for 4 h to obtain a first intermediate product.

[0145] 0.2% of antimony trioxide, 1‰ of triphenyl phosphate, and 1‰ of antioxidant 1010 based on the molar amount of dimethyl 2,5-furandicarboxylate were added to the first intermediate product. The vacuum was 100 Pa to 1000 Pa, and pre-polycondensation was carried out at 200 °C for 0.5 h to obtain a second intermediate product.

[0146] Then, the second intermediate product was reacted at 280 °C under a vacuum of less than 20 Pa for 2 h to obtain the furandicarboxylic acid copolyester.

[0147] After testing, the relative number-average molecular weight of the furandicarboxylic acid copolyester was 27,600 g / mol, the relative weight-average molecular weight was 47,100 g / mol, and the glass transition temperature was 174.6 °C.

[0148] In the furandicarboxylic acid copolyester, the molar ratio of ethylene glycol structural unit: 1,4-cyclohexanedimethanol structural unit: dihydroxyethoxypolyaryl hydrocarbon structural unit = 5:25:70.

[0149] The tensile strength of the furandicarboxylic acid copolyester is 124 MPa, the tensile modulus is 3102 MPa, and the elongation at break is 5%.

[0150] Example 9

[0151] 92.1 g of dimethyl 2,5-furandicarboxylate, 50.1 g of 1,4-cyclohexanedimethanol, 80.7 g of dihydroxyethoxypolyaryl hydrocarbon, and 41.9 g of propylene glycol were added to a polymerization reactor, and then 0.2% of anhydrous zinc acetate based on the molar amount of dimethyl 2,5-furandicarboxylate was added. Under an inert atmosphere, an esterification reaction was carried out at 200 °C for 4 h to obtain a first intermediate product.

[0152] 0.1% of antimony trioxide, 0.5‰ of triphenyl phosphate, and 0.5‰ of antioxidant 1010 based on the molar amount of dimethyl 2,5-furandicarboxylate were added to the first intermediate product. The vacuum was 100 Pa to 1000 Pa, and pre-polycondensation was carried out at 220 °C for 1 h to obtain a second intermediate product.

[0153] Then, the second intermediate product is reacted at 270 °C under a vacuum of 20 Pa or less for 3 h to obtain the copolyester of furandicarboxylic acid.

[0154] After testing, the relative number-average molecular weight of the copolyester of furandicarboxylic acid is 33,700 g / mol, the relative weight-average molecular weight is 46,300 g / mol, and the glass transition temperature is 115.3 °C.

[0155] Example 10

[0156] 92.1 g of dimethyl 2,5-furandicarboxylate, 50.1 g of 1,4-cyclohexanedimethanol, 80.7 g of dihydroxyethoxylated polyphenyl aromatic hydrocarbon, and 49.6 g of butanediol are added to a polymerization reactor, and then 0.2% of anhydrous zinc acetate based on the molar amount of dimethyl 2,5-furandicarboxylate is added. Under an inert atmosphere, an esterification reaction is carried out at 200 °C for 4 h to obtain a first intermediate product.

[0157] 0.1% of antimony trioxide, 0.5‰ of triphenyl phosphate, and 0.5‰ of antioxidant 1010 based on the molar amount of dimethyl 2,5-furandicarboxylate are added to the first intermediate product, and a pre-polycondensation is carried out at 220 °C for 1 h under a vacuum of 100 Pa to 1000 Pa to obtain a second intermediate product.

[0158] Then, the second intermediate product is reacted at 270 °C under a vacuum of 20 Pa or less for 3 h to obtain the copolyester of furandicarboxylic acid.

[0159] After testing, the relative number-average molecular weight of the copolyester of furandicarboxylic acid is 30,300 g / mol, the relative weight-average molecular weight is 44,600 g / mol, and the glass transition temperature is 108.3 °C.

[0160] Example 11

[0161] 92.1 g of dimethyl 2,5-furandicarboxylate, 50.1 g of 1,4-cyclohexanedimethanol, 80.7 g of dihydroxyethoxylated polyphenyl aromatic hydrocarbon, and 79.3 g of 2,2,4,4-tetramethyl-1,3-cyclobutanedimethanol are added to a polymerization reactor, and then 0.2% of anhydrous zinc acetate based on the molar amount of dimethyl 2,5-furandicarboxylate is added. Under an inert atmosphere, an esterification reaction is carried out at 200 °C for 4 h to obtain a first intermediate product.

[0162] 0.1% of antimony trioxide, 0.5‰ of triphenyl phosphate, and 0.5‰ of antioxidant 1010 based on the molar amount of dimethyl 2,5-furandicarboxylate are added to the first intermediate product, and a pre-polycondensation is carried out at 220 °C for 1 h under a vacuum of 100 Pa to 1000 Pa to obtain a second intermediate product.

[0163] Then, the second intermediate product is reacted at 270 °C under a vacuum of 20 Pa or less for 3 h to obtain the furandicarboxylic acid copolyester.

[0164] Upon detection, the relative number-average molecular weight of the furandicarboxylic acid copolyester is 35400 g / mol, the relative weight-average molecular weight is 49800 g / mol, and the glass transition temperature is 124.5 °C.

[0165] Example 12

[0166] 92.1 g of dimethyl 2,5-furandicarboxylate, 50.1 g of 1,4-cyclohexanedimethanol, 80.7 g of dihydroxyethoxylated polyphenylene aromatic hydrocarbon, and 80.4 g of isosorbide are added to a polymerization reactor, and then 0.2% of zinc acetate anhydrous based on the molar amount of dimethyl 2,5-furandicarboxylate is added. Under an inert atmosphere, an esterification reaction is carried out at 200 °C for 4 h to obtain a first intermediate product.

[0167] 0.1% of antimony trioxide, 0.5‰ of triphenyl phosphate, and 0.5‰ of antioxidant 1010 based on the molar amount of dimethyl 2,5-furandicarboxylate are added to the first intermediate product, and a pre-polycondensation is carried out at 220 °C for 1 h under a vacuum of 100 Pa to 1000 Pa to obtain a second intermediate product.

[0168] Then, the second intermediate product is reacted at 280 °C under a vacuum of 20 Pa or less for 3 h to obtain the furandicarboxylic acid copolyester.

[0169] Upon detection, the relative number-average molecular weight of the furandicarboxylic acid copolyester is 28300 g / mol, the relative weight-average molecular weight is 36400 g / mol, and the glass transition temperature is 138.6 °C.

[0170] Example 13

[0171] 36.8 g of dimethyl 2,5-furandicarboxylate, 58.3 g of dimethyl terephthalate, 28.8 g of 1,4-cyclohexanedimethanol, 161.5 g of dihydroxyethoxylated polyphenylene aromatic hydrocarbon, and 34.1 g of ethylene glycol are added to a polymerization reactor, and then 0.2% of zinc acetate anhydrous based on the molar amount of dimethyl 2,5-furandicarboxylate is added. Under an inert atmosphere, an esterification reaction is carried out at 200 °C for 4 h to obtain a first intermediate product.

[0172] 0.1% of antimony trioxide, 0.5‰ of triphenyl phosphate, and 0.5‰ of antioxidant 1010 based on the molar amount of dimethyl 2,5-furandicarboxylate are added to the first intermediate product, and a pre-polycondensation is carried out at 200 °C for 0.5 h under a vacuum of 100 Pa to 1000 Pa to obtain a second intermediate product.

[0173] Then, the second intermediate product is reacted at 280 °C under a vacuum of 20 Pa or less for 2 h to obtain the furandicarboxylic acid copolyester.

[0174] Upon detection, the relative number-average molecular weight of this copolyester is 25,500 g / mol, the relative weight-average molecular weight is 37,200 g / mol, and the glass transition temperature is 160.1 °C.

[0175] Example 14

[0176] 55.3 g of dimethyl 2,5-furandicarboxylate, 36.8 g of dimethyl terephthalate, 28.8 g of 1,4-cyclohexanedimethanol, 161.5 g of dihydroxyethoxylated polyphenyl aromatic hydrocarbon, and 34.1 g of ethylene glycol are added to a polymerization reactor, and then 0.2% of zinc acetate anhydrous based on the molar amount of dimethyl 2,5-furandicarboxylate is added. Under an inert atmosphere, an esterification reaction is carried out at 200 °C for 4 h to obtain a first intermediate product.

[0177] 0.1% of antimony trioxide, 0.5‰ of triphenyl phosphate, and 0.5‰ of antioxidant 1010 based on the molar amount of dimethyl 2,5-furandicarboxylate are added to the first intermediate product, and a pre-polycondensation is carried out at 200 °C for 0.5 h under a vacuum of 100 Pa to 1000 Pa to obtain a second intermediate product.

[0178] Then, the second intermediate product is reacted at 280 °C under a vacuum of 20 Pa or less for 2 h to obtain the furandicarboxylic acid copolyester.

[0179] Upon detection, the relative number-average molecular weight of this copolyester is 29,600 g / mol, the relative weight-average molecular weight is 36,200 g / mol, and the glass transition temperature is 164.2 °C.

[0180] Comparative Example 1

[0181] 92.1 g of dimethyl 2,5-furandicarboxylate, 72.1 g of 1,4-cyclohexanedimethanol, and 34.1 g of ethylene glycol are added to a polymerization reactor, and then 0.15% of zinc acetate anhydrous based on the molar amount of dimethyl 2,5-furandicarboxylate is added. Under an inert atmosphere, a reaction is carried out at 180 °C for 6 h to obtain a first intermediate product.

[0182] 0.2% of antimony trioxide, 1‰ of triphenyl phosphate, and 1‰ of antioxidant 1010 based on the molar amount of dimethyl 2,5-furandicarboxylate are added to the first intermediate product, and a pre-polycondensation is carried out at 240 °C for 1 h under a vacuum of 100 Pa to 1000 Pa to obtain a second intermediate product.

[0183] Then, the second intermediate product is reacted at 260 °C under a vacuum of 20 Pa or less for 4 h to obtain the furandicarboxylic acid copolyester.

[0184] After testing, the relative number-average molecular weight of the furan dicarboxylic acid copolyester is 33,800 g / mol, the relative weight-average molecular weight is 57,100 g / mol, and the glass transition temperature is 69.6 °C.

[0185] In this furan dicarboxylic acid copolyester, the molar ratio of ethylene glycol structural unit: 1,4-cyclohexanedimethanol structural unit: bis(hydroxyethoxy)polyphenyl aromatic hydrocarbon structural unit = 10:90:0.

[0186] The tensile strength of this furan dicarboxylic acid copolyester is 62 MPa, the tensile modulus is 2134 MPa, and the elongation at break is 154%.

[0187] Comparative Example 2

[0188] Add 97.1 g of dimethyl terephthalate and 34.1 g of ethylene glycol to the polymerization reactor, and then add 1.5% of anhydrous zinc acetate based on the molar amount of dimethyl terephthalate. React at 180 °C for 4 h under an inert atmosphere to obtain the first intermediate product.

[0189] Add 0.2% of antimony trioxide, 1‰ of triphenyl phosphate, and 1‰ of antioxidant 1010 based on the molar amount of dimethyl terephthalate to the first intermediate product. Carry out pre-polycondensation at 200 °C for 0.5 h under a vacuum of 100 Pa to 1000 Pa to obtain the second intermediate product.

[0190] Then react the second intermediate product at 280 °C under a vacuum of less than 20 Pa for 2 h to obtain the copolyester.

[0191] After testing, the relative number-average molecular weight of this copolyester is 36,600 g / mol, the relative weight-average molecular weight is 45,100 g / mol, and the glass transition temperature is 73.4 °C.

[0192] Comparative Example 3

[0193] Add 97.1 g of dimethyl terephthalate, 14.4 g of 1,4-cyclohexanedimethanol, and 27.9 g of ethylene glycol to the polymerization reactor, and then add 1.5% of anhydrous zinc acetate based on the molar amount of dimethyl terephthalate. React at 180 °C for 4 h under an inert atmosphere to obtain the first intermediate product.

[0194] Add 0.2% of antimony trioxide, 1‰ of triphenyl phosphate, and 1‰ of antioxidant 1010 based on the molar amount of dimethyl terephthalate to the first intermediate product. Carry out pre-polycondensation at 200 °C for 0.5 h under a vacuum of 100 Pa to 1000 Pa to obtain the second intermediate product.

[0195] Then react the second intermediate product at 280 °C under a vacuum of less than 20 Pa for 2 h to obtain the copolyester.

[0196] The number-average relative molecular mass of the copolyester was detected to be 39,000 g / mol, the weight-average relative molecular mass was 49,100 g / mol, and the glass transition temperature was 76.4 °C.

[0197] Comparative Example 4

[0198] 97.1 g of dimethyl terephthalate, 28.8 g of 1,4-cyclohexanedimethanol, and 21.7 g of ethylene glycol were added to a polymerization reactor, and then 1.5% of zinc acetate anhydride based on the molar amount of dimethyl terephthalate was added. Under an inert atmosphere, the reaction was carried out at 180 °C for 4 h to obtain a first intermediate product.

[0199] 0.2% of antimony trioxide, 1‰ of triphenyl phosphate, and 1‰ of antioxidant 1010 based on the molar amount of dimethyl terephthalate were added to the first intermediate product. The vacuum was 100 Pa to 1000 Pa, and pre-polycondensation was carried out at 200 °C for 0.5 h to obtain a second intermediate product.

[0200] Then, the second intermediate product was reacted at 280 °C under a vacuum of less than 20 Pa for 2 h to obtain a copolyester.

[0201] The number-average relative molecular mass of the copolyester was detected to be 42,100 g / mol, the weight-average relative molecular mass was 53,300 g / mol, and the glass transition temperature was 79.4 °C.

[0202] Comparative Example 5

[0203] 97.1 g of dimethyl terephthalate, 43.3 g of 1,4-cyclohexanedimethanol, and 15.6 g of ethylene glycol were added to a polymerization reactor, and then 0.15% of zinc acetate anhydride based on the molar amount of dimethyl terephthalate was added. Under an inert atmosphere, the reaction was carried out at 180 °C for 4 h to obtain a first intermediate product.

[0204] 0.2% of antimony trioxide, 1‰ of triphenyl phosphate, and 1‰ of antioxidant 1010 based on the molar amount of dimethyl terephthalate were added to the first intermediate product. The vacuum was 100 Pa to 1000 Pa, and pre-polycondensation was carried out at 200 °C for 0.5 h to obtain a second intermediate product.

[0205] Then, the second intermediate product was reacted at 280 °C under a vacuum of less than 20 Pa for 2 h to obtain a copolyester.

[0206] The number-average relative molecular mass of the copolyester was detected to be 45,500 g / mol, the weight-average relative molecular mass was 57,100 g / mol, and the glass transition temperature was 81.7 °C.

[0207] Comparative Example 6

[0208] 97.1 g of dimethyl terephthalate and 79.3 g of 1,4-cyclohexanedimethanol were added to a polymerization reactor, and then 0.15% of anhydrous zinc acetate based on the molar amount of dimethyl terephthalate was added. Under an inert atmosphere, the reaction was carried out at 180 °C for 4 h to obtain a first intermediate product.

[0209] 0.2% of antimony trioxide, 1‰ of triphenyl phosphate and 1‰ of antioxidant 1010 based on the molar amount of dimethyl terephthalate were added to the first intermediate product. The vacuum was 100 Pa - 1000 Pa, and pre-polycondensation was carried out at 200 °C for 0.5 h to obtain a second intermediate product.

[0210] Then the second intermediate product was reacted at 280 °C under a vacuum of less than 20 Pa for 2 h to obtain a copolyester.

[0211] After testing, the relative number-average molecular weight of the copolyester was 48200 g / mol, the relative weight-average molecular weight was 59100 g / mol, and the glass transition temperature was 86.7 °C.

[0212] Comparative Example 7

[0213] 97.1 g of dimethyl terephthalate and 41.9 g of propylene glycol were added to a polymerization reactor, and then 0.15% of anhydrous zinc acetate based on the molar amount of dimethyl terephthalate was added. Under an inert atmosphere, the reaction was carried out at 180 °C for 4 h to obtain a first intermediate product.

[0214] 0.2% of antimony trioxide, 1‰ of triphenyl phosphate and 1‰ of antioxidant 1010 based on the molar amount of dimethyl terephthalate were added to the first intermediate product. The vacuum was 100 Pa - 1000 Pa, and pre-polycondensation was carried out at 200 °C for 0.5 h to obtain a second intermediate product.

[0215] Then the second intermediate product was reacted at 280 °C under a vacuum of less than 20 Pa for 2 h to obtain a copolyester.

[0216] After testing, the relative number-average molecular weight of the copolyester was 31000 g / mol, the relative weight-average molecular weight was 34600 g / mol, and the glass transition temperature was 49.8 °C.

[0217] Comparative Example 8

[0218] 97.1 g of dimethyl terephthalate, 22.8 g of propylene glycol and 36.1 g of 1,4-cyclohexanedimethanol were added to a polymerization reactor, and then 0.15% of anhydrous zinc acetate based on the molar amount of dimethyl terephthalate was added. Under an inert atmosphere, the reaction was carried out at 180 °C for 4 h to obtain a first intermediate product.

[0219] Add 0.2% of antimony trioxide, 1‰ of triphenyl phosphate and 1‰ of antioxidant 1010 based on the molar amount of dimethyl terephthalate to the first intermediate product, with a vacuum degree of 100 Pa to 1000 Pa, and pre-polycondense at 200 °C for 0.5 h to obtain the second intermediate product.

[0220] Then react the second intermediate product at 280 °C under a vacuum degree of less than 20 Pa for 2 h to obtain the copolyester.

[0221] Upon detection, the relative number-average molecular weight of the copolyester is 36000 g / mol, the relative weight-average molecular weight is 40600 g / mol, and the glass transition temperature is 54.8 °C.

[0222] Comparative Example 9

[0223] Add 97.1 g of dimethyl terephthalate, 11.4 g of propylene glycol, and 57.7 g of 1,4-cyclohexanedimethanol to the polymerization reactor, and then add 0.15% of anhydrous zinc acetate based on the molar amount of dimethyl terephthalate. React at 180 °C for 4 h under an inert atmosphere to obtain the first intermediate product.

[0224] Add 0.2% of antimony trioxide, 01‰ of triphenyl phosphate and 1‰ of antioxidant 1010 based on the molar amount of dimethyl terephthalate to the first intermediate product, with a vacuum degree of 100 Pa to 1000 Pa, and pre-polycondense at 200 °C for 0.5 h to obtain the second intermediate product.

[0225] Then react the second intermediate product at 280 °C under a vacuum degree of less than 20 Pa for 2 h to obtain the copolyester.

[0226] Upon detection, the relative number-average molecular weight of the copolyester is 36000 g / mol, the relative weight-average molecular weight is 40600 g / mol, and the glass transition temperature is 59.1 °C.

[0227] Comparative Example 10

[0228] Add 97.1 g of dimethyl terephthalate and 49.6 g of butanediol to the polymerization reactor, and then add 0.15% of anhydrous zinc acetate based on the molar amount of dimethyl terephthalate. React at 180 °C for 4 h under an inert atmosphere to obtain the first intermediate product.

[0229] Add 0.2% of antimony trioxide, 1‰ of triphenyl phosphate and 1‰ of antioxidant 1010 based on the molar amount of dimethyl terephthalate to the first intermediate product, with a vacuum degree of 100 Pa to 1000 Pa, and pre-polycondense at 200 °C for 0.5 h to obtain the second intermediate product.

[0230] Then react the second intermediate product at 280 °C under a vacuum degree of less than 20 Pa for 2 h to obtain the copolyester.

[0231] After detection, the relative number-average molecular weight of this copolyester is 34000 g / mol, the relative weight-average molecular weight is 43600 g / mol, and the glass transition temperature is 45.2 °C.

[0232] Comparative Example 11

[0233] 97.1 g of dimethyl terephthalate, 27.0 g of butanediol, and 36.1 g of 1,4-cyclohexanedimethanol were added to a polymerization reactor, and then 0.15% of anhydrous zinc acetate based on the molar amount of dimethyl terephthalate was added. Under an inert atmosphere, the reaction was carried out at 180 °C for 4 h to obtain a first intermediate product.

[0234] 0.2% of antimony trioxide, 1‰ of triphenyl phosphate, and 1‰ of antioxidant 1010 based on the molar amount of dimethyl terephthalate were added to the first intermediate product. The vacuum was 100 Pa - 1000 Pa, and pre-polycondensation was carried out at 200 °C for 0.5 h to obtain a second intermediate product.

[0235] Then the second intermediate product was reacted at 280 °C under a vacuum of less than 20 Pa for 2 h to obtain a copolyester.

[0236] After detection, the relative number-average molecular weight of this copolyester is 39300 g / mol, the relative weight-average molecular weight is 47400 g / mol, and the glass transition temperature is 50.7 °C.

[0237] Comparative Example 12

[0238] 97.1 g of dimethyl terephthalate, 43.3 g of 2,2,4,4-tetramethyl-1,3-cyclobutanedimethanol, and 36.1 g of 1,4-cyclohexanedimethanol were added to a polymerization reactor, and then 0.15% of anhydrous zinc acetate based on the molar amount of dimethyl terephthalate was added. Under an inert atmosphere, the reaction was carried out at 180 °C for 4 h to obtain a first intermediate product.

[0239] 0.2% of antimony trioxide, 1‰ of triphenyl phosphate, and 1‰ of antioxidant 1010 based on the molar amount of dimethyl terephthalate were added to the first intermediate product. The vacuum was 100 Pa - 1000 Pa, and pre-polycondensation was carried out at 200 °C for 0.5 h to obtain a second intermediate product.

[0240] Then the second intermediate product was reacted at 280 °C under a vacuum of less than 20 Pa for 2 h to obtain a copolyester.

[0241] After detection, the relative number-average molecular weight of this copolyester is 29500 g / mol, the relative weight-average molecular weight is 34800 g / mol, and the glass transition temperature is 74.8 °C.

[0242] Comparative Example 13

[0243] 97.1 g of dimethyl terephthalate, 21.6 g of 2,2,4,4 - tetramethyl - 1,3 - cyclobutanedimethanol, and 57.5 g of 1,4 - cyclohexanedimethanol were added to a polymerization reactor, and then 0.15% of anhydrous zinc acetate based on the molar amount of dimethyl terephthalate was added. Under an inert atmosphere, the reaction was carried out at 180 °C for 4 h to obtain a first intermediate product.

[0244] 0.2% of antimony trioxide, 1‰ of triphenyl phosphate, and 1‰ of antioxidant 1010 based on the molar amount of dimethyl terephthalate were added to the first intermediate product. The vacuum was 100 Pa - 1000 Pa, and pre - polycondensation was carried out at 200 °C for 0.5 h to obtain a second intermediate product.

[0245] Then the second intermediate product was reacted at 280 °C under a vacuum of less than 20 Pa for 2 h to obtain a copolyester.

[0246] After testing, the relative number - average molecular weight of the copolyester was 27700 g / mol, the relative weight - average molecular weight was 30600 g / mol, and the glass transition temperature was 70.3 °C.

[0247] Comparative Example 14

[0248] 97.1 g of dimethyl terephthalate, 49.3 g of isosorbide, and 36.1 g of 1,4 - cyclohexanedimethanol were added to a polymerization reactor, and then 0.15% of anhydrous zinc acetate based on the molar amount of dimethyl terephthalate was added. Under an inert atmosphere, the reaction was carried out at 180 °C for 4 h to obtain a first intermediate product.

[0249] 0.2% of antimony trioxide, 1‰ of triphenyl phosphate, and 1‰ of antioxidant 1010 based on the molar amount of dimethyl terephthalate were added to the first intermediate product. The vacuum was 100 Pa - 1000 Pa, and pre - polycondensation was carried out at 200 °C for 0.5 h to obtain a second intermediate product.

[0250] Then the second intermediate product was reacted at 280 °C under a vacuum of less than 20 Pa for 2 h to obtain a copolyester.

[0251] After testing, the relative number - average molecular weight of the copolyester was 23500 g / mol, the relative weight - average molecular weight was 32400 g / mol, and the glass transition temperature was 88.5 °C.

[0252] In addition, the inventors of this case also referred to the foregoing examples and conducted tests with other raw materials, process operations, and process conditions described in this specification, and all obtained relatively ideal results.

[0253] The above has shown and described the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited by the above embodiments. What is described in the above embodiments and the specification only illustrates the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention will have various changes and improvements, and these changes and improvements all fall within the scope of the present invention claimed.

Claims

1. A bio-based polyester with high glass transition temperature and high mechanical strength, characterized in that: The structural formula of the bio-based polyester with high glass transition temperature and high mechanical strength is shown in the following formula (1): Here, x is an integer of 5 to 70, y is an integer of 0 to 100, z is an integer of 30 to 100, and R is a diol residue having 2 to 8 carbon atoms.

2. The bio-based polyester with high glass transition temperature and high mechanical strength according to claim 1, characterized in that: The diol includes a cyclic diol and / or an aliphatic diol. Preferably, the diol includes any of the following structures:

3. The bio-based polyester with high glass transition temperature and high mechanical strength according to claim 1, characterized in that: The high glass transition temperature and high mechanical strength bio-based polyester has a glass transition temperature of 69.6° C. to 174.6° C., a tensile strength of 62 MPa to 134 MPa, and a tensile modulus of 2134 MPa to 3102 MPa.

4. A method for preparing a bio-based polyester with high glass transition temperature and high mechanical strength, characterized in that: include: Conducting an esterification reaction on a first mixed reaction system comprising bis-hydroxyethoxy polyphenyl aromatic hydrocarbons, a dibasic acid and / or a dibasic acid ester, a diol, and an esterification or transesterification catalyst to obtain a first intermediate product; Under vacuum conditions, subjecting the intermediate product to a pre-polycondensation reaction to obtain a second intermediate product; Under vacuum conditions, the second intermediate product is subjected to a polycondensation reaction to obtain a bio-based polyester with a high glass transition temperature and high mechanical strength; Wherein, the bis-hydroxyethoxy polyphenyl aromatic hydrocarbon has the following structure: The dibasic acid includes furandicarboxylic acid, and the diol includes a cyclic diol and / or an aliphatic diol.

5. The preparation method according to claim 4, characterized in that: The dibasic acid further comprises terephthalic acid, and the dibasic acid ester comprises terephthalic acid ester; Preferably, the dibasic acid ester comprises dimethyl furandicarboxylate; And / or, the diol comprises any of the following structures:

6. The preparation method according to claim 5, characterized in that: include: Under a protective atmosphere, allowing the first mixed reaction system to undergo an esterification reaction at 180 to 200° C. for 4 to 6 hours to obtain a second mixed reaction system; and / or, the molar ratio of the bis-hydroxyethoxy polyphenyl aromatic hydrocarbon to furandicarboxylic acid and / or furandicarboxylic acid ester is 5 to 70:100; and / or, the molar ratio of the combination of the diol and the bis-hydroxyethoxy polyphenyl aromatic hydrocarbon to the furandicarboxylic acid and / or the furandicarboxylic acid ester is 1.6 to 2.1:1; Preferably, the molar ratio of the diol to terephthalic acid and / or terephthalate is 1.6 to 2.1:1; Preferably, the molar ratio of the esterification or transesterification catalyst to furandicarboxylic acid and / or furandicarboxylic acid ester is 1.5 to 2:1000; Preferably, the molar ratio of the esterification or transesterification catalyst to terephthalic acid and / or terephthalate is 1.5 to 2:1000; Preferably, the esterification or transesterification catalyst comprises a zinc-based catalyst, and particularly preferably comprises anhydrous zinc acetate.

7. The preparation method according to claim 4, characterized in that: include: subjecting a second mixed reaction system comprising the first intermediate product, a polycondensation catalyst and a stabilizer to a pre-polycondensation reaction under vacuum conditions to obtain a pre-polycondensation product, i.e., a second intermediate product; Preferably, the second mixed reaction system is reacted at a temperature of 200 to 240° C. and a vacuum degree of 100 Pa to 1000 Pa for 0.5 to 1 h to obtain a second intermediate product; and / or, the molar ratio of the polycondensation catalyst to furandicarboxylic acid and / or furandicarboxylic acid ester is 1 to 2:1000; and / or, the molar ratio of the polycondensation catalyst to terephthalic acid and / or terephthalic acid ester is 1 to 2:1000; preferably, the polycondensation catalyst comprises an antimony-based catalyst, and particularly preferably comprises antimony trioxide; and / or, the molar ratio of the stabilizer to furandicarboxylic acid and / or furandicarboxylic acid ester is 0.5 to 1:1000; and / or, the molar ratio of the stabilizer to terephthalic acid and / or terephthalic acid ester is 0.5 to 1:1000; preferably, the stabilizer comprises triphenyl phosphate; Preferably, the second mixed reaction system further comprises an antioxidant; preferably, the molar ratio of the antioxidant to furandicarboxylic acid and / or furandicarboxylic acid ester is 0.5 to 1:1000; preferably, the molar ratio of the antioxidant to terephthalic acid and / or terephthalic acid ester is 0.5 to 1:1000; particularly preferably, the antioxidant comprises antioxidant-1010.

8. The preparation method according to claim 4, characterized in that: include: The second intermediate product is subjected to polycondensation reaction for 2 to 4 hours under the conditions of vacuum degree less than 20 Pa and reaction temperature of 260° C. to obtain the bio-based polyester with high glass transition temperature and high mechanical strength.

9. A bio-based polyester with high glass transition temperature and high mechanical strength prepared by the preparation method according to any one of claims 4 to 8.

10. Use of the high glass transition temperature and high mechanical strength bio-based polyester according to any one of claims 1 to 3 and 9 in the preparation of firefighting equipment, baby bottles, water cups, kitchen appliances, food packaging materials, hot-fill beverage bottles, device supports, optical base films, decorative materials or automotive accessories.

Images