CN112592467B

CN112592467B - High glass transition temperature low melting point polyester, polyester product, and preparation method and application thereof

Info

Publication number: CN112592467B
Application number: CN202110213165.7A
Authority: CN
Inventors: 王静刚; 张小琴; 樊林; 刘小青; 朱锦
Original assignee: Ningbo Institute of Material Technology and Engineering of CAS
Current assignee: Ningbo Institute of Material Technology and Engineering of CAS
Priority date: 2021-02-26
Filing date: 2021-02-26
Publication date: 2021-04-30
Anticipated expiration: 2041-02-26
Also published as: CN112592467A

Abstract

The invention discloses a polyester with high glass transition temperature and low melting point, a polyester product, a preparation method and application thereof. The preparation method comprises the following steps: the method comprises the steps of copolymerizing dihydroxyethoxy polycyclic aromatic hydrocarbon, first dibasic acid or an esterified product thereof, second dibasic acid or an esterified product thereof and dihydric alcohol to prepare the bio-based polyester with high glass transition temperature and low melting point, wherein the first dibasic acid is furan dicarboxylic acid. According to the invention, the dihydroxyethoxy polycyclic aromatic hydrocarbon with excellent rigidity and high terminal hydroxyl activity is copolymerized with the bio-based polyfuranate compound, and the heat resistance of the copolyester is further improved by introducing the rigid alicyclic dihydric alcohol, so that the finally obtained polyester has excellent heat resistance and processing fluidity, the glass transition temperature is 95-160 ℃, the melt viscosity is lower than 1000Pa & S within the temperature range of 240-260 ℃, and the copolyester can be widely used for stirring cups of devices such as wall-breaking food processors, portable fruit juice makers and noodle makers, juice extracting barrels of juice extractors, milk bottle cup bodies and other products.

Description

High glass transition temperature low melting point polyester, polyester product, and preparation method and application thereof

Technical Field

The invention relates to polyester, in particular to bio-based polyester with high glass transition temperature and low melting point, a polyester product, and a preparation method and application thereof, and belongs to the technical field of high polymer materials.

Background

Polyethylene terephthalate (PET) is synthesized from terephthalic acid and ethylene glycol, is widely applied to the fields of chemical fibers, packaging materials, engineering plastics and the like, and has an annual global yield of more than 7000 million tons, wherein 4000 million tons are produced in China. At present, the main raw material terephthalic acid (TPA) for producing PET completely depends on petrochemical p-xylene (PX), and the green manufacture of PX and derivatives thereof is an important proposition for maintaining the sustainable development of the polyester industry. The bio-based polymer material takes sustainable biomass and platform compounds thereof as raw materials, which can reduce the consumption of the polymer material on petrochemical resources and CO₂And (4) discharging. Therefore, the biomass resource is used for developing the bio-based polyester capable of replacing petroleum base, which is beneficial to saving petrochemical resources and protecting environment, and realizes the real green manufacture and recycling of the polyester.

Furan dicarboxylic acid prepared from furfural, furoic acid or 5-hydroxymethylfurfural of biomass has rigid furan rings and symmetrical carboxyl groups, and the oxygen barrier properties of polyethylene furandicarboxylate (PEF) prepared from ethylene glycol are respectively 6.8 times, 5.5 times and 3.6 times that of PET. The glass transition temperature of PEF is 87 ℃ which is 17 ℃ higher than 70 ℃ of PET, but the melting point of PEF is 217 ℃ which is 43 ℃ lower than 260 ℃ of PET, and the PEF has the excellent processing characteristics of low melting point, low-temperature melt viscosity and prevention of high-temperature oxidation and degradation of polyester. However, the glass transition temperature of PEF is 87 ℃, and when used for products such as stirring cups of broken food machines, stirring cups of portable fruit juice machines, juicing barrels of juice machines, stirring cups of noodle machines, milk bottle cup bodies and the like, the heat resistance is obviously insufficient, and further improvement of heat resistance and high fluidity at low temperature are required.

Disclosure of Invention

The invention mainly aims to provide a bio-based polyester with high glass transition temperature and low melting point and a preparation method thereof, so as to overcome the defect of insufficient heat resistance of the conventional bio-based PEF polyester with low melting point.

The invention also aims to provide application of the bio-based polyester with high glass transition temperature and low melting point.

The invention also aims to provide a processing method of the polyester product.

In order to achieve the purpose, the invention adopts the following technical scheme:

the embodiment of the invention provides a preparation method of bio-based polyester with high glass transition temperature and low melting point, which comprises the following steps:

reacting a first mixed reaction system containing a first dibasic acid or an esterified product thereof, dihydroxy ethoxy polycyclic aromatic hydrocarbon, dihydric alcohol and an esterification or ester exchange catalyst at 160-220 ℃ to obtain an intermediate product, wherein the first dibasic acid is furan dicarboxylic acid;

reacting a second mixed reaction system containing the intermediate product, a polycondensation catalyst and a stabilizer at 200-260 ℃ under a vacuum condition to prepare the bio-based polyester with high glass transition temperature and low melting point;

the dihydroxyethoxy polycyclic aromatic hydrocarbon has a structure shown in a formula (1):

。

the embodiment of the invention also provides the bio-based polyester with high glass transition temperature and low melting point prepared by the method, wherein the glass transition temperature of the bio-based polyester with high glass transition temperature and low melting point is 95-160 ℃, and the melt viscosity of the bio-based polyester with high glass transition temperature and low melting point is 100-1000 Pa.S within the temperature range of 240-260 ℃.

Embodiments of the present invention also provide a composition for synthesizing bio-based high glass transition temperature low melting point polyester, comprising:

the component (a) comprises a first dibasic acid or an esterified product thereof, wherein the first dibasic acid adopts furan dicarboxylic acid;

component (b) comprising a bishydroxyethoxy polycyclic aromatic hydrocarbon; and

component (d) comprising a diol comprising a cyclic diol and/or an aliphatic diol;

。

further, the composition further comprises: and the component (c) comprises a second dibasic acid or an ester thereof, wherein the second dibasic acid comprises an aromatic dibasic acid and/or an aliphatic dibasic acid.

The embodiment of the invention also provides application of the bio-based high-glass transition temperature low-melting point polyester in the field of preparing products such as stirring cups, juice extracting barrels of juice extractors, milk bottle cup bodies and the like of devices such as broken-wall cooking machines, portable juice extractors, noodle makers and the like.

Correspondingly, the embodiment of the invention also provides a preparation method of the polyester granules, which comprises the following steps: inputting the bio-based polyester with high glass transition temperature and low melting point into a co-rotating double-screw extruder for melt extrusion and granulation; wherein the working parameters of the co-rotating twin-screw extruder comprise: the temperature of the charging barrel is 240-260 ℃, and the temperature of the die head is 240-260 ℃.

Correspondingly, the embodiment of the invention also provides a processing method of the polyester film or the sheet material, which comprises the following steps:

inputting the bio-based high glass transition temperature low melting point polyester into a single screw extruder, carrying out melt extrusion at 240-260 ℃, and casting a molten fluid onto a rotating cooling drum to obtain a casting thick sheet with the thickness of 1500-5500 mu m;

and preheating the cast thick sheet to 80-140 ℃, longitudinally stretching for 3-4 times, then preheating to 80-140 ℃ again, and transversely stretching for 3-4.5 times to obtain the polyester film or the plate.

Compared with the prior art, the invention has the beneficial effects that:

1) according to the embodiment of the invention, the dihydroxyethoxy polycyclic aromatic hydrocarbon and the furan dicarboxylic acid or the esterified product thereof are adopted to synthesize the polyester, the dihydroxyethoxy polycyclic aromatic hydrocarbon can be efficiently subjected to esterification or ester exchange reaction with the furan dicarboxylic acid or the esterified product thereof by utilizing the characteristics of multiple benzene rings in the structure, great rigidity in the structure and high-activity terminal hydroxyethyl, the glass transition temperature of the copolyester can be obviously increased, meanwhile, the alicyclic diol has the characteristics of higher rigidity and a space non-planar structure than ethylene glycol, the heat resistance of the copolyester is further improved, meanwhile, because the furan dicarboxylic acid ester bond and the furan ring have a special included angle of 129 degrees, the melt viscosity of the copolyester is lower than 1000Pa & lt S at 240-260 ℃, compared with the processing degree of the PET polyester at more than 280 ℃, the processing temperature of the copolyester phase is low, the fluidity is good, the molding is easy, and the thermal oxidation stability is good, the energy is saved, the glass-like hollow container is very suitable for preparing the glass-like hollow container, and the heat resistance and the processability are excellent;

2) the 2, 5-furandicarboxylic acid adopted by the embodiment of the invention can be derived from renewable substances such as starch or cellulose, and the like, so that the sustainable development of the high polymer material can be powerfully promoted;

3) the preparation method provided by the embodiment of the invention can promote the high polymer material industry to get rid of high dependence on petroleum resources;

4) the bio-based polyester with high glass transition temperature and low melting point provided by the embodiment of the invention has excellent heat resistance and processing fluidity, and can be widely applied to hollow containers, plates or film products in the fields of stirring cups of broken-wall cooking machines, stirring cups of portable fruit juice machines, juice extracting barrels of juice extracting machines, stirring cups of noodle machines, milk bottle cup bodies and the like.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.

FIG. 1 is a drawing showing poly (ethylene glycol) copolyester of 2, 5-furandicarboxylic acid dihydroxy ethoxy polycyclic aromatic hydrocarbon prepared in example 1 of the present invention¹An H-NMR spectrum;

FIG. 2 is a DSC plot of poly (2, 5-furandicarboxylic acid) bishydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol copolyester prepared in example 1 of the present invention;

FIG. 3 is a TGA spectrum of poly (2, 5-furandicarboxylic acid) bishydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol copolyester prepared in example 1 of the present invention.

Detailed Description

As described above, in view of the defects of the prior art, the present inventors have made extensive studies and practice to provide a novel bio-based polyester with high glass transition temperature and low melting point, which is prepared by copolymerizing dihydroxyethoxy polycyclic aromatic hydrocarbon with 2, 5-furandicarboxylic acid or its ester, and other dibasic acids or its ester, and diol. The present invention will be more fully understood from the following detailed description, which should be read in conjunction with the accompanying drawings. Detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention, which can be embodied in various forms. Therefore, specific functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed embodiment.

The technical solution, its implementation and principles, etc. will be further explained as follows.

One aspect of the embodiments of the present invention provides a method for preparing a bio-based polyester with high glass transition temperature and low melting point, comprising:

。

in some embodiments, the first dibasic acid or the esterified product thereof is prepared from bio-based furoic acid or 5-hydroxymethylfurfural, and the first dibasic acid includes any one or a combination of two or more of 2, 5-furandicarboxylic acid, 2, 4-furandicarboxylic acid, 2, 3-furandicarboxylic acid, 3, 4-furandicarboxylic acid, and the like, but is not limited thereto.

Accordingly, the first dibasic acid or its ester includes any one or a combination of two or more of 2, 5-furandicarboxylic acid or its ester, 2, 4-furandicarboxylic acid or its ester, 2, 3-furandicarboxylic acid or its ester, 3, 4-furandicarboxylic acid or its ester, and the like, but is not limited thereto.

Further, the furandicarboxylic acid or an esterified product thereof may specifically include, but is not limited to, dimethyl 2, 5-furandicarboxylate, 2, 5-furandicarboxylic acid, dimethyl 2, 3-furandicarboxylate, dimethyl 3, 4-furandicarboxylate, dimethyl 2, 4-furandicarboxylate, and the like.

In some embodiments, the glycol includes, but is not limited to, cyclic glycols, aliphatic glycols, and the like.

In some embodiments of the foregoing embodiments of the present invention, the cyclic diol includes any one or a combination of two or more of cis-1, 4-cyclohexanedimethanol, trans-1, 4-cyclohexanedimethanol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, 1, 4-cyclohexanediol, 1, 3-cyclohexanediol, 1, 2-cyclohexanediol, dicyclopentanediol, 1-methyl-dicyclopentanediol, 1, 5-dimethyldicyclopentanediol, tricyclodecanedimethanol, tetrafluoroterephthalyl alcohol, tricyclodecanediol, bicycloheptanediol, tricyclopentanediol, tetracyclodiol, and the like, but is not limited thereto.

In some embodiments of the foregoing embodiments of the present invention, the aliphatic diol includes any one or a combination of two or more of ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methyl-1, 3-propanediol, and the like, but is not limited thereto.

That is, in another aspect, the diol has the following specific structure:

。

in some embodiments, the first mixed reaction system may further include a second dibasic acid or an ester thereof, and the second dibasic acid includes an aromatic dibasic acid, an aliphatic dibasic acid, and the like, but is not limited thereto.

Accordingly, the second dibasic acid or its ester includes, but is not limited to, an aromatic dibasic acid or its ester, an aliphatic dibasic acid or its ester, and the like.

In some embodiments of the foregoing embodiments of the present invention, the aromatic dibasic acid comprises any one or a combination of two or more of terephthalic acid, isophthalic acid, phthalic acid, biphenyldicarboxylic acid, naphthalenedicarboxylic acid, and the like, but is not limited thereto.

The esterified compound corresponding to the aromatic dibasic acid includes any one or a combination of two or more of dimethyl terephthalate, dimethyl isophthalate, dimethyl phthalate, dimethyl bibenzoate, dimethyl naphthalenedicarboxylate, and the like, but is not limited thereto.

In some embodiments of the foregoing embodiments of the present invention, the aliphatic dibasic acid comprises any one or a combination of two or more of cyclohexanedicarboxylic acid, succinic acid, adipic acid, and the like, but is not limited thereto.

Further, the esterified compound corresponding to the aliphatic dibasic acid includes any one or a combination of two or more of dimethyl cyclohexanedicarboxylate, dimethyl succinate, dimethyl adipate and the like, but is not limited thereto.

In some embodiments, the method of making comprises:

reacting the first mixed reaction system for 1.5-6.0h at 160-220 ℃ under a protective atmosphere to obtain an intermediate product; and

and (3) reacting the second mixed reaction system for 1.0-8 h under the conditions that the temperature is 200-260 ℃ and the vacuum degree is less than 100Pa, so as to obtain the bio-based polyester with high glass transition temperature and low melting point.

In some embodiments, the method of making the bio-based high glass transition temperature low melting point polyester specifically comprises: reacting first dibasic acid or an esterified product thereof, dihydroxy ethoxy polycyclic aromatic hydrocarbon, second dibasic acid or an esterified product thereof, dihydric alcohol, an esterification or ester exchange catalyst for 1.5 to 6.0 hours at the temperature of between 160 and 220 ℃ under a protective atmosphere to obtain a first reaction mixture; and reacting the first reaction mixture for 1.0-8 h under the action of a polycondensation catalyst and a stabilizer under the conditions that the temperature is 200-260 ℃ and the vacuum degree is less than 100Pa, so as to obtain the bio-based polyester with high glass transition temperature and low melting point.

In some embodiments, the molar ratio of the bis-hydroxyethoxy polycyclic aromatic hydrocarbon to the first dibasic acid or its ester and the combination of the second dibasic acid or its ester is 5 to 95:100, i.e., in other words, the bis-hydroxyethoxy polycyclic aromatic hydrocarbon is present in an amount of 5mol% to 95mol% based on the total molar amount of the first dibasic acid or its ester and the second dibasic acid or its ester.

In some embodiments, the molar ratio of the first dibasic acid or ester thereof to the combination of the first dibasic acid or ester thereof and the second dibasic acid or ester thereof is from 10 to 100: 100; that is, in another aspect, the first dibasic acid or its ester is present in an amount of 10mol% to 100mol% based on the total molar amount of the first dibasic acid or its ester and the second dibasic acid or its ester.

In some embodiments, the molar ratio of the glycol to the combination of the first dibasic acid or ester thereof and the second dibasic acid or ester thereof is from 120 to 300: 100; that is, in another aspect, the diol is present in an amount of 120mol% to 300mol% based on the total molar amount of the first dibasic acid or its ester and the second dibasic acid or its ester.

In some embodiments, the molar ratio of the esterification or transesterification catalyst to the combination of the first dibasic acid or ester thereof and the second dibasic acid or ester thereof is from 0.3 to 3.0: 1000.

In some embodiments, the molar ratio of the polycondensation catalyst to the combination of the first dibasic acid or ester thereof and the second dibasic acid or ester thereof is from 0.3 to 3.0: 1000.

In some embodiments, the molar ratio of the stabilizer to the combination of the first dibasic acid or ester thereof and the second dibasic acid or ester thereof is from 0.4 to 3.0: 1000.

That is, in another aspect, the content of the esterification or ester exchange catalyst is 0.3 mol% to 3.0 mol% per mill, the content of the polycondensation catalyst is 0.3 mol% to 3.0 mol% per mill, and the content of the stabilizer is 0.4 mol% to 3.0 mol% per mill, calculated by the total molar amount of the first dibasic acid or the ester thereof and the second dibasic acid or the ester thereof.

In some embodiments, the esterification or transesterification catalyst may include any one or a combination of two or more of a zinc-based catalyst, a manganese-based catalyst, a titanium-based catalyst, an antimony-based catalyst, and the like, but is not limited thereto.

Further, the zinc-based catalyst includes zinc acetate, but is not limited thereto.

Further, the manganese-based catalyst includes manganese acetate, but is not limited thereto.

Further, the titanium-based catalyst includes any one or a combination of two of tetrabutyl titanate, isopropyl titanate, and the like, but is not limited thereto.

Further, the antimony-based catalyst includes any one or a combination of two or more of antimony trioxide, ethylene glycol antimony, antimony acetate, polyethylene glycol antimony, and the like, but is not limited thereto.

In some embodiments, the polycondensation catalyst includes any one or a combination of two or more of a titanium-based catalyst, a tin-based catalyst, an antimony-based catalyst, a germanium-based catalyst, and the like, but is not limited thereto.

Further, the titanium-based catalyst includes any one or a combination of two or more of tetrabutyl titanate, isopropyl titanate, titanium dioxide, an inorganic supported titanium catalyst, and the like, but is not limited thereto.

Further, the tin-based catalyst includes any one or a combination of two or more of dibutyltin oxide, stannous isooctanoate, monobutyl triisooctanoate, dioctyltin oxide, and the like, but is not limited thereto.

Further, the germanium-based catalyst includes, but is not limited to, germanium dioxide, germanium oxide, and the like.

In some embodiments, the stabilizer is a phosphorus-based stabilizer, preferably including any one or a combination of two or more of phosphorous acid, hypophosphorous acid, pyrophosphoric acid, ammonium phosphate, trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, triphenyl phosphite, diphenyl phosphite, ammonium dihydrogen phosphate, and the like, but not limited thereto.

Another aspect of an embodiment of the present invention provides a bio-based high glass transition temperature low melting polyester that can be formed by any of the methods of the preceding embodiments.

Further, the bio-based polyester with high glass transition temperature and low melting point has excellent heat resistance and processing fluidity, the glass transition temperature is 95-160 ℃, the melt viscosity is less than 1000Pa & lt.S, and preferably 100-1000 Pa & lt.S, within the temperature range of 240-260 ℃.

Yet another aspect of an embodiment of the present invention provides a composition for synthesizing a bio-based high glass transition temperature low melting point polyester, comprising:

。

in some embodiments, the composition further comprises: and the component (c) comprises a second dibasic acid or an ester thereof, wherein the second dibasic acid comprises an aromatic dibasic acid and/or an aliphatic dibasic acid.

In some embodiments, the molar ratio of the component (b) to the combination of the component (a) and the component (c) is from 5 to 95: 100.

In some embodiments, the molar ratio of component (a) to the combination of component (a) and component (c) is 10 to 100: 100.

In some embodiments, the molar ratio of the component (d) to the combination of the component (a) and the component (c) is from 120 to 300: 100.

That is, in another aspect, the components used to synthesize the bio-based high glass transition temperature low melting point polyester comprise:

component (a): a first dibasic acid or an esterified product thereof, wherein the first dibasic acid is furan dicarboxylic acid;

a component (b): bis-hydroxyethoxy polycyclic aromatic hydrocarbons;

optional component (c): the second dibasic acid or the ester thereof comprises aromatic dibasic acid, aliphatic dibasic acid, ester corresponding to the aromatic dibasic acid, ester corresponding to the aliphatic dibasic acid or the combination of the aromatic dibasic acid and the aliphatic dibasic acid;

a component (d): glycols, including cyclic glycols, aliphatic glycols, or combinations thereof,

wherein the total molar amount of components (a) + (c);

the content of the component (b) is 5-95 mol%;

the content of the component (a) is 10-100 mol%;

the content of the component (d) is 120-300 mol%.

The selection of the type and the structure of the first dibasic acid or the ester thereof as the component (a), the dihydroxy ethoxy polycyclic aromatic hydrocarbon as the component (b), the second dibasic acid or the ester thereof as the component (c) and the dihydric alcohol as the component (d) are as described above, and are not repeated herein.

The invention also provides application of the bio-based high-glass-transition-temperature low-melting-point polyester in glass hollow containers, plates or film products such as stirring cups of broken-wall cooking machines, stirring cups of carry-on juice extractors, juice extraction barrels of juice extractors, stirring cups of noodle makers and milk bottle cup bodies.

Accordingly, another aspect of an embodiment of the present invention also provides a method for preparing a polyester article, such as polyester granules, comprising: inputting the bio-based polyester with high glass transition temperature and low melting point into a co-rotating double-screw extruder for melt extrusion and granulation; wherein the working parameters of the co-rotating twin-screw extruder comprise: the temperature of the charging barrel is 240-260 ℃, and the temperature of the die head is 240-260 ℃.

Correspondingly, the embodiment of the invention also provides a processing method of the polyester product, which comprises the following steps: the bio-based polyester with high glass transition temperature and low melting point is made into the required polyester product by at least one of extrusion and injection.

Accordingly, another aspect of the embodiments of the present invention also provides a method for processing a polyester film or sheet, including:

For another example, an embodiment of the present invention further provides a multilayer composite film, which includes a first structural layer and a second structural layer sequentially stacked, wherein the first structural layer and the second structural layer are bonded together, and the first structural layer is a film formed of the bio-based high-glass transition temperature low-melting point polyester. The second structural layer can be formed by inorganic materials, organic materials or composite materials thereof. The multilayer composite film can be applied to optical materials such as a baby bottle body, a water cup, kitchen electrical products, food packaging, a hot-filling beverage bottle, an optical base film and the like, a protective film on the surface of decorative materials and the like, and is not limited thereto.

By the technical scheme, the synthesized dihydroxy ethoxy polycyclic aromatic hydrocarbon has excellent rigidity and high activity of terminal hydroxyl, the glass transition temperature of the copolyester can be obviously improved after copolymerization with bio-based polyethylene furan dicarboxylate (PEF), and the heat resistance of the copolyester is further improved by introducing rigid alicyclic dihydric alcohol on the basis, and meanwhile, because the furan dicarboxylate bond and the furan ring have a special 129-degree included angle, the melt viscosity is lower than 1000Pa & lt & gtS at the temperature of 240 plus 260 ℃, compared with the processing degree of PET polyester above 280 ℃, the processing temperature of the copolyester phase is low, the flowability is good, the molding is easy, the thermal oxidation stability is good, energy is saved, the dihydroxy ethoxy polycyclic aromatic hydrocarbon is very suitable for preparing glass-like hollow containers, and the heat resistance and the processing performance are excellent.

The technical solutions of the present invention will be described in further detail below with reference to several preferred embodiments and accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers.

In the following examples, NMR spectroscopy¹H-NMR used was a Bruker 400 AVANCE III Spectrometeron-Instrument measurement, 400MHz, CF₃COOD。

In the following examples, thermal analysis was carried out using differential scanning calorimetry (Mettler Toledo DSC) at a temperature rise rate of 10 deg.C/min at N₂The atmosphere is carried out, and the temperature range is-50-300 ℃. Thermogravimetric analysis (TGA) was performed on a Perkin-Elmer Diamond TG/DTA with a heating rate of 20 ℃/min and a temperature range of 50-800 ℃.

The melt index was measured using a YK-3651A melt index apparatus, with a weight of 1200g according to ASTM D1238, and the data was calculated using the average of 5 samples.

Example 1

Adding dimethyl 2, 5-furandicarboxylate, dihydroxyethoxy polycyclic aromatic hydrocarbon and ethylene glycol into a reactor according to the molar ratio of 1:0.20:2.1, then adding anhydrous zinc acetate with the molar weight of 0.8 thousandth of the dimethyl 2, 5-furandicarboxylate, gradually heating to 180 ℃ under the protection of nitrogen, reacting for 4.0h, then adding antimony trioxide with the molar weight of 1.0 thousandth of the dimethyl 2, 5-furandicarboxylate and 1.0 thousandth of trimethyl phosphate, gradually heating to 240 ℃, reducing the vacuum degree to 20Pa, reacting for 3.5h to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol copolyester of poly 2, 5-furandicarboxylate with the structure as formula (2) and the intrinsic viscosity of 0.75 dL/g, and performing nuclear magnetic nuclear magnetism on the ethylene glycol¹H-NMR is shown in FIG. 1, DSC curve is shown in FIG. 2, glass transition temperature is 109 ℃, and weight loss under heat T_5%At 380 ℃ a TGA profile is shown in FIG. 3. And it had excellent low temperature melt fluidity with a weight of 1200g at 240 ℃ and a melt index of 43g, and a melt viscosity of 300 Pa.s at 240 ℃.

Formula (2), wherein m, n are integers from 1 to 10, and z is an integer from 10 to 100.

Example 2

Adding dimethyl 2, 5-furandicarboxylate, dihydroxyethoxy polycyclic aromatic hydrocarbon and ethylene glycol into a reactor according to a molar ratio of 1:0.10:2.1, then adding anhydrous zinc acetate with the molar weight of 0.7 thousandth of the dimethyl 2, 5-furandicarboxylate, gradually heating to 185 ℃ under the protection of nitrogen, reacting for 3.5 hours, then adding antimony trioxide with the molar weight of 0.7 thousandth of the dimethyl 2, 5-furandicarboxylate and phosphorous acid with the molar weight of 0.8 thousandth of the dimethyl 2, 5-furandicarboxylate, gradually heating to 235 ℃, reducing the vacuum degree to 10Pa, reacting for 3.5 hours to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol copolyester of 2, 5-furandicarboxylate, wherein the intrinsic viscosity of the dihydroxyethoxy polycyclic aromatic hydrocarbon is 0.76 dL/g, the glass transition temperature of 99 ℃, 240 ℃, 1200g of weight, the melt index of 51g, and the melt viscosity of 220Pa S at 240 ℃.

Example 3

Adding dimethyl 2, 5-furandicarboxylate, dihydroxyethoxy polycyclic aromatic hydrocarbon and ethylene glycol into a reactor according to a molar ratio of 1:0.30:2.1, then adding anhydrous zinc acetate with the molar weight of the dimethyl 2, 5-furandicarboxylate of 0.8 per mill, gradually heating to 180 ℃ under the protection of nitrogen, reacting for 3.5 hours, then adding antimony acetate with the molar weight of the dimethyl 2, 5-furandicarboxylate of 1.0 per mill and 1.5 per mill trimethyl phosphate, gradually heating to 246 ℃, reducing the vacuum degree to 30Pa, and reacting for 4.5 hours to obtain poly-2, 5-furandicarboxylate dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol copolyester, wherein the intrinsic viscosity is 0.73 dL/g, the glass transition temperature is 117 ℃, and the melt viscosity is 350Pa S at 240 ℃.

Example 4

Adding 2, 4-furandicarboxylic acid dimethyl ester, dihydroxy ethoxy polycyclic aromatic hydrocarbon and ethylene glycol into a reactor according to a molar ratio of 1:0.05:2.0, then adding tetrabutyl titanate with the molar weight of the 2, 4-furandicarboxylic acid dimethyl ester being 0.6 per mill, gradually heating to 160 ℃ under the protection of nitrogen, reacting for 6.0 hours, then adding diphenyl phosphate with the molar weight of the 2, 4-furandicarboxylic acid dimethyl ester being 0.6 per mill, gradually heating to 241 ℃, reducing the vacuum degree to 20Pa, and reacting for 4.5 hours to obtain poly-2, 4-furandicarboxylic acid dihydroxy ethoxy polycyclic aromatic hydrocarbon ethylene glycol copolyester, wherein the structure is shown in formula (3), the intrinsic viscosity is 0.68dL/g, the glass transition temperature is 95 ℃, and the melt viscosity is 150Pa & lt & gt at 240 ℃.

Formula (3), wherein m, n are integers from 1 to 10, and z is an integer from 10 to 100.

Example 5

Adding 2, 3-furandicarboxylic acid dimethyl ester, dihydroxy ethoxy polycyclic aromatic hydrocarbon and ethylene glycol into a reactor according to a molar ratio of 1:0.4:1.8, then adding anhydrous zinc acetate with the molar weight of the 2, 3-furandicarboxylic acid dimethyl ester being 0.8 per mill, under the protection of nitrogen, gradually heating to 190 ℃, reacting for 4.6 hours, then adding polyethylene glycol antimony with the molar weight of the 2, 3-furandicarboxylic acid dimethyl ester being 1.2 per mill, and triphenyl phosphate with the molar weight of 0.7 per mill, gradually heating to 245 ℃, reducing the vacuum degree to 35Pa, reacting for 4.0 hours, and obtaining the dihydroxy ethoxy polycyclic aromatic hydrocarbon ethylene glycol copolyester of 2, 3-furandicarboxylic acid, wherein the structure is shown in formula (4), the intrinsic viscosity is 0.78 dL/g, the glass transition temperature is 124 ℃, and the melt viscosity is 320Pa S at 245 ℃.

Formula (4), wherein m, n are integers from 1 to 10, and z is an integer from 10 to 100.

Example 6

Adding 3, 4-furandicarboxylic acid dimethyl ester, dihydroxy ethoxy polycyclic aromatic hydrocarbon and ethylene glycol into a reactor according to a molar ratio of 1:0.5:2.1, then adding anhydrous manganese acetate with the molar weight of 1.5 thousandths of 3, 4-furandicarboxylic acid dimethyl ester, gradually heating to 185 ℃ under the protection of nitrogen, reacting for 3.0h, then adding antimony trioxide with the molar weight of 1.5 thousandths of 3, 4-furandicarboxylic acid dimethyl ester, dibutyltin oxide with the molar weight of 1.5 thousandths of 1.9 thousandths of diphenyl phosphite, gradually heating to 245 ℃, reducing the vacuum degree to 15Pa, and reacting for 3.0h to obtain the poly-3, 4-furandicarboxylic acid dihydroxy ethoxy polycyclic aromatic hydrocarbon ethylene glycol copolyester with the structure formula (5), the intrinsic viscosity of 0.71 dL/g, the glass transition temperature of 131 ℃, and the melt viscosity of 380Pa S at 245 ℃.

Formula (5), wherein m, n are integers from 1 to 10, and z is an integer from 10 to 100.

Example 7

Adding dimethyl 2, 5-furandicarboxylate, dihydroxyethoxy polycyclic aromatic hydrocarbon and ethylene glycol into a reactor according to a molar ratio of 1:0.6:2.1, then adding anhydrous zinc acetate with the molar weight of 1.2 thousandths of the dimethyl 2, 5-furandicarboxylate, gradually heating to 182 ℃ under the protection of nitrogen, reacting for 4.0h, then adding antimony trioxide with the molar weight of 1.0 thousandths of the dimethyl 2, 5-furandicarboxylate and 1.0 thousandths of triphenyl phosphate, gradually heating to 246 ℃, reducing the vacuum degree to 20Pa, and reacting for 3.2h to obtain the poly-2, 5-furandicarboxylate dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol copolyester, wherein the intrinsic viscosity is 0.71 dL/g, the glass transition temperature is 138 ℃, and the melt viscosity is 400Pa S at 245 ℃.

Example 8

Adding dimethyl 2, 5-furandicarboxylate, dihydroxyethoxy polycyclic aromatic hydrocarbon and ethylene glycol into a reactor according to a molar ratio of 1:0.7:2.1, then adding anhydrous zinc acetate with the molar weight of the dimethyl 2, 5-furandicarboxylate of 0.8 per mill, gradually heating to 182 ℃ under the protection of nitrogen, reacting for 3.6 hours, then adding stannous isooctoate with the molar weight of the dimethyl 2, 5-furandicarboxylate of 1.5 per mill and dimethyl phosphate of 2.5 per mill, gradually heating to 246 ℃, reducing the vacuum degree to 12Pa, reacting for 3.5 hours, and obtaining poly (ethylene-2, 5-furandicarboxylate) dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol copolyester with the intrinsic viscosity of 0.68dL/g, the glass transition temperature of 146 ℃, and the melt viscosity of 450Pa S at 245 ℃.

Example 9

Adding 2, 5-furandicarboxylic acid dimethyl ester, dihydroxyethoxy polycyclic aromatic hydrocarbon and ethylene glycol into a reactor according to a molar ratio of 1:0.8:2.1, then adding anhydrous zinc acetate with the molar weight of 1.3 thousandths of 2, 5-furandicarboxylic acid dimethyl ester, gradually heating to 180 ℃ under the protection of nitrogen, reacting for 4.0h, then adding antimony trioxide with the molar weight of 0.8 thousandths of 2, 5-furandicarboxylic acid dimethyl ester and 1.0 thousandths of diphenyl phosphate, gradually heating to 248 ℃, reducing the vacuum degree to 10Pa, and reacting for 3.8h to obtain poly-2, 5-furandicarboxylic acid dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol copolyester, wherein the intrinsic viscosity is 0.66 dL/g, the glass transition temperature is 155 ℃, and the melt viscosity is 510Pa S at 245 ℃.

Example 10

Adding 2, 5-furandicarboxylic acid dimethyl ester, dihydroxyethoxy polycyclic aromatic hydrocarbon and glycol into a reactor according to the molar ratio of 1:0.95:2.1, then adding anhydrous zinc acetate with the molar weight of 1.2 thousandths of 2, 5-furandicarboxylic acid dimethyl ester, gradually heating to 200 ℃ under the protection of nitrogen, reacting for 4.5 hours, then adding antimony trioxide with the molar weight of 2.0 thousandths of 2, 5-furandicarboxylic acid dimethyl ester and 2.0 thousandths of diphenyl phosphate, gradually heating to 260 ℃, reducing the vacuum degree to 7.5Pa, and reacting for 4.5 hours to obtain poly-2, 5-furandicarboxylic acid dihydroxyethoxy polycyclic aromatic hydrocarbon glycol copolyester, wherein the intrinsic viscosity is 0.61 dL/g, the glass transition temperature is 158 ℃, and the melt viscosity is 345Pa S at 260 ℃.

Example 11

Adding dimethyl 2, 5-furandicarboxylate, dihydroxyethoxy polycyclic aromatic hydrocarbon, ethylene glycol, cis-1, 4-cyclohexanedimethanol and trans-1, 4-cyclohexanedimethanol into a reactor according to the molar ratio of 1:0.30:1.9:0.1:0.1, then adding anhydrous zinc acetate with the molar amount of 1.2 thousandth of the dimethyl 2, 5-furandicarboxylate, gradually heating to 180 ℃ under the protection of nitrogen, reacting for 3.2 hours, then adding ethylene glycol antimony with the molar amount of 1.2 thousandth of the dimethyl 2, 5-furandicarboxylate and 1.5 thousandth of trimethyl phosphate, gradually heating to 245 ℃, reducing the vacuum degree to 25Pa, reacting for 4.0 hours to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 4-cyclohexanedimethanol poly (2, 5-furandicarboxylate), the structure of which is shown in formula (6) is 0.76 dL/g, glass transition temperature 115 ℃ and melt viscosity 300 Pa.S at 245 ℃.

Formula (6), wherein x, y, m, n are integers from 1 to 10, and z is an integer from 10 to 100.

Example 12

Adding 2, 5-furandicarboxylic acid dimethyl ester, dihydroxy ethoxy polycyclic aromatic hydrocarbon, ethylene glycol and cis-1, 4-cyclohexanedimethanol into a reactor according to the molar ratio of 1:0.30:1.9:0.2, then adding anhydrous zinc acetate with the molar weight of the 2, 5-furandicarboxylic acid dimethyl ester of 0.7 thousandth, gradually heating to 180 ℃ under the protection of nitrogen, reacting for 4.5 hours, then adding ethylene glycol antimony with the molar weight of the 2, 5-furandicarboxylic acid dimethyl ester of 1.0 thousandth, trimethyl phosphate with the molar weight of 1.0 thousandth, gradually heating to 245 ℃, reducing the vacuum degree to 25Pa, reacting for 4.0 hours to obtain 2, 5-furandicarboxylic acid dihydroxy ethoxy polycyclic aromatic hydrocarbon ethylene glycol cis-1, 4-cyclohexanedimethanol copolyester with the structure of formula (7), the intrinsic viscosity of 0.75/dL and the glass transition temperature of 113 ℃, melt viscosity was 280 Pa.s at 245 ℃.

Formula (7), wherein x, m, n are integers from 1 to 10, and z is an integer from 10 to 100.

Example 13

Adding dimethyl 2, 5-furandicarboxylate, dihydroxy ethoxy polycyclic aromatic hydrocarbon, ethylene glycol and trans-1, 4-cyclohexanedimethanol into a reactor according to the molar ratio of 1:0.30:1.9:0.2, then adding anhydrous zinc acetate with the molar weight of 0.9 per mill of dimethyl 2, 5-furandicarboxylate, gradually heating to 180 ℃ under the protection of nitrogen, reacting for 3.5h, then adding ethylene glycol antimony with the molar weight of 1.0 per mill of dimethyl 2, 5-furandicarboxylate and 1.0 per mill of trimethyl phosphate, gradually heating to 245 ℃, reducing the vacuum degree to 25Pa, reacting for 4.0h to obtain poly 2, 5-furandicarboxylate dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol trans-1, 4-cyclohexanedimethanol copolyester with the structure shown in formula (8), its intrinsic viscosity was 0.74dL/g, glass transition temperature 119 ℃ and melt viscosity 400 Pa.S at 245 ℃.

Formula (8), wherein x, m, n are integers from 1 to 10, and z is an integer from 10 to 100.

Example 14

Adding dimethyl 2, 5-furandicarboxylate, dihydroxy ethoxy polycyclic aromatic hydrocarbon, hexanediol and 1, 2-cyclohexanedimethanol into a reactor according to a molar ratio of 1:0.30:1.9:0.6, then adding anhydrous zinc acetate with the molar weight of 0.6 per mill of dimethyl 2, 5-furandicarboxylate, gradually heating to 180 ℃ under the protection of nitrogen, reacting for 3.5h, then antimony trioxide with the molar weight of 2.5 per thousand of dimethyl 2, 5-furandicarboxylate and trimethyl phosphate with the molar weight of 3.0 per thousand are added, the temperature is gradually increased to 240 ℃, the vacuum degree is reduced to 60Pa, the reaction is carried out for 4.5 hours, and poly 2, 5-furandicarboxylate dihydroxy ethoxy polycyclic aromatic hydrocarbon hexanediol 1, 2-cyclohexanedimethanol copolyester with the structure as formula (9) is obtained, its intrinsic viscosity was 0.78 dL/g, glass transition temperature 109 ℃ and melt viscosity 255 Pa.S at 245 ℃.

Formula (9), wherein x, m, n are integers from 1 to 10, and z is an integer from 10 to 100.

Example 15

Adding dimethyl 2, 5-furandicarboxylate, dihydroxy ethoxy polycyclic aromatic hydrocarbon, butanediol and 1, 3-cyclohexanedimethanol into a reactor according to a molar ratio of 1:0.30:1.9:0.5, then adding anhydrous zinc acetate with the molar weight of 1.0 per mill of dimethyl 2, 5-furandicarboxylate, gradually heating to 185 ℃ under the protection of nitrogen, reacting for 4.0h, then antimony trioxide with the molar weight of 1.0 per thousand of dimethyl 2, 5-furandicarboxylate and 1.5 per thousand of trimethyl phosphate are added, the temperature is gradually increased to 240 ℃, the vacuum degree is reduced to 30Pa, the reaction is carried out for 4.5 hours, and poly 2, 5-furandicarboxylate dihydroxy ethoxy polycyclic aromatic hydrocarbon butanediol 1, 3-cyclohexanedimethanol copolyester with the structure shown in formula (10) is obtained, its intrinsic viscosity was 0.82 dL/g, glass transition temperature 112 ℃, melt viscosity 420 Pa. S at 245 ℃.

Formula (10), wherein x, m, n are integers from 1 to 10, and z is an integer from 10 to 100.

Example 16

Adding dimethyl 2, 5-furandicarboxylate, dihydroxyethoxy polycyclic aromatic hydrocarbon, ethylene glycol and 1, 4-cyclohexanediol into a reactor according to the molar ratio of 1:0.3:2.1:0.2, then adding dibutyltin oxide with the molar weight of 2.4 per mill of dimethyl 2, 5-furandicarboxylate, gradually heating to 180 ℃ under the protection of nitrogen, reacting for 6.0h, then antimony trioxide with the molar weight of 2.0 per thousand of dimethyl 2, 5-furandicarboxylate and 1.5 per thousand of trimethyl phosphate are added, the temperature is gradually raised to 250 ℃, the vacuum degree is reduced to 10Pa, the reaction is carried out for 4.5 hours, and poly 2, 5-furandicarboxylate dihydroxy ethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 4-cyclohexanediol copolyester with the structure as formula (11) is obtained, its intrinsic viscosity was 0.62 dL/g, glass transition temperature 125 ℃ and melt viscosity 410 Pa.S at 250 ℃.

Formula (11), wherein x, m, n are integers from 1 to 10, and z is an integer from 10 to 100.

Example 17

Adding dimethyl 2, 4-furandicarboxylate, dihydroxy ethoxy polycyclic aromatic hydrocarbon, ethylene glycol and 1, 4-cyclohexanediol into a reactor according to the molar ratio of 1:0.30:2.1:0.1, then adding dibutyltin oxide with the molar weight of 2.5 per mill of dimethyl 2, 4-furandicarboxylate, gradually heating to 220 ℃ under the protection of nitrogen, reacting for 1.5h, then antimony trioxide with the molar weight of 1.5 per thousand of dimethyl 2, 4-furandicarboxylate and 1.5 per thousand of trimethyl phosphate are added, the temperature is gradually increased to 240 ℃, the vacuum degree is reduced to 15Pa, the reaction is carried out for 5.0h, and poly 2, 4-furandicarboxylate dihydroxy ethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 4-cyclohexanediol copolyester with the structure as formula (12) is obtained, its intrinsic viscosity was 0.60 dL/g, glass transition temperature 120 ℃ and melt viscosity 305 Pa.S at 250 ℃.

Formula (12), wherein x, m, n are integers from 1 to 10, and z is an integer from 10 to 100.

Example 18

Adding dimethyl 2, 5-furandicarboxylate, dihydroxy ethoxy polycyclic aromatic hydrocarbon, ethylene glycol and 1, 3-cyclohexanediol into a reactor according to a molar ratio of 1:0.30:2.1:0.1, then adding dibutyltin oxide with a molar amount of 1.5 thousandth of 2, 5-furandicarboxylate, gradually heating to 175 ℃ under the protection of nitrogen, reacting for 6.0h, then adding antimony trioxide with a molar amount of 0.8 thousandth of 2, 5-furandicarboxylate and 1.2 thousandth of trimethyl phosphate, gradually heating to 245 ℃, reducing the vacuum degree to 10Pa, and reacting for 3.5h to obtain the poly-2, 5-furandicarboxylate dihydroxy ethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 3-cyclohexanediol copolyester with a structure formula (13), an intrinsic viscosity of 0.68dL/g, a glass transition temperature of 120 ℃, and a melt viscosity of 420Pa S at 245 ℃.

Formula (13), wherein x, m, n are integers from 1 to 10, and z is an integer from 10 to 100.

Example 19

Adding dimethyl 2, 5-furandicarboxylate, dihydroxy ethoxy polycyclic aromatic hydrocarbon, ethylene glycol and 1, 2-cyclohexanediol into a reactor according to a molar ratio of 1:0.30:2.1:0.1, then adding dibutyltin oxide with a molar amount of 1.6 per thousand of 2, 5-furandicarboxylate, gradually heating to 185 ℃ under the protection of nitrogen, reacting for 5.0h, then adding antimony trioxide with a molar amount of 0.8 per thousand of 2, 5-furandicarboxylate and 1.2 per thousand of trimethyl phosphate, gradually heating to 245 ℃, reducing the vacuum degree to 15Pa, and reacting for 3.6h to obtain the poly-2, 5-furandicarboxylate dihydroxy ethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 2-cyclohexanediol copolyester with a structure formula (14), an intrinsic viscosity of 0.68dL/g, a glass transition temperature of 118 ℃, and a melt viscosity of 480Pa S at 245 ℃.

Formula (14), wherein x, m, n are integers from 1 to 10, and z is an integer from 10 to 100.

Example 20

Adding 2, 5-furandicarboxylic acid, dihydroxyethoxy polycyclic aromatic hydrocarbon, ethylene glycol and dicyclopentadiene into a reactor according to a molar ratio of 1:0.30:2.1:0.1, then adding dibutyltin oxide with a molar amount of 1.6 per mill of 2, 5-furandicarboxylic acid, gradually heating to 210 ℃ under the protection of nitrogen, reacting for 6.0 hours, then adding antimony trioxide with a molar amount of 1.8 per mill of 2, 5-furandicarboxylic acid and 1.8 per mill of trimethyl phosphate, gradually heating to 246 ℃, reducing the vacuum degree to 10Pa, and reacting for 3.5 hours to obtain the poly-2, 5-furandicarboxylic acid dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol dicyclopentadiene copolyester with a structure shown in formula (15), an intrinsic viscosity of 0.64 dL/g, a glass transition temperature of 124 ℃, and a melt viscosity of 520Pa S at 245 ℃.

Formula (15), wherein x, m, n are integers from 1 to 10, and z is an integer from 10 to 100.

Example 21

Adding 2, 5-furandicarboxylic acid, dihydroxyethoxy polycyclic aromatic hydrocarbon, ethylene glycol and 1-methyl dicyclopentanediol into a reactor according to a molar ratio of 1:0.30:2.1:0.1, then adding dibutyltin oxide with the molar amount of 1.8 thousandth of 2, 5-furandicarboxylic acid, gradually heating to 215 ℃ under the protection of nitrogen, reacting for 5.5 hours, then adding antimony trioxide with the molar amount of 1.5 thousandth of 2, 5-furandicarboxylic acid and trimethyl phosphate with the molar amount of 1.6 thousandth of 1.5 thousandth of 2, 5-furandicarboxylic acid, gradually heating to 245 ℃, reducing the vacuum degree to 20Pa, and reacting for 4.5 hours to obtain the poly-2, 5-furandicarboxylic acid dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol 1-methyl dicyclopentanediol copolyester with the structure of formula (16), the intrinsic viscosity of 0.73 dL/g, the glass transition temperature of 125 ℃, and the melt viscosity of 480Pa S at 245 ℃.

Formula (16), wherein x, m, n are integers from 1 to 10, and z is an integer from 10 to 100.

Example 22

Adding 2, 5-furandicarboxylic acid dimethyl ester, dihydroxy-ethoxy polycyclic aromatic hydrocarbon, ethylene glycol and 1-methyl dicyclopentanediol into a reactor according to a molar ratio of 1:0.30:2.1:0.2, then adding anhydrous zinc acetate with the molar weight of the dimethyl 2, 5-furandicarboxylate of 0.8 thousandth, gradually heating to 185 ℃ under the protection of nitrogen, reacting for 3.5 hours, then adding antimony trioxide with the molar weight of the dimethyl 2, 5-furandicarboxylate of 0.8 thousandth and 1.6 thousandth of trimethyl phosphate, gradually heating to 245 ℃, reducing the vacuum degree to 20Pa, and reacting for 3.5 hours to obtain the poly-2, 5-furandicarboxylic acid dihydroxy-ethoxy polycyclic aromatic hydrocarbon ethylene glycol 1-methyl dicyclopentanediol copolyester, wherein the intrinsic viscosity is 0.72/g, the glass transition temperature is 128 ℃, and the melt viscosity is 440Pa S at 245 ℃.

Example 23

Adding dimethyl 2, 5-furandicarboxylate, dihydroxy ethoxy polycyclic aromatic hydrocarbon, ethylene glycol and 1, 5-dimethyl dicyclopentanediol into a reactor according to the molar ratio of 1:0.30:2.1:0.1, then adding anhydrous zinc acetate with the molar weight of 1.4 thousandth of the dimethyl 2, 5-furandicarboxylate, gradually heating to 185 ℃ under the protection of nitrogen, reacting for 4.5h, then adding antimony trioxide with the molar weight of 0.8 thousandth of the dimethyl 2, 5-furandicarboxylate and 1.2 thousandth of trimethyl phosphate, gradually heating to 245 ℃, reducing the vacuum degree to 20Pa, reacting for 3.5h,

the poly (2, 5-furandicarboxylic acid) bishydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 5-dimethyldicyclopentanediol copolyester is obtained, and has the structure shown in the formula (17), wherein the intrinsic viscosity is 0.63 dL/g, the glass transition temperature is 126 ℃, and the melt viscosity is 380Pa & lt & gt at 245 ℃.

Formula (17), wherein x, m, n are integers from 1 to 10, and z is an integer from 10 to 100.

Example 24

Adding dimethyl 2, 5-furandicarboxylate, dihydroxy ethoxy polycyclic aromatic hydrocarbon, ethylene glycol and tricyclodecane dimethanol into a reactor according to a molar ratio of 1:0.30:2.1:0.2, then adding stannous octoate with the molar amount of dimethyl 2, 5-furandicarboxylate of 1.0 thousandth, gradually heating to 185 ℃ under the protection of nitrogen, reacting for 4.0h, then adding polyethylene glycol antimony with the molar amount of dimethyl 2, 5-furandicarboxylate of 1.0 thousandth and trimethyl phosphate with the molar amount of 1.5 thousandth, gradually heating to 245 ℃, reducing the vacuum degree to 20Pa, and reacting for 3.5h to obtain poly (dihydroxy ethoxy polycyclic aromatic hydrocarbon ethylene glycol tricyclodecane dimethanol 2, 5-furandicarboxylate copolyester with the structure of formula (18), the intrinsic viscosity of 0.62 dL/g, the glass transition temperature of 124 ℃, and the melt viscosity of 610Pa S at 245 ℃.

Formula (18), wherein x, m, n are integers from 1 to 10, and z is an integer from 10 to 100.

Example 25

Dimethyl 2, 5-furandicarboxylate, dihydroxy ethoxy polycyclic aromatic hydrocarbon, ethylene glycol and tricyclodecane glycol are mixed according to a molar ratio of 1:0.3: 1.8: 0.3, adding the mixture into a reactor, adding anhydrous manganese acetate with the molar weight of 1.5 per mill of dimethyl 2, 5-furandicarboxylate, gradually heating to 190 ℃ under the protection of nitrogen, reacting for 2.8 hours, then adding polyethylene glycol antimony with the molar weight of 0.8 per mill of dimethyl 2, 5-furandicarboxylate and 1.2 per mill of triphenyl phosphate, gradually heating to 252 ℃, reducing the vacuum degree to 15Pa, and reacting for 4.0 hours to obtain the poly (dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol tricyclodecanediol) copolyester of 2, 5-furandicarboxylate, wherein the structure is shown as formula (19), the intrinsic viscosity is 0.62 dL/g, the glass transition temperature is 129 ℃, and the melt viscosity is 580Pa S at 250 ℃.

Formula (19), wherein x, m, n are integers from 1 to 10, and z is an integer from 10 to 100.

Example 26

Adding dimethyl 2, 5-furandicarboxylate, dihydroxy ethoxy polycyclic aromatic hydrocarbon, ethylene glycol and bicycloheptane diol into a reactor according to the molar ratio of 1:0.5:2.1:0.3, then adding anhydrous manganese acetate with the molar weight of 0.9 per mill of dimethyl 2, 5-furandicarboxylate, gradually heating to 180 ℃ under the protection of nitrogen, reacting for 4.0h, then adding antimony trioxide with the molar weight of 1.2 per thousand of dimethyl 2, 5-furandicarboxylate, dibutyltin oxide with the molar weight of 1.1 per thousand of diphenyl phosphite and 1.0 per thousand of diphenyl phosphite, gradually heating to 245 ℃, reducing the vacuum degree to 15Pa, reacting for 6.0h to obtain poly 2, 5-furandicarboxylate bishydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol bicycloheptane diol copolyester with the structure shown as a formula (20), its intrinsic viscosity was 0.76 dL/g, glass transition temperature 141 ℃ and melt viscosity 700 Pa.S at 245 ℃.

Formula (20), wherein x, m, n are integers from 1 to 10, and z is an integer from 10 to 100.

Example 27

Adding 2, 5-furandicarboxylic acid dimethyl ester, dihydroxy ethoxy polycyclic aromatic hydrocarbon, ethylene glycol and tricyclopentanediol into a reactor according to a molar ratio of 1:0.5:2.1:0.1, then adding anhydrous manganese acetate with the molar weight of 2, 5-furandicarboxylic acid dimethyl ester being 1.0 thousandth of that, gradually heating to 180 ℃ under the protection of nitrogen, reacting for 4.0h, then adding antimony trioxide with the molar weight of 0.8 thousandth of that of 2, 5-furandicarboxylic acid dimethyl ester and diphenyl phosphite with the molar weight of 1.0 thousandth of that, gradually heating to 250 ℃, reducing the vacuum degree to 10Pa, and reacting for 4.0h to obtain the poly-2, 5-furandicarboxylic acid dihydroxy ethoxy polycyclic aromatic hydrocarbon ethylene glycol tricyclopentanediol copolyester with the structure formula (21), the intrinsic viscosity of 0.77/g, the glass transition temperature of 136 ℃, and the melt viscosity of 700Pa S at 250 ℃.

Formula (21), wherein x, m, n are integers from 1 to 10, and z is an integer from 10 to 100.

Example 28

Adding 2, 5-furandicarboxylic acid dimethyl ester, dihydroxy ethoxy polycyclic aromatic hydrocarbon, ethylene glycol and tetrafluoro-p-xylene glycol into a reactor according to a molar ratio of 1:0.3:2.1:0.2, then adding anhydrous manganese acetate with the molar weight of 2, 5-furandicarboxylic acid dimethyl ester being 1.0 thousandth, gradually heating to 195 ℃ under the protection of nitrogen, reacting for 4.0 hours, then adding antimony trioxide with the molar weight of 0.8 thousandth of 2, 5-furandicarboxylic acid dimethyl ester and diphenyl phosphite with the molar weight of 2.0 thousandth, gradually heating to 260 ℃, reducing the vacuum degree to 10Pa, and reacting for 4.0 hours to obtain poly-2, 5-furandicarboxylic acid dihydroxy ethoxy polycyclic aromatic hydrocarbon ethylene glycol tetrafluoro-p-xylene glycol copolyester with the structure formula (22), the intrinsic viscosity of 0.dL 69/g, the glass transition temperature of 135 ℃, and the melt viscosity of 760Pa S at 250 ℃.

Formula (22), wherein x, m, n are integers from 1 to 10, and z is an integer from 10 to 100.

Example 29

Adding 2, 5-furandicarboxylic acid dimethyl ester, dihydroxy ethoxy polycyclic aromatic hydrocarbon, ethylene glycol and tetracyclic diol into a reactor according to a molar ratio of 1:0.3:2.1:0.3, then adding tetrabutyl titanate with the molar weight of the 2, 5-furandicarboxylic acid dimethyl ester being 1.2 thousandth of that of, under the protection of nitrogen, gradually heating to 185 ℃, reacting for 4.0h, then adding diphenyl phosphite with the molar weight of the 2, 5-furandicarboxylic acid dimethyl ester being 1.0 thousandth of that of, gradually heating to 250 ℃, reducing the vacuum degree to 15Pa, and reacting for 4.0h to obtain the poly (furan dicarboxylic acid) dihydroxy ethoxy polycyclic aromatic hydrocarbon ethylene glycol tetracyclic diol copolyester, wherein the structure is shown as formula (23), the intrinsic viscosity is 0.61 dL/g, the glass transition temperature is 141 ℃, and the melt viscosity is 810Pa S at 250 ℃.

Formula (23), wherein x, m, n are integers from 1 to 10, and z is an integer from 10 to 100.

Example 30

Adding dimethyl 2, 5-furandicarboxylate, dimethyl terephthalate, dihydroxyethoxy polycyclic aromatic hydrocarbon, ethylene glycol and 1, 4-cyclohexanedimethanol into a reactor according to a molar ratio of 0.8:0.2:0.4:2.1:0.3, then adding anhydrous manganese acetate with a molar amount of 1.2 thousandths (dimethyl 2, 5-furandicarboxylate + dimethyl terephthalate), gradually heating to 185 ℃ under the protection of nitrogen, reacting for 4.0h, then adding antimony trioxide with a molar amount of 0.7 thousandths (dimethyl 2, 5-furandicarboxylate + dimethyl terephthalate) and 2.0 thousandths diphenyl phosphite, gradually heating to 250 ℃, reducing the vacuum degree to 25Pa, reacting for 3.5h to obtain the poly (dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 4-cyclohexanedimethanol with a structure of (24), its intrinsic viscosity was 0.75 dL/g, glass transition temperature 133 ℃ and melt viscosity 850 Pa.S at 250 ℃.

Formula (24), wherein o, p, q, x, m, n are integers from 1 to 10, and z is an integer from 10 to 100.

Example 31

Adding dimethyl 2, 5-furandicarboxylate, dimethyl terephthalate, dihydroxyethoxy polycyclic aromatic hydrocarbon, ethylene glycol and 1, 4-cyclohexanedimethanol into a reactor according to the molar ratio of 0.5:0.5:0.4:2.1:0.3, then adding anhydrous manganese acetate with the molar amount of 1.5 thousandths (dimethyl 2, 5-furandicarboxylate + dimethyl terephthalate), gradually heating to 190 ℃ under the protection of nitrogen, reacting for 4.0h, then adding antimony trioxide with the molar amount of 0.3 thousandths (dimethyl 2, 5-furandicarboxylate + dimethyl terephthalate) and 0.4 thousandths of diphenyl phosphite, gradually heating to 255 ℃, reducing the vacuum degree to 15Pa, reacting for 4.2h to obtain the poly (dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 4-cyclohexanedimethanol for 2, 5-furandicarboxylate with the intrinsic viscosity of 0.63 dL/g, glass transition temperature 130 ℃ and melt viscosity 950 Pa.S at 250 ℃.

Example 32

Dimethyl 2, 5-furandicarboxylate, dimethyl terephthalate, dihydroxy ethoxy polycyclic aromatic hydrocarbon, ethylene glycol and 1, 4-cyclohexanedimethanol in a molar ratio of 0.1: 0.9: adding the mixture into a reactor at a ratio of 0.4:2.1:0.3, adding anhydrous manganese acetate with a molar weight of 1.5 thousandth (2, 5-dimethyl furandicarboxylate + dimethyl terephthalate), gradually heating to 195 ℃ under the protection of nitrogen, reacting for 4.5 hours, then adding antimony trioxide with a molar weight of 1.7 thousandth (2, 5-dimethyl furandicarboxylate + dimethyl terephthalate) and diphenyl phosphite with a molar weight of 2.0 thousandth, gradually heating to 260 ℃, reducing the vacuum degree to 5.5Pa, and reacting for 1.0 hour to obtain poly (2, 5-dimethyl furandicarboxylate dihydroxy ethoxy aromatic glycol-1, 4-cyclohexanedimethanol copolyester, wherein the intrinsic viscosity is 0.62 dL/g, the glass transition temperature is 130 ℃, and the melt viscosity is 650Pa S at 260 ℃.

Example 33

Adding dimethyl 2, 5-furandicarboxylate, dimethyl terephthalate, dihydroxyethoxy polycyclic aromatic hydrocarbon, propylene glycol and 1, 4-cyclohexanedimethanol into a reactor according to the molar ratio of 0.2:0.8:0.4:2.1:0.2, then adding anhydrous manganese acetate with the molar amount of 1.0 thousandth (dimethyl 2, 5-furandicarboxylate + dimethyl terephthalate), gradually heating to 195 ℃ under the protection of nitrogen, reacting for 4.5h, then adding antimony acetate with the molar amount of 1.0 thousandth (dimethyl 2, 5-furandicarboxylate + dimethyl terephthalate), 2.0 thousandth pyrophosphoric acid, gradually heating to 250 ℃, reducing the vacuum degree to 17Pa, reacting for 1.5h to obtain the poly (dimethyl 2, 5-furandicarboxylate/terephthalic acid dihydroxyethoxy polycyclic aromatic hydrocarbon propylene glycol 1, 4-cyclohexanedimethanol copolyester with the structure as formula (25), its intrinsic viscosity was 0.62 dL/g, glass transition temperature 120 ℃ and melt viscosity 550 Pa.S at 250 ℃.

Formula (25), wherein o, p, q, x, m, n are integers from 1 to 10, and z is an integer from 10 to 100.

Example 34

Adding dimethyl 2, 5-furandicarboxylate, dihydroxy ethoxy polycyclic aromatic hydrocarbon, neopentyl glycol and trans-1, 4-cyclohexanedimethanol into a reactor according to the molar ratio of 1:0.30:1.9:0.4, then adding anhydrous zinc acetate with the molar weight of the dimethyl 2, 5-furandicarboxylate of 0.9 thousandth, gradually heating to 180 ℃ under the protection of nitrogen, reacting for 3.5 hours, then adding ethylene glycol antimony with the molar weight of the dimethyl 2, 5-furandicarboxylate of 1.0 thousandth, trimethyl phosphate with the molar weight of 1.0 thousandth, gradually heating to 245 ℃, reducing the vacuum degree to 25Pa, reacting for 4.0 hours to obtain the trans-1, 4-neopentyl glycol copolyester of the dihydroxy ethoxy polycyclic aromatic hydrocarbon of the poly 2, 5-furandicarboxylate, the structure is shown as formula (26), the intrinsic viscosity is 0.74dL/g, the glass transition temperature is 116 ℃, melt viscosity 400 Pa.s at 245 ℃.

Formula (26), wherein x, m, n are integers from 1 to 10, and z is an integer from 10 to 100.

Example 35

Adding dimethyl 2, 5-furandicarboxylate, dihydroxy ethoxy polycyclic aromatic hydrocarbon, 2-methyl-1, 3-propanediol and trans-1, 4-cyclohexanedimethanol into a reactor according to the molar ratio of 1:0.30:1.9:0.4, then adding anhydrous zinc acetate with the molar amount of 0.9 thousandth of dimethyl 2, 5-furandicarboxylate, gradually heating to 180 ℃ under the protection of nitrogen, reacting for 3.5h, then adding ethylene glycol antimony with the molar amount of 1.0 thousandth of dimethyl 2, 5-furandicarboxylate and 1.0 thousandth of trimethyl phosphate, gradually heating to 245 ℃, reducing the vacuum degree to 25Pa, reacting for 4.0h to obtain the poly-2, 5-furandicarboxylate dihydroxy ethoxy polycyclic aromatic hydrocarbon 2-methyl-1, 3-propanediol trans-1, 4-cyclohexanedimethanol copolyester with the structure as shown in formula (27), its intrinsic viscosity was 0.78 dL/g, glass transition temperature 115 ℃ and melt viscosity 330 Pa.S at 245 ℃.

Formula (27), wherein x, m, n are integers from 1 to 10, and z is an integer from 10 to 100.

Example 36

Adding 2, 5-furandicarboxylic acid dimethyl ester, isophthalic acid dimethyl ester, dihydroxy ethoxy polycyclic aromatic hydrocarbon and ethylene glycol into a reactor according to the molar ratio of 0.7:0.3:0.4:2.0, then adding anhydrous zinc acetate with the molar amount of 0.9 per thousand (2, 5-furandicarboxylic acid dimethyl ester and isophthalic acid dimethyl ester), gradually heating to 180 ℃ under the protection of nitrogen, reacting for 4.0h, then adding polyethylene glycol antimony with the molar amount of 1.0 per thousand (2, 5-furandicarboxylic acid dimethyl ester and isophthalic acid dimethyl ester), 1.1 per thousand triphenyl phosphate, gradually heating to 245 ℃, reducing the vacuum degree to 35Pa, reacting for 4.0h to obtain the dihydroxy ethoxy polycyclic aromatic hydrocarbon ethylene glycol copolyester of 2, 5-furandicarboxylic acid isophthalic acid, wherein the structural formula is (28), the intrinsic viscosity is 0.84 dL/g, the glass transition temperature is 123 ℃, melt viscosity 320 Pa.s at 245 ℃.

Formula (28), wherein x, o, m, n are integers from 1 to 10, and z is an integer from 10 to 100.

Example 37

Adding 2, 5-furandicarboxylic acid dimethyl ester, phthalic acid dimethyl ester, dihydroxy ethoxy polycyclic aromatic hydrocarbon and ethylene glycol into a reactor according to the molar ratio of 0.7:0.3:0.4:2.0, then adding anhydrous zinc acetate with the molar weight of 0.9 per thousand (2, 5-furandicarboxylic acid dimethyl ester + phthalic acid dimethyl ester), gradually heating to 180 ℃ under the protection of nitrogen, reacting for 4.0h, then adding polyethylene glycol antimony with the molar weight of 1.0 per thousand (2, 5-furandicarboxylic acid dimethyl ester + phthalic acid dimethyl ester), 1.1 per thousand triphenyl phosphate, gradually heating to 245 ℃, reducing the vacuum degree to 30Pa, reacting for 4.0h to obtain the dihydroxy ethoxy polycyclic aromatic hydrocarbon ethylene glycol copolyester of 2, 5-furandicarboxylic acid phthalic acid, wherein the structure is shown as formula (29), the intrinsic viscosity is 0.77/dL/g, the glass transition temperature is 121 ℃, melt viscosity was 280 Pa.s at 245 ℃.

Formula (29), wherein x, o, m, n are integers from 1 to 10, and z is an integer from 10 to 100.

Example 38

Adding 2, 5-furandicarboxylic acid dimethyl ester, biphenyl dicarboxylic acid dimethyl ester, dihydroxy ethoxy polycyclic aromatic hydrocarbon and ethylene glycol into a reactor according to the molar ratio of 0.7:0.3:0.4:1.2, then adding anhydrous zinc acetate with the molar amount of 1.2 thousandths (2, 5-furandicarboxylic acid dimethyl ester + biphenyl dicarboxylic acid dimethyl ester), gradually heating to 190 ℃ under the protection of nitrogen, reacting for 4.0h, then adding polyethylene glycol antimony with the molar amount of 1.2 thousandths (2, 5-furandicarboxylic acid dimethyl ester + biphenyl dicarboxylic acid dimethyl ester), 1.5 thousandths of triphenyl phosphate, gradually heating to 255 ℃, reducing the vacuum degree to 30Pa, reacting for 4.0h to obtain the 2, 5-furandicarboxylic acid biphenyl dicarboxylic acid dihydroxy ethoxy polycyclic aromatic hydrocarbon ethylene glycol copolyester with the structure of formula (30), the intrinsic viscosity of 0.71/dL, the glass transition temperature of 128 ℃, melt viscosity 785 Pa.s at 255 ℃.

Formula (30), wherein x, o, m, n are integers from 1 to 10, and z is an integer from 10 to 100.

Example 39

Adding 2, 5-furandicarboxylic acid dimethyl ester, cyclohexanedicarboxylic acid dimethyl ester, dihydroxyethoxy polycyclic aromatic hydrocarbon and ethylene glycol into a reactor according to the molar ratio of 0.7:0.3:0.3:3.0, then adding anhydrous zinc acetate with the molar amount of 3.0 thousandths (2, 5-furandicarboxylic acid dimethyl ester and cyclohexanedicarboxylic acid dimethyl ester), gradually heating to 170 ℃ under the protection of nitrogen, reacting for 4.0h, then adding germanium dioxide with the molar amount of 1.2 thousandths (2, 5-furandicarboxylic acid dimethyl ester and cyclohexanedicarboxylic acid dimethyl ester) and 1.5 thousandths of triphenyl phosphate, gradually heating to 200 ℃, reducing the vacuum degree to 20Pa, reacting for 8.0h to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol copolyester of 2, 5-furandicarboxylic acid cyclohexanedicarboxylic acid, wherein the structure is shown as a formula (31), the intrinsic viscosity is 0.65/dL, the glass transition temperature is 109 ℃, melt viscosity was 360 Pa.s at 240 ℃.

Formula (31), wherein x, o, m, n are integers from 1 to 10, and z is an integer from 10 to 100.

Comparative example 1

Adding 2, 5-furandicarboxylic acid dimethyl ester and ethylene glycol into a reactor according to the molar ratio of 1:2.1, then adding anhydrous zinc acetate with the molar weight of the 2, 5-furandicarboxylic acid dimethyl ester of 0.8 per mill, gradually heating to 180 ℃ under the protection of nitrogen, reacting for 4.0 hours, then adding antimony trioxide with the molar weight of the 2, 5-furandicarboxylic acid dimethyl ester of 1.0 per mill and trimethyl phosphate with the molar weight of 1.0 per mill, gradually heating to 240 ℃, reducing the vacuum degree to 20Pa, and reacting for 3.5 hours to obtain poly-2, 5-furandicarboxylic acid ethylene glycol ester, wherein the intrinsic viscosity is 0.73 dL/g, the glass transition temperature is 87 ℃, and the thermal weight loss T is_5%375 deg.C, 240 deg.C, 1200g weight, 45g melt index, 380 Pa. S melt viscosity at 240 deg.C.

Comparative example 2

Adding dimethyl terephthalate and ethylene glycol into a reactor according to a molar ratio of 1:2.1, then adding anhydrous zinc acetate with the molar weight of dimethyl terephthalate being 0.8 per mill, gradually heating to 180 ℃ under the protection of nitrogen, reacting for 4.0 hours, then adding antimony trioxide with the molar weight of dimethyl terephthalate being 1.0 per mill and trimethyl phosphate with the molar weight of 1.0 per mill, gradually heating to 285 ℃, reducing the vacuum degree to 45Pa, reacting for 4.0 hours, and obtaining polyethylene terephthalate, wherein the intrinsic viscosity is 0.78 dL/g, the glass transition temperature is 70 ℃, 240 ℃, 1200g of a weight cannot be melted, 260 ℃, cannot be melted, the melt viscosity is 15400Pa S at 270 ℃, and the melt viscosity is 1600Pa S at 280 ℃, and the melt index is 18 g.

Comparative example 3

This comparative example differs from example 1 in that: replacing the bis-hydroxyethoxy polycyclic aromatic hydrocarbon with the following structure:

the copolyester obtained had an intrinsic viscosity of 0.68dL/g, a glass transition temperature of 88 ℃ and a melt viscosity of 400 Pa.S at 240 ℃.

When the bio-based polyester with high glass transition temperature and low melting point obtained by the above embodiment of the invention is used, the bio-based polyester with high glass transition temperature and low melting point can be processed into a required polyester product by processes of extrusion granulation, injection molding, extrusion molding, weaving and the like according to the requirements of practical application in a manner known in the art. For example:

example 40: the poly 2, 5-furandicarboxylic acid dihydroxy ethoxy polycyclic aromatic hydrocarbon ethylene glycol copolyester obtained in example 1 was subjected to melt extrusion and granulation in a co-rotating twin-screw extruder. The working parameters of the co-rotating double-screw extruder are as follows: the temperature of the charging barrel is 240-260 ℃, and the temperature of the die head is 240-260 ℃. And then injecting the sample into a standard sample by using an injection molding machine, wherein the injection molding machine has the parameters as follows: the cylinder temperature is 245-260 ℃, the pressure maintaining time is 3-10 s, the standard sample is tested according to ASTM D638-08 and GB/T1843-2008 respectively, and the results show that the tensile property, the elongation at break and the notch impact strength of the standard sample are ideal.

Example 41: the poly (2, 5-furandicarboxylic acid) bishydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol copolyester obtained in example 2 and an antioxidant 1010 were mixed in the following ratio of 1:0.1 percent of the mass ratio is mixed to prepare spinning melt, and then spinning is carried out, wherein the spinning technological parameters are as follows: the filtered pressure during spinning is 30-70kg/cm²(ii) a The extrusion temperature is 238-255 ℃; the cooling temperature is 10-20 ℃; the winding speed is 1000-3000 m/min; the extrusion swelling ratio of the spinning melt is 1.10-1.20. The polyester fiber yarn prepared by the method has higher tensile strength and elongation at break.

Example 42: feeding the poly (2, 5-furandicarboxylic acid) dihydroxy ethoxy polycyclic aromatic hydrocarbon ethylene glycol copolyester obtained in the example 1 into a single-screw extruder, carrying out melt extrusion at 240-260 ℃, casting a molten fluid onto a rotating cooling roller to obtain a casting thick sheet with the thickness of 1500-5500 μm, preheating the casting thick sheet to 80-140 ℃, longitudinally stretching the casting thick sheet for 3-4 times, then preheating to 80-140 ℃, transversely stretching for 3-4.5 times, and then carrying out heat setting at 70-130 ℃ to obtain the polyester film.

The polyester film can be applied in various fields. For example, it can be combined with inorganic materials, organic materials or composite materials thereof by adhesives to form optical materials, decorative materials and the like such as a baby bottle body, a water cup, a kitchen electrical product, a food package, a hot-fill beverage bottle, an optical base film and the like with a composite laminated structure.

In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.

The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.

The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.

Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.

Unless specifically stated otherwise, use of the terms "comprising", "including", "having" or "having" is generally to be understood as open-ended and not limiting.

It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.

While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.

Claims

1. A preparation method of bio-based polyester with high glass transition temperature and low melting point is characterized by comprising the following steps:

formula (1).

2. The method of claim 1, wherein: the first dibasic acid or the esterified product thereof is prepared from bio-based furoic acid or 5-hydroxymethyl furfural, and the first dibasic acid comprises any one or the combination of more than two of 2, 5-furandicarboxylic acid, 2, 4-furandicarboxylic acid, 2, 3-furandicarboxylic acid and 3, 4-furandicarboxylic acid;

and/or the dihydric alcohol comprises a cyclic dihydric alcohol and/or an aliphatic dihydric alcohol; the cyclic diol comprises any one or the combination of more than two of cis-1, 4-cyclohexanedimethanol, trans-1, 4-cyclohexanedimethanol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, 1, 4-cyclohexanediol, 1, 3-cyclohexanediol, 1, 2-cyclohexanediol, dicyclopentanediol, 1-methyl-dicyclopentanediol, 1, 5-dimethyl-dicyclopentanediol, tricyclodecanedimethanol, tetrafluoroterephthalyl alcohol, tricyclodecanediol, bicycloheptanediol, tricyclopentanediol and tetracyclodiol; the aliphatic dihydric alcohol comprises any one or the combination of more than two of ethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol and 2-methyl-1, 3-propanediol;

and/or the first mixed reaction system further comprises a second dibasic acid or an esterified product thereof, wherein the second dibasic acid comprises an aromatic dibasic acid and/or an aliphatic dibasic acid, and the aromatic dibasic acid comprises any one or a combination of more than two of terephthalic acid, isophthalic acid, phthalic acid, biphenyl dicarboxylic acid and naphthalene dicarboxylic acid; the esterified compound corresponding to the aromatic dibasic acid comprises any one or the combination of more than two of dimethyl terephthalate, dimethyl isophthalate, dimethyl phthalate, dimethyl bibenzoate and dimethyl naphthalenedicarboxylate; the aliphatic dibasic acid comprises any one or the combination of more than two of cyclohexanedicarboxylic acid, succinic acid and adipic acid; the esterified matter corresponding to the aliphatic dibasic acid comprises any one or the combination of more than two of dimethyl cyclohexanedicarboxylate, dimethyl succinate and dimethyl adipate.

3. The method according to claim 2, comprising:

reacting the second mixed reaction system for 1.0-8 h under the conditions that the temperature is 200-260 ℃ and the vacuum degree is less than 100Pa, so as to obtain the bio-based polyester with high glass transition temperature and low melting point;

and/or the molar ratio of the dihydroxyethoxy polycyclic aromatic hydrocarbon to the combination of the first dibasic acid or the ester thereof and the second dibasic acid or the ester thereof is 5-95: 100;

and/or the molar ratio of the first dibasic acid or the ester thereof to the combination of the first dibasic acid or the ester thereof and the second dibasic acid or the ester thereof is 10-100: 100;

and/or the molar ratio of the dihydric alcohol to the combination of the first dibasic acid or the ester thereof and the second dibasic acid or the ester thereof is 120-300: 100;

and/or the molar ratio of the esterification or ester exchange catalyst to the combination of the first dibasic acid or the ester thereof and the second dibasic acid or the ester thereof is 0.3-3.0: 1000;

and/or the molar ratio of the polycondensation catalyst to the combination of the first dibasic acid or the ester thereof and the second dibasic acid or the ester thereof is 0.3-3.0: 1000;

and/or the molar ratio of the stabilizer to the combination of the first dibasic acid or the ester thereof and the second dibasic acid or the ester thereof is 0.4-3.0: 1000;

and/or the esterification or ester exchange catalyst comprises any one or the combination of more than two of zinc catalyst, manganese catalyst, titanium catalyst and antimony catalyst;

and/or the polycondensation catalyst comprises any one or the combination of more than two of a titanium catalyst, a tin catalyst, an antimony catalyst and a germanium catalyst;

and/or the stabilizer is selected from a phosphorus stabilizer, and the phosphorus stabilizer comprises any one or a combination of more than two of phosphorous acid, hypophosphorous acid, pyrophosphoric acid, ammonium phosphate, trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, triphenyl phosphite, diphenyl phosphite, ammonium phosphite and ammonium dihydrogen phosphate.

4. The production method according to claim 3, characterized in that: the zinc-based catalyst comprises zinc acetate; and/or, the manganese-based catalyst comprises manganese acetate; and/or the titanium catalyst comprises one or the combination of more than two of tetrabutyl titanate, isopropyl titanate, titanium dioxide and inorganic supported titanium catalyst; and/or the antimony catalyst comprises any one or the combination of more than two of antimony trioxide, ethylene glycol antimony, antimony acetate and polyethylene glycol antimony; and/or the tin catalyst comprises any one or the combination of more than two of dibutyltin oxide, stannous isooctanoate, monobutyl triisotin octoate and dioctyltin oxide; and/or the germanium-based catalyst comprises germanium dioxide and/or germanium oxide.

5. The bio-based high glass transition temperature low melting point polyester prepared by the method of any one of claims 1 to 4, wherein the bio-based high glass transition temperature low melting point polyester has a glass transition temperature of 95 to 160 ℃ and a melt viscosity of 100 to 1000 Pa-S at a temperature range of 240 to 260 ℃.

6. A composition for synthesizing bio-based high glass transition temperature low melting point polyesters, comprising:

formula (1).

7. The composition of claim 6, wherein the composition further comprises: a component (c) comprising a second dibasic acid or an ester thereof, the second dibasic acid comprising an aromatic dibasic acid and/or an aliphatic dibasic acid;

the molar ratio of the component (b) to the combination of the component (a) and the component (c) is 5-95: 100; the molar ratio of the component (a) to the combination of the component (a) and the component (c) is 10-100: 100; the molar ratio of the component (d) to the combination of the component (a) and the component (c) is 120-300: 100;

the aromatic dibasic acid comprises one or more of terephthalic acid, isophthalic acid, phthalic acid, biphenyldicarboxylic acid and naphthalenedicarboxylic acid; the esterified compound corresponding to the aromatic dibasic acid comprises any one or the combination of more than two of dimethyl terephthalate, dimethyl isophthalate, dimethyl phthalate, dimethyl bibenzoate and dimethyl naphthalenedicarboxylate; the aliphatic dibasic acid comprises any one or the combination of more than two of cyclohexanedicarboxylic acid, succinic acid and adipic acid; the esterified matter corresponding to the aliphatic dibasic acid comprises any one or the combination of more than two of dimethyl cyclohexanedicarboxylate, dimethyl succinate and dimethyl adipate;

and/or the first dibasic acid or the esterified product thereof is prepared from bio-based furoic acid or 5-hydroxymethyl furfural, and the first dibasic acid comprises any one or the combination of more than two of 2, 5-furandicarboxylic acid, 2, 4-furandicarboxylic acid, 2, 3-furandicarboxylic acid and 3, 4-furandicarboxylic acid;

and/or the cyclic diol comprises any one or the combination of more than two of cis-1, 4-cyclohexanedimethanol, trans-1, 4-cyclohexanedimethanol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, 1, 4-cyclohexanediol, 1, 3-cyclohexanediol, 1, 2-cyclohexanediol, dicyclopentanediol, 1-methyl-dicyclopentanediol, 1, 5-dimethyldicyclopentanediol, tricyclodecanedimethanol, tetrafluoroterephthalyl alcohol, tricyclodecanediol, bicycloheptanediol, tricyclopentanediol and tetracyclodiol;

and/or the aliphatic dihydric alcohol comprises any one or the combination of more than two of ethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol and 2-methyl-1, 3-propanediol.

8. A method for producing polyester particles, characterized by comprising: inputting the bio-based polyester with high glass transition temperature and low melting point as defined in claim 5 into a co-rotating twin-screw extruder for melt extrusion and granulation; wherein the working parameters of the co-rotating twin-screw extruder comprise: the temperature of the charging barrel is 240-260 ℃, and the temperature of the die head is 240-260 ℃.

9. A method of processing a polyester film or sheet, comprising:

feeding the bio-based high glass transition temperature low melting point polyester of claim 5 into a single screw extruder, melt-extruding at 240-260 ℃, and casting the molten fluid onto a rotating cooling drum to obtain a casting slab with a thickness of 1500-5500 μm;

10. A multilayer composite film comprising a first structural layer and a second structural layer laminated in this order, wherein the first structural layer and the second structural layer are bonded to each other, and the first structural layer is a film formed of the bio-based high-glass-transition-temperature low-melting-point polyester according to claim 5.