CN112574400B

CN112574400B - High glass transition temperature and high transparency polyester, polyester product, its preparation method and application

Info

Publication number: CN112574400B
Application number: CN202110213179.9A
Authority: CN
Inventors: 王静刚; 刘小青; 张小琴; 樊林; 慎昂; 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: 2021-05-07
Anticipated expiration: 2041-02-26
Also published as: CN112574400A

Abstract

The invention discloses a high glass transition temperature and high transparency polyester, a polyester product, a preparation method and application thereof. The high glass transition temperature and high transparency polyester has the structure shown in the following formula:

Wherein, x and y are both integers of 1 to 10, z is an integer of 10 to 100, and R is a residue of a dihydric alcohol having 2 to 20 carbon atoms. The glass transition temperature of the polyester is 90-160°C, and the visible light transmittance is excellent, which can effectively solve the problem that PET polyester is used in baby bottle cups, drinking cups, kitchen appliances, hot-filling beverage bottles, optical base films, etc. The problem of insufficient heat resistance in decorative materials, automobile manufacturing and other fields.

Description

High glass transition temperature and high transparency polyester, polyester product, preparation method and application thereof

Technical Field

The invention relates to polyester, in particular to high-glass-transition-temperature high-transparency polyester and a preparation method and application thereof, and belongs to the technical field of high polymer materials.

Background

At present, the yield of Chinese polyethylene terephthalate (PET) exceeds 4000 ten thousand tons, the global yield exceeds 7000 thousand tons, and more than 500 thousand tons of the PET is used for packaging containers such as beverage bottles and the like, and the PET needs to have the characteristics of high transparency and impact resistance, but the glass transition temperature of the PET is only 70 ℃, and the PET generates thermal deformation when the temperature is higher than the temperature, so that the PET cannot be used in occasions with the use temperature of more than 70 ℃, such as water cups, kitchen electrical products, high-temperature disinfection products, automobile manufacturing, electronic display films and the like.

Disclosure of Invention

The invention mainly aims to provide a high-glass-transition-temperature high-transparency polyester and a preparation method thereof, so as to overcome the defects of insufficient impact resistance and heat resistance in the prior art.

Another object of the present invention is to provide the use of the high glass transition temperature high transparent polyester.

Another object of the present invention is to provide a method for processing a polyester film.

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

the embodiment of the invention provides a high-glass transition temperature and high-transparency polyester, which has a structure shown in a formula (I):

formula (I)

Wherein x and y are integers of 1-10, z is an integer of 10-100, and R is a residue of a dihydric alcohol with 2-20 carbon atoms.

In some embodiments, the glycol comprises any one of the following structures:

、

。

further, the high-glass transition temperature and high-transparency polyester has a glass transition temperature of 90-160 ℃ and a visible light transmittance of over 85% at a wavelength of 700 nm.

The embodiment of the invention also provides a preparation method of the high-glass transition temperature and high-transparency polyester, which comprises the following steps:

reacting a first mixed reaction system containing dihydroxy ethoxy polycyclic aromatic hydrocarbon, terephthalic acid or an esterified product thereof, dihydric alcohol and an esterification or ester exchange catalyst to obtain an intermediate product;

continuously reacting a second mixed reaction system containing the intermediate product, a polycondensation catalyst and a stabilizer under a vacuum condition to prepare the high-glass-transition-temperature high-transparency polyester;

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

。

the embodiment of the invention also provides application of the high-glass transition temperature and high-transparency polyester in preparation of products such as fire-fighting equipment, baby feeding bottles, water cups, kitchen electrical products, food packaging materials, hot-filling beverage bottles, optical base films, decorative materials or automobile accessories.

Correspondingly, the embodiment of the invention also provides a preparation method of the polyester granules, which comprises the following steps: inputting the high-glass transition temperature and high-transparency polyester 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 275-295 ℃, and the temperature of the die head is 280-295 ℃.

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

inputting the high-glass transition temperature and high-transparency polyester into a double-screw extruder, carrying out melt extrusion at 270-295 ℃, controlling the outflow speed of a molten fluid by a melt delivery pump, controlling the temperature of the melt delivery pump to be 275-295 ℃, and casting the molten fluid onto a rotating cooling roller to obtain a casting thick sheet with the thickness of 1500-5500 mu m;

and preheating the casting thick sheet to 85-170 ℃, longitudinally stretching for 3-4 times, preheating to 85-170 ℃ again, and transversely stretching for 3-4.5 times to obtain the polyester film.

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

1) the embodiment of the invention synthesizes the polyester by adopting the dihydroxy ethoxy polycyclic aromatic hydrocarbon and the alicyclic rigid dihydric alcohol, the structure of the dihydroxyethoxy polycyclic aromatic hydrocarbon has a plurality of benzene rings and has very high rigidity, and the hydroxyethyl group with high activity, so that the hydroxyethyl group can efficiently generate esterification or ester exchange reaction with terephthalic acid or ester, on the basis, the copolyester with high molecular weight is finally prepared by copolymerizing the copolyester with the alicyclic diol and utilizing the characteristics of the alicyclic diol, namely the alicyclic diol has higher rigidity and a spatial non-planar structure than the aliphatic diol, so that the glass transition temperature, the transparency and the shock resistance of the copolyester are improved, the glass transition temperature (up to 160 ℃) of the PET copolyester is greatly improved, the PET copolyester has high transparency and visible light transmittance, and the crystallization of the copolyester is prevented (the visible light transmittance at the cut-off of 700nm is more than 85%);

2) the high-glass-transition-temperature high-transparency polyester prepared by the invention has the advantages of high glass transition temperature, good heat resistance and excellent visible light transmittance, has excellent impact resistance, and can be widely applied to the product fields of optical materials, decorative materials, automobile manufacturing and the like, such as baby bottle bodies, water cups, kitchen electrical products (stirring cup cold cups of wall-breaking cooking machines, portable fruit juice machine stirring cups, juice extractor barrels, noodle machine stirring cups and the like), food packaging, hot-filling beverage bottles, optical base films 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 shows the nuclear magnetism of poly (hydroxyethoxy) poly (ethylene glycol terephthalate) copolyester prepared in example 1 of the present invention¹An H-NMR spectrum;

FIG. 2 is a DSC chart of poly (hydroxyethoxy poly (arylene glycol) terephthalate copolyester prepared according to example 1 of the present invention;

FIG. 3 is a TGA spectrum of poly (hydroxyethoxy poly (arylene glycol) terephthalate) copolyester prepared according to 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 extensive practices to provide a novel copolyester having a glass transition temperature of 90 to 160 ℃ and an excellent visible light transmittance, which is prepared by copolymerizing an aromatic ring having excellent rigidity and a highly active bishydroxyethoxy polycyclic aromatic hydrocarbon with terephthalic acid, ethylene glycol, and a rigid alicyclic 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 class of high glass transition temperature, high transparent polyesters having the structure shown in formula (i):

formula (I)

In some embodiments, the diols include cyclic diols and/or aliphatic diols, and the like, which may include any one or more of the following diols: any one or a combination of two or more of ethylene glycol, 1, 4-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, 1, 2-cyclohexanedimethanol, 1, 4-cyclohexanediol, dicyclopentanediol, dimethyldicyclopentanediol, monomethyldicyclopentanediol, tricyclodecanedimethanol, tricyclodecanediol, bicycloheptanediol, tricyclopentanediol, tetrafluoroterephthalyl alcohol, tetracyclodiol, and the like, but is not limited thereto.

Specifically, the diol may include any one of the following structures:

、

。

Another aspect of embodiments of the present invention provides a method of preparing the high glass transition temperature high transparent polyester, which includes:

。

in some embodiments, the glycol is any one or more of the following: any one or a combination of two or more of ethylene glycol, 1, 4-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, 1, 2-cyclohexanedimethanol, 1, 4-cyclohexanediol, dicyclopentanediol, dimethyldicyclopentanediol, monomethyldicyclopentanediol, tricyclodecanedimethanol, tricyclodecanediol, bicycloheptanediol, tricyclopentanediol, tetrafluoroterephthalyl alcohol, tetracyclodiol, and the like, but is not limited thereto.

Specifically, the diol may include any one of the following structures:

、

。

in some embodiments, the terephthalic acid or its esters may include terephthalic acid, dimethyl terephthalate, diethyl terephthalate, and the like, but are not limited thereto.

In some embodiments, the method of making comprises:

reacting the first mixed reaction system for 1.5-5.0 h at 160-260 ℃ under a protective atmosphere to obtain an intermediate product; and

and (3) reacting the second mixed reaction system for 1.5-6.0 h under the conditions that the temperature is 260-300 ℃ and the vacuum degree is less than 200Pa, so as to obtain the high-glass-transition-temperature and high-transparency polyester.

In some embodiments, the method of making specifically comprises:

the preparation method of the high-glass transition temperature and high-transparency polyester specifically comprises the following steps: the method comprises the following steps of (1) reacting dihydroxyethoxy polycyclic aromatic hydrocarbon, terephthalic acid or an esterified product thereof, dihydric alcohol and an esterification or ester exchange catalyst at 160-260 ℃ for 1.5-5.0 h to obtain a first product; and then adding a polycondensation catalyst and a stabilizer, reacting for 1.5-6.0 h at 260-300 ℃ and under the vacuum degree of 200Pa, and obtaining the high-glass-transition-temperature high-transparency polyester.

In some embodiments, the molar ratio of the bis-hydroxyethoxy polycyclic aromatic hydrocarbon to terephthalic acid or an esterified product thereof is 5 to 90: 100.

In some embodiments, the molar ratio of the combination of glycol and bis-hydroxyethoxy polycyclic aromatic hydrocarbon (molar amount of glycol + molar amount of bis-hydroxyethoxy polycyclic aromatic hydrocarbon) to terephthalic acid or its esterified product is 1.2-3.0: 1.

In some embodiments, the molar ratio of the esterification or transesterification catalyst to terephthalic acid or an esterified product thereof is 0.3 to 3: 1000.

In some embodiments, the molar ratio of the polycondensation catalyst to terephthalic acid or an esterified product thereof is 0.3 to 3: 1000.

In some embodiments, the molar ratio of the stabilizer to terephthalic acid or an esterified product thereof is 0.4 to 5: 1000.

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 or more of tetrabutyl titanate, isopropyl titanate, titanium dioxide, an inorganic supported titanium catalyst, 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 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.

The invention also provides application of the high-glass transition temperature and high-transparency polyester in preparing fire-fighting equipment, baby feeding bottles, water cups, kitchen electrical products (such as stirring cup cold cups of broken food machines, portable juicer stirring cups, juicer juicing barrels, noodle machine stirring cups and the like), food packaging materials, hot-filling beverage bottles, optical materials such as optical base films, decorative materials or products such as automobile accessories.

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 high-glass transition temperature and high-transparency polyester 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 275-295 ℃, and the temperature of the die head is 280-295 ℃.

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

preheating the casting thick sheet to 85-170 ℃, longitudinally stretching for 3-4 times, then preheating to 85-170 ℃ again, and transversely stretching for 3-4.5 times to finally obtain the polyester film.

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 stacked 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 high glass transition temperature and high transparent 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 structure of the dihydroxy ethoxy polycyclic aromatic hydrocarbon adopted in the embodiment of the invention has multiple benzene rings, the structure has high rigidity, and the hydroxy ethyl with high activity can efficiently perform esterification or ester exchange reaction with terephthalic acid or an esterified substance to prepare the copolyester with high molecular weight, so that the glass transition temperature of the PET copolyester is effectively increased. Meanwhile, the multiple benzene rings have excellent visible light transmission performance, so that the copolyester glass ring transition temperature is increased, and meanwhile, the copolyester glass ring has high transparency and visible light transmission rate. On the basis, alicyclic rigid dihydric alcohol is further introduced to further replace the ethylene glycol in the copolyester. Because the alicyclic diol has greater rigidity than ethylene glycol, the glass transition temperature of the copolyester can be further increased, and the spatial non-planar structure of the alicyclic diol prevents the crystallization of the copolyester. The introduction of alicyclic diol on the basis of the poly (p-phenyleneterephthalate) dihydroxy ethoxy polycyclic aromatic hydrocarbon ethylene glycol copolyester further improves the glass transition temperature of the copolyester to 160 ℃, and the visible light transmittance at 700nm is more than 85%. Therefore, the multifunctional cup can be widely applied to the fields of baby bottle bodies, water cups, kitchen electrical products (stirring cup cold cups of wall breaking cooking machines, stirring cups of portable fruit juice machines, juice extracting barrels of juice extractors, stirring cups of noodle machines and the like), hot filling beverage bottles, optical base films, decorative materials, automobile manufacturing and the like.

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 was measured on a Bruker 400 AVANCE III Spectrometer type instrument at 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 ℃. Elongation at break test: an Instron model 5567 universal materials tester was used. The sample bar dimensions were 20.0mm long, 2.0mm wide and 1.0mm thick, and the stretching speed was 20 mm/min.

Example 1

Adding dimethyl terephthalate, dihydroxyethoxy polycyclic aromatic hydrocarbon and ethylene glycol into a reactor according to the molar ratio of 1:0.10:2.1, then adding anhydrous zinc acetate with the molar weight of 0.6 per thousand of dimethyl terephthalate, gradually heating to 180 ℃ under the protection of nitrogen, reacting for 4.0h, then adding antimony trioxide with the molar weight of 0.8 per thousand of dimethyl terephthalate and 0.8 per thousand of phosphorous acid, and gradually reactingHeating to 280 deg.C, reducing vacuum degree to 30Pa, reacting for 3.0h to obtain poly (p-phenyleneterephthalate) dihydroxy-ethoxy polycyclic aromatic hydrocarbon glycol copolyester with structure as formula (III) and intrinsic viscosity of 0.85dL/g, and performing nuclear magnetism¹H-NMR is shown in FIG. 1, DSC curve is shown in FIG. 2, glass transition temperature is 98 deg.C, and weight loss under heat T_5%The temperature was 418 ℃ and the TGA spectrum was as shown in FIG. 3, and the visible light transmittance at 700nm cut-off was 90%.

The formula (III) is shown in the specification, wherein x and y are integers from 1 to 10, and z is an integer from 10 to 100.

Example 2

Adding dimethyl terephthalate, dihydroxyethoxy polycyclic aromatic hydrocarbon and ethylene glycol into a reactor according to the molar ratio of 1:0.20:2.1, then adding anhydrous manganese acetate with the molar weight of the dimethyl terephthalate of 0.8 per thousand, gradually heating to 170 ℃ under the protection of nitrogen, reacting for 4.5 hours, then adding ethylene glycol antimony with the molar weight of the dimethyl terephthalate of 1.0 per thousand and 1.0 per thousand trimethyl phosphate, gradually heating to 282 ℃, reducing the vacuum degree to 40Pa, and reacting for 3.5 hours to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol copolyester of the poly (terephthalic acid), wherein the structure is shown in formula (III), the intrinsic viscosity is 0.82dL/g, the glass transition temperature is 107 ℃, and the visible light transmittance at 700nm cutoff is 91%.

Example 3

Adding dimethyl terephthalate, dihydroxyethoxy polycyclic aromatic hydrocarbon and ethylene glycol into a reactor according to the molar ratio of 1:0.30:2.1, then adding anhydrous zinc acetate with the molar weight of 1.0 thousandth of dimethyl terephthalate, gradually heating to 185 ℃ under the protection of nitrogen, reacting for 3.5 hours, then adding antimony acetate with the molar weight of 1.2 thousandth of dimethyl terephthalate and 1.2 thousandth of trimethyl phosphate, gradually heating to 286 ℃, reducing the vacuum degree to 60Pa, and reacting for 2.8 hours to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol copolyester of the poly (terephthalic acid), wherein the structure is shown in formula (III), the intrinsic viscosity is 0.83dL/g, the glass transition temperature is 115 ℃, and the visible light transmittance at 700nm cutoff is 92%.

Example 4

Adding dimethyl terephthalate, dihydroxy ethoxy polycyclic aromatic hydrocarbon and ethylene glycol into a reactor according to the molar ratio of 1:0.05:2.0, then adding tetrabutyl titanate with the molar weight of the dimethyl terephthalate of 0.8 thousandth, gradually heating to 160 ℃ under the protection of nitrogen, reacting for 5.0 hours, then adding diphenyl phosphate with the molar weight of the dimethyl terephthalate of 0.6 thousandth, gradually heating to 278 ℃, reducing the vacuum degree to 20Pa, and reacting for 3.5 hours to obtain the dihydroxy ethoxy polycyclic aromatic hydrocarbon ethylene glycol copolyester with the structure shown in formula (III), wherein the intrinsic viscosity is 0.88dL/g, the glass transition temperature is 93 ℃, and the visible light transmittance at 700nm is 93%.

Example 5

Adding dimethyl terephthalate, dihydroxyethoxy polycyclic aromatic hydrocarbon and ethylene glycol into a reactor according to the molar ratio of 1:0.4:1.8, then adding anhydrous zinc acetate with the molar weight of the dimethyl terephthalate of 0.4 per thousand, gradually heating to 190 ℃ under the protection of nitrogen, reacting for 4.6 hours, then adding polyethylene glycol antimony with the molar weight of the dimethyl terephthalate of 0.9 per thousand and triphenyl phosphate of 0.7 per thousand, gradually heating to 285 ℃, reducing the vacuum degree to 35Pa, and reacting for 4.0 hours to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol copolyester of the poly (terephthalic acid), wherein the structure is shown in formula (III), the intrinsic viscosity is 0.78dL/g, the glass transition temperature is 122 ℃, and the visible light transmittance at 700nm cutoff is 89%.

Example 6

Adding dimethyl terephthalate, dihydroxyethoxy polycyclic aromatic hydrocarbon and ethylene glycol into a reactor according to the molar ratio of 1:0.5:2.1, then adding anhydrous manganese acetate with the molar weight of the dimethyl terephthalate of 0.9 per thousand, gradually heating to 185 ℃ under the protection of nitrogen, reacting for 3.6 hours, then adding antimony trioxide with the molar weight of the dimethyl terephthalate of 0.5 per thousand, 0.6 per thousand dibutyltin oxide and 0.9 per thousand diphenyl phosphite, gradually heating to 280 ℃, reducing the vacuum degree to 15Pa, and reacting for 5.0 hours to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol copolyester of the structure formula (III), wherein the intrinsic viscosity is 0.80dL/g, the glass transition temperature is 130 ℃, and the visible light transmittance at 700nm is 89%.

Example 7

Adding dimethyl terephthalate, dihydroxyethoxy polycyclic aromatic hydrocarbon and ethylene glycol into a reactor according to the molar ratio of 1:0.6:2.1, then adding anhydrous zinc acetate with the molar weight of 1.1 per thousand of dimethyl terephthalate, gradually heating to 182 ℃ under the protection of nitrogen, reacting for 4.0h, then adding antimony trioxide with the molar weight of 1.3 per thousand of dimethyl terephthalate and triphenyl phosphate with the molar weight of 1.1 per thousand of dimethyl terephthalate, gradually heating to 283 ℃, reducing the vacuum degree to 14Pa, and reacting for 5.2h to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol copolyester of the poly (terephthalic acid), wherein the structure is shown in formula (III), the intrinsic viscosity is 0.75dL/g, the glass transition temperature is 137 ℃, and the visible light transmittance at 700nm cutoff is 89%.

Example 8

Adding dimethyl terephthalate, dihydroxyethoxy polycyclic aromatic hydrocarbon and ethylene glycol into a reactor according to the molar ratio of 1:0.7:2.1, then adding anhydrous zinc acetate with the molar weight of 1.5 thousandth of dimethyl terephthalate, gradually heating to 178 ℃ under the protection of nitrogen, reacting for 4.2 hours, then adding stannous isooctanoate with the molar weight of 2.5 thousandth of dimethyl terephthalate and 1.5 thousandth of dimethyl phosphate, gradually heating to 286 ℃, reducing the vacuum degree to 12Pa, and reacting for 3.5 hours to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol copolyester of the poly (terephthalic acid), wherein the structure is shown in formula (III), the intrinsic viscosity is 0.70dL/g, the glass transition temperature is 145 ℃, and the visible light transmittance at 700nm cutoff is 88%.

Example 9

Adding dimethyl terephthalate, dihydroxyethoxy polycyclic aromatic hydrocarbon and ethylene glycol into a reactor according to the molar ratio of 1:0.8:2.1, then adding anhydrous zinc acetate with the molar weight of 1.6 per thousand of dimethyl terephthalate, gradually heating to 180 ℃ under the protection of nitrogen, reacting for 4.0h, then adding antimony trioxide with the molar weight of 1.0 per thousand of dimethyl terephthalate and diphenyl phosphate with the molar weight of 2.0 per thousand, gradually heating to 288 ℃, reducing the vacuum degree to 10Pa, and reacting for 3.5h to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol copolyester of the poly (terephthalic acid), wherein the structure is shown in formula (III), the intrinsic viscosity is 0.68dL/g, the glass transition temperature is 153 ℃, and the visible light transmittance at 700nm cutoff is 86%.

Example 10

Adding dimethyl terephthalate, dihydroxyethoxy polycyclic aromatic hydrocarbon and ethylene glycol into a reactor according to the molar ratio of 1:0.9:2.1, then adding anhydrous zinc acetate with the molar weight of 2.0 thousandth of dimethyl terephthalate, gradually heating to 190 ℃ under the protection of nitrogen, reacting for 4.5 hours, then adding antimony trioxide with the molar weight of 1.0 thousandth of dimethyl terephthalate and 1.0 thousandth of diphenyl phosphate, gradually heating to 290 ℃, reducing the vacuum degree to 7.5Pa, and reacting for 4.0 hours to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol copolyester of the poly (terephthalic acid), wherein the structure is shown in formula (III), the intrinsic viscosity is 0.66dL/g, the glass transition temperature is 159 ℃, and the visible light transmittance at 700nm cutoff is 85%.

Example 11

Adding dimethyl terephthalate, dihydroxyethoxy polycyclic aromatic hydrocarbon, ethylene glycol, cis-1, 4-cyclohexanedimethanol and trans-1, 4-cyclohexanedimethanol into a reactor according to the molar ratio of 1:0.20:1.9:0.1:0.1, then adding anhydrous zinc acetate with the molar weight of dimethyl terephthalate of 0.9 per mill, gradually heating to 180 ℃ under the protection of nitrogen, reacting for 3.5h, then adding ethylene glycol antimony with the molar weight of dimethyl terephthalate of 1.0 per mill and trimethyl phosphate with the molar weight of 1.0 per mill, gradually heating to 282 ℃, reducing the vacuum degree to 25Pa, reacting for 4.0h to obtain the poly (p-phenyleneterephthalate) dihydroxy-ethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 4-cyclohexanedimethanol copolyester with the structure shown in formula (IV), the intrinsic viscosity is 0.66dL/g, the glass transition temperature is 108 ℃, and the visible light transmittance at 700nm cutoff is 91%.

The formula (IV) is shown in the specification, wherein x, y, m and n are integers from 1 to 10, and z is an integer from 10 to 100.

Example 12

Adding dimethyl terephthalate, dihydroxyethoxy polycyclic aromatic hydrocarbon, ethylene glycol and cis-1, 4-cyclohexanedimethanol into a reactor according to the molar ratio of 1:0.20:1.9:0.2, then adding anhydrous zinc acetate with the molar weight of 0.9 thousandth of dimethyl terephthalate, gradually heating to 180 ℃ under the protection of nitrogen, reacting for 3.5 hours, then adding ethylene glycol antimony with the molar weight of 1.0 thousandth of dimethyl terephthalate and 1.0 thousandth of trimethyl phosphate, gradually heating to 282 ℃, reducing the vacuum degree to 25Pa, and reacting for 4.0 hours to obtain the poly (p-phenylenediethoxy polycyclic aromatic hydrocarbon ethylene glycol cis-1, 4-cyclohexanedimethanol copolyester with the structure shown in formula (V), the intrinsic viscosity of 0.70dL/g, the glass transition temperature of 104 ℃, and the visible light transmittance of 91 percent at the cut-off value of 700 nm.

The formula (V) is shown in the specification, wherein x, y and m are integers from 1 to 10, and z is an integer from 10 to 100.

Example 13

Adding dimethyl terephthalate, dihydroxyethoxy polycyclic aromatic hydrocarbon, ethylene glycol and trans-1, 4-cyclohexanedimethanol into a reactor according to the molar ratio of 1:0.20:1.9:0.2, then adding anhydrous zinc acetate with the molar weight of 0.9 thousandth of dimethyl terephthalate, gradually heating to 180 ℃ under the protection of nitrogen, reacting for 3.5 hours, then adding ethylene glycol antimony with the molar weight of 1.0 thousandth of dimethyl terephthalate and 1.0 thousandth of trimethyl phosphate, gradually heating to 282 ℃, reducing the vacuum degree to 25Pa, and reacting for 4.0 hours to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol trans-1, 4-cyclohexanedimethanol copolyester with the structure as shown in formula (VI), the intrinsic viscosity of 0.70dL/g, the glass transition temperature of 113 ℃ and the visible light transmittance of 91 percent at the cut-off wavelength of 700 nm.

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

Example 14

Adding dimethyl terephthalate, dihydroxyethoxy polycyclic aromatic hydrocarbon, ethylene glycol and 1, 2-cyclohexanedimethanol into a reactor according to the molar ratio of 1:0.20:1.9:0.2, then adding anhydrous zinc acetate with the molar weight of 0.8 thousandth of the dimethyl terephthalate, gradually heating to 180 ℃ under the protection of nitrogen, reacting for 3.5 hours, then adding antimony trioxide with the molar weight of 2.5 thousandth of the dimethyl terephthalate and trimethyl phosphate with the molar weight of 3.0 thousandth of the dimethyl terephthalate, gradually heating to 280 ℃, reducing the vacuum degree to 60Pa, and reacting for 4.5 hours to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 2-cyclohexanedimethanol copolyester with the structure of formula (VII), the intrinsic viscosity of the copolyester is 0.62dL/g, the glass transition temperature of 107 ℃, and the visible light transmittance at 700nm cut-off of 89%.

The formula (VII) is shown in the specification, wherein x, y and m are integers from 1 to 10, and z is an integer from 10 to 100.

Example 15

Adding dimethyl terephthalate, dihydroxyethoxy polycyclic aromatic hydrocarbon, ethylene glycol and 1, 3-cyclohexanedimethanol into a reactor according to the molar ratio of 1:0.20:1.9:0.2, then adding anhydrous zinc acetate with the molar weight of 2.0 thousandths of the dimethyl terephthalate, gradually heating to 185 ℃ under the protection of nitrogen, reacting for 3.0 hours, then adding antimony trioxide with the molar weight of 1.0 thousandths of the dimethyl terephthalate and 1.0 thousandths of trimethyl phosphate, gradually heating to 280 ℃, reducing the vacuum degree to 30Pa, and reacting for 4.5 hours to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 3-cyclohexanedimethanol copolyester with the structure as formula (VIII), the intrinsic viscosity of the copolyester being 0.72dL/g, the glass transition temperature of 109 ℃ and the visible light transmittance at 700nm cutoff of 89%.

The formula (VIII), wherein x, y and m are integers of 1-10, and z is an integer of 10-100.

Example 16

Adding dimethyl terephthalate, dihydroxyethoxy polycyclic aromatic hydrocarbon, ethylene glycol and 1, 4-cyclohexanediol into a reactor according to the molar ratio of 1:0.30:2.1:0.2, then adding anhydrous zinc acetate with the molar weight of 1.0 thousandth of dimethyl terephthalate, 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 dimethyl terephthalate and 1.0 thousandth of trimethyl phosphate, gradually heating to 280 ℃, reducing the vacuum degree to 10Pa, and reacting for 3.5h to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 4-cyclohexanediol copolyester with the structure formula (IX), the intrinsic viscosity of the copolyester is 0.68dL/g, the glass transition temperature of the copolyester is 119 ℃, and the visible light transmittance at 700nm cut-off is 90%.

The formula (IX), wherein x, y and m are integers of 1-10, and z is an integer of 10-100.

Example 17

Adding terephthalic acid, dihydroxyethoxy 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 anhydrous manganese acetate with the molar weight of 0.8 thousandth of the terephthalic acid, gradually heating to 240 ℃ under the protection of nitrogen, reacting for 4.0h, then adding antimony trioxide with the molar weight of 1.0 thousandth of the terephthalic acid and trimethyl phosphate with the molar weight of 1.5 thousandth of the terephthalic acid, gradually heating to 280 ℃, reducing the vacuum degree to 15Pa, and reacting for 3.5h to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 4-cyclohexanediol copolyester with the structure shown in formula (IX), wherein the intrinsic viscosity is 0.75dL/g, the glass transition temperature is 117 ℃, and the visible light transmittance at 700nm is 89%.

Example 18

Adding terephthalic acid, dihydroxyethoxy polycyclic aromatic hydrocarbon, ethylene glycol and 1, 4-cyclohexanedimethanol into a reactor according to the molar ratio of 1:0.30:2.1:0.5, then adding anhydrous manganese acetate with the molar weight of 0.5 thousandth of the terephthalic acid, gradually heating to 230 ℃ under the protection of nitrogen, reacting for 4.0h, then adding antimony trioxide with the molar weight of 0.6 thousandth of the terephthalic acid and trimethyl phosphate with the molar weight of 0.6 thousandth of the terephthalic acid, gradually heating to 282 ℃, reducing the vacuum degree to 15Pa, and reacting for 3.0h to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 4-cyclohexanedimethanol copolyester with the structure shown in formula (X), the intrinsic viscosity of the dihydroxyethoxy polycyclic aromatic hydrocarbon is 0.88dL/g, the glass transition temperature is 116 ℃, and the visible light transmittance at 700nm cut-off is 89%.

The formula (X), wherein X, y and m are integers of 1-10, and z is an integer of 10-100.

Example 19

Adding dimethyl terephthalate, dihydroxyethoxy polycyclic aromatic hydrocarbon, ethylene glycol and 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 0.8 thousandth of dimethyl terephthalate, gradually heating to 185 ℃ under the protection of nitrogen, reacting for 3.5 hours, then adding antimony trioxide with the molar weight of 0.8 thousandth of dimethyl terephthalate and trimethyl phosphate with the molar weight of 0.8 thousandth of dimethyl terephthalate, gradually heating to 282 ℃, reducing the vacuum degree to 10Pa, and reacting for 3.5 hours to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol dicyclopentanediol copolyester with the structure shown in formula (XI), the intrinsic viscosity of the dihydroxyethoxy polycyclic aromatic hydrocarbon is 0.68dL/g, the glass transition temperature of 120 ℃ and the visible light transmittance at 700nm of 88 percent.

The formula (XI) is shown in the specification, wherein x, y and m are integers from 1 to 10, and z is an integer from 10 to 100.

Example 20

Adding dimethyl terephthalate, dihydroxy ethoxy polycyclic aromatic hydrocarbon, ethylene glycol and monomethyl 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 dimethyl terephthalate of 0.8 thousandth, under the protection of nitrogen, gradually heating to 185 ℃, reacting for 3.5 hours, then adding antimony trioxide with the molar weight of dimethyl terephthalate of 0.8 thousandth and trimethyl phosphate with the molar weight of 1.6 thousandth, gradually heating to 285 ℃, reducing the vacuum degree to 20Pa, reacting for 3.5 hours, and obtaining the dihydroxy ethoxy polycyclic aromatic hydrocarbon ethylene glycol monomethyl dicyclopentanediol copolyester of the formula (XII), wherein the structure is shown in formula (XII), the intrinsic viscosity is 0.72dL/g, the glass transition temperature is 122 ℃, and the visible light transmittance at 700nm cut-off is 88%.

The formula (XII) is shown in the specification, wherein x, y and m are integers from 1 to 10, and z is an integer from 10 to 100.

Example 21

Adding dimethyl terephthalate, dihydroxyethoxy polycyclic aromatic hydrocarbon, ethylene glycol and 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 0.8 thousandth of dimethyl terephthalate, gradually heating to 185 ℃ under the protection of nitrogen, reacting for 4.5 hours, then adding antimony trioxide with the molar weight of 0.8 thousandth of dimethyl terephthalate and trimethyl phosphate with the molar weight of 1.2 thousandth of dimethyl terephthalate, gradually heating to 285 ℃, reducing the vacuum degree to 20Pa, and reacting for 3.5 hours to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol dimethyl dicyclopentanediol copolyester with the structure shown in formula (XIII), wherein the intrinsic viscosity is 0.73dL/g, the glass transition temperature is 123 ℃, and the visible light transmittance at 700nm cut-off is 87%.

Formula (XIII), wherein x, y and m are integers of 1-10, and z is an integer of 10-100.

Example 22

Adding dimethyl terephthalate, dihydroxyethoxy polycyclic aromatic hydrocarbon, ethylene glycol and tricyclodecane dimethanol into a reactor according to the molar ratio of 1:0.30:0.7:0.2, then adding anhydrous zinc acetate with the molar weight of 1.0 thousandth of dimethyl terephthalate, gradually heating to 185 ℃ under the protection of nitrogen, reacting for 4.0 hours, then adding antimony trioxide with the molar weight of 1.0 thousandth of dimethyl terephthalate and trimethyl phosphate with the molar weight of 1.5 thousandth of dimethyl terephthalate, gradually heating to 285 ℃, reducing the vacuum degree to 20Pa, and reacting for 3.5 hours to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol tricyclodecane dimethanol copolyester with the structure shown in formula (XIV), wherein the intrinsic viscosity is 0.60dL/g, the glass transition temperature is 121 ℃, and the visible light transmittance at 700nm cut-off is 90%.

The formula (XIV) is shown in the specification, wherein x, y and m are integers from 1 to 10, and z is an integer from 10 to 100.

Example 23

Adding terephthalic acid, dihydroxyethoxy polycyclic aromatic hydrocarbon, ethylene glycol and tricyclodecanediol into a reactor according to the molar ratio of 1:0.4:1.8:0.2, then adding anhydrous zinc acetate with the molar weight of 0.7 per thousand of the terephthalic acid, gradually heating to 170 ℃ under the protection of nitrogen, reacting for 5.0h, then adding polyethylene glycol antimony with the molar weight of 0.8 per thousand of the terephthalic acid and 1.2 per thousand of triphenyl phosphate, gradually heating to 285 ℃, reducing the vacuum degree to 25Pa, and reacting for 4.0h to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol tricyclodecanediol copolyester of the terephthalic acid, wherein the intrinsic viscosity is 0.72dL/g, the glass transition temperature is 131 ℃, and the visible light transmittance at 700nm cutoff is 87%.

Example 24

Adding dimethyl terephthalate, dihydroxyethoxy 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 thousandth of dimethyl terephthalate, 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 dimethyl terephthalate, dibutyltin oxide with the molar weight of 0.9 thousandth of dimethyl terephthalate and 1.0 thousandth of diphenyl phosphite, gradually heating to 280 ℃, and reducing the vacuum degree to 15Pa, and reacting for 6.0h to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol bicycloheptane diol copolyester with the structure shown as formula (XV), the intrinsic viscosity of 0.82dL/g, the glass transition temperature of 138 ℃ and the visible light transmittance of 700nm cut-off of 90%.

The formula (XV) is shown in the specification, wherein x, y and m are integers from 1 to 10, and z is an integer from 10 to 100.

Example 25

Adding dimethyl terephthalate, dihydroxyethoxy polycyclic aromatic hydrocarbon, ethylene glycol and tricyclopentanediol into a reactor according to the molar ratio of 1:0.5:2.1:0.1, then adding anhydrous manganese acetate with the molar weight of 1.0 thousandth of dimethyl terephthalate, 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 dimethyl terephthalate and 1.0 thousandth of diphenyl phosphite, gradually heating to 285 ℃, reducing the vacuum degree to 10Pa, and reacting for 4.0h to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol tricyclopentanediol copolyester with the structure shown in formula (XVI), the intrinsic viscosity of 0.77dL/g, the glass transition temperature of 136 ℃ and the visible light transmittance at 700nm cutoff of 87%.

The formula (XVI), wherein x, y and m are integers of 1-10, and z is an integer of 10-100.

Example 26

Adding dimethyl terephthalate, dihydroxyethoxy polycyclic aromatic hydrocarbon, ethylene glycol and tetrafluoro-p-xylene glycol into a reactor according to the molar ratio of 1:0.3:2.1:0.2, then adding anhydrous manganese acetate with the molar weight of 1.0 thousandth of dimethyl terephthalate, gradually heating to 185 ℃ under the protection of nitrogen, reacting for 4.0h, then adding antimony trioxide with the molar weight of 0.8 thousandth of dimethyl terephthalate and 2.0 thousandth of diphenyl phosphite, gradually heating to 290 ℃, reducing the vacuum degree to 15Pa, and reacting for 4.0h to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol tetrafluoro-p-xylene glycol copolyester with the structure shown in formula (XVII), the intrinsic viscosity of 0.69dL/g, the glass transition temperature of 132 ℃ and the visible light transmittance of 85 nm at the cut-off of 700 nm.

The formula (XVII) is shown in the specification, wherein x, y and m are integers from 1 to 10, and z is an integer from 10 to 100.

Example 27

Adding dimethyl terephthalate, dihydroxyethoxy polycyclic aromatic hydrocarbon, ethylene glycol and tetracyclic glycol into a reactor according to the molar ratio of 1:0.3:2.1:0.3, then adding tetrabutyl titanate with the molar weight of 1.2 thousandth of dimethyl terephthalate, gradually heating to 185 ℃ under the protection of nitrogen, reacting for 4.0h, then adding diphenyl phosphite with the molar weight of 1.0 thousandth of dimethyl terephthalate, gradually heating to 285 ℃, reducing the vacuum degree to 15Pa, and reacting for 4.0h to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol tetracyclic glycol copolyester with the structure shown in formula (XVIII), wherein the intrinsic viscosity is 0.66dL/g, the glass transition temperature is 138 ℃, and the visible light transmittance at 700nm cutoff is 86%.

The formula (XVIII) is shown in the specification, wherein x, y and m are integers from 1 to 10, and z is an integer from 10 to 100.

Example 28

Adding terephthalic acid, dihydroxyethoxy polycyclic aromatic hydrocarbon and ethylene glycol into a reactor according to the molar ratio of 1:0.10:2.1, then adding anhydrous zinc acetate with the molar weight of dimethyl terephthalate of 0.3 per thousand, gradually heating to 260 ℃ under the protection of nitrogen, reacting for 1.5 hours, then adding antimony trioxide with the molar weight of dimethyl terephthalate of 3.0 per thousand and phosphorous acid of 5.0 per thousand, gradually heating to 300 ℃, reducing the vacuum degree to 100Pa, and reacting for 1.5 hours to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol copolyester of the terephthalic acid, wherein the structure is shown in formula (III), the intrinsic viscosity is 0.60dL/g, the glass transition temperature is 96 ℃, and the visible light transmittance at 700nm is 88%.

Example 29

Adding terephthalic acid, dihydroxyethoxy polycyclic aromatic hydrocarbon and ethylene glycol into a reactor according to the molar ratio of 1:0.10:2.1, then adding anhydrous zinc acetate with the molar weight of dimethyl terephthalate of 3.0 thousandths, gradually heating to 160 ℃ under the protection of nitrogen, reacting for 5.0 hours, then adding antimony trioxide with the molar weight of dimethyl terephthalate of 0.3 thousandths and phosphorous acid with the molar weight of 0.4 thousandths, gradually heating to 260 ℃, reducing the vacuum degree to 15Pa, and reacting for 6.0 hours to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol copolyester of the terephthalic acid, wherein the structure is shown in formula (III), the intrinsic viscosity is 0.66dL/g, the glass transition temperature is 97 ℃, and the visible light transmittance at 700nm is 89%.

Comparative example 1

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 1.0 thousandth of dimethyl terephthalate, gradually heating to 185 ℃ under the protection of nitrogen, reacting for 4.0h, then adding antimony trioxide with the molar weight of 0.8 thousandth of dimethyl terephthalate and 1.0 thousandth of diphenyl phosphite, gradually heating to 282 ℃, reducing the vacuum degree to 50Pa, and reacting for 3.5h to obtain the polyethylene glycol terephthalate, wherein the intrinsic viscosity of the polyethylene glycol terephthalate is 0.75dL/g, the glass transition temperature of the polyethylene glycol terephthalate is 70 ℃, and the visible light transmittance at 700nm cut-off is 90%.

Comparative example 2

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

the intrinsic viscosity of the obtained copolyester is 0.70dL/g, the glass transition temperature is 72 ℃, and the visible light transmittance at 700nm cutoff is 80%.

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.

When the high glass transition temperature and high transparency polyester obtained by the above embodiments of the present invention is used, the polyester can be processed into a desired polyester product by processes of extrusion granulation, injection molding, extrusion molding, weaving, etc. according to the requirements of practical application in a manner known in the art. For example:

example 30: the poly (ethylene terephthalate) dihydroxy ethoxy polycyclic aromatic hydrocarbon 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 cylinder temperature is 275-285 deg.C, and the die head temperature is 280-290 deg.C. 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 278-285 ℃, the dwell time is 5-10 s, and 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 31: the poly (hydroxyethoxy) polycyclic aromatic hydrocarbon ethylene glycol copolyester obtained in example 2 and an antioxidant 1010 were mixed according to a 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 60-100 kg/cm²(ii) a The extrusion temperature is 275-285 ℃; the cooling temperature is 15-25 ℃; the winding speed is 2000 m/min; the swell ratio of the spun melt was 1.15. The polyester fiber yarn prepared by the method has higher tensile strength and elongation at break.

Example 32: feeding the poly (p-phenyleneterephthalate) dihydroxy ethoxy polycyclic aromatic hydrocarbon ethylene glycol copolyester obtained in the embodiment 1 into a single screw extruder, carrying out melt extrusion at 270-285 ℃, casting a molten fluid on a rotating cooling roller to obtain a casting thick sheet with the thickness of 1500-5500 microns, preheating the casting thick sheet to 105-115 ℃, longitudinally stretching the casting thick sheet by 3-4 times, then preheating to 105-115 ℃, transversely stretching by 3-4.5 times, and carrying out heat setting at 80-110 ℃ 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.

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 high glass transition temperature and high transparency polyester, characterized in that the high glass transition temperature and high transparency polyester has the structure shown in formula (I):

Formula (I)

Wherein, x and y are both integers from 1 to 10, z is an integer from 10 to 100, R is the residue of a dihydric alcohol with 2 to 20 carbon atoms, and the dihydric alcohol is selected from ethylene glycol and the following A combination of any of the structures:

The glass transition temperature of the high glass transition temperature and high transparency polyester is 90-160° C., and the visible light transmittance at the cut-off wavelength of 700 nm is greater than 85%.

2. a preparation method of high glass transition temperature high transparent polyester is characterized in that comprising:

The first mixed reaction system containing bis-hydroxyethoxy polycyclic aromatic hydrocarbons, terephthalic acid or its esters, glycols, esterification or transesterification catalysts is reacted at 160-260 ° C for 1.5-5.0 h to obtain an intermediate product ;

The second mixed reaction system comprising the intermediate product, the polycondensation catalyst and the stabilizer is reacted for 1.5 to 6.0 h under the conditions that the temperature is 260-300 ° C and the vacuum degree is below 200 Pa, so as to obtain the high-temperature reaction system as claimed in claim 1. High glass transition temperature transparent polyester;

Wherein, the bishydroxyethoxy polycyclic aromatic hydrocarbon has the structure shown in formula (II):

;

The dihydric alcohol is selected from the combination of ethylene glycol and any of the following structures:

.

3 . The preparation method according to claim 2 , wherein the molar ratio of the bishydroxyethoxy polycyclic aromatic hydrocarbon to terephthalic acid or its ester product is 5-90:100. 4 .

4 . The preparation method according to claim 2 , wherein the molar ratio of the combination of the dihydric alcohol and bishydroxyethoxy polycyclic aromatic hydrocarbon to terephthalic acid or its ester product is 1.2-3.0:1. 5 .

5 . The preparation method according to claim 2 , wherein the molar ratio of the esterification or transesterification catalyst to terephthalic acid or its ester product is 0.3 to 3:1000. 6 .

6 . The preparation method according to claim 2 , wherein the molar ratio of the polycondensation catalyst to terephthalic acid or its ester product is 0.3 to 3:1000. 7 .

7 . The preparation method according to claim 2 , wherein the molar ratio of the stabilizer to terephthalic acid or its ester compound is 0.4 to 5:1000. 8 .

8 . The preparation method according to claim 2 , wherein the esterification or transesterification catalyst is selected from any one or two or more of zinc-based catalysts, manganese-based catalysts, titanium-based catalysts, and antimony-based catalysts. 9 . The combination;

And/or, the polycondensation catalyst is selected from any one or a combination of two or more of titanium-based catalysts, tin-based catalysts, antimony-based catalysts, and germanium-based catalysts;

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

9 . The preparation method according to claim 8 , wherein: the zinc-based catalyst is zinc acetate; or the manganese-based catalyst is manganese acetate; or the titanium-based catalyst is selected from tetrabutyl titanate , any one or a combination of two or more of isopropyl titanate, titanium dioxide, and inorganic supported titanium catalysts; or, the antimony-based catalyst is selected from antimony trioxide, antimony ethylene glycol, antimony acetate, polyethylene glycol Any one or a combination of two or more in the antimony alkoxide; or, the tin-based catalyst is selected from any one or two of dibutyl tin oxide, stannous isooctate, monobutyl tin triisooctoate, and dioctyl tin oxide. more than one combination; or, the germanium-based catalyst is selected from any one or a combination of two of germanium dioxide and germanium oxide.

10. The high glass transition temperature and high transparent polyester of claim 1 is used in the preparation of fire fighting equipment, baby bottles, water cups, kitchen appliances, food packaging materials, hot-filling beverage bottles, optical base films, decorative materials or auto parts Applications.

11. A method for preparing polyester granules, characterized by comprising: inputting the high glass transition temperature and high transparency polyester of claim 1 into a co-rotating twin-screw extruder for melt extrusion and granulation; wherein, The working parameters of the co-rotating twin-screw extruder include: the temperature of the barrel is 275°C to 295°C, and the temperature of the die head is 280°C to 295°C.

12. A processing method of polyester film, characterized in that it comprises:

The high glass transition temperature and high transparency polyester of claim 1 is fed into a twin-screw extruder, melted and extruded at 270°C to 295°C, the temperature of the melt transfer pump is 275 to 295°C, and the molten fluid is cast to On a rotating cooling drum, a cast thick sheet with a thickness of 1500 μm to 5500 μm is obtained;

The cast slab is preheated to 85-170°C and then stretched 3-4 times longitudinally, then preheated to 85-170°C again and stretched 3-4.5 times laterally to obtain a polyester film.

13. A multilayer composite film, characterized in that it comprises a first structural layer and a second structural layer that are stacked in sequence, the first structural layer and the second structural layer are bonded and combined, and the first structural layer is A film formed of the high glass transition temperature and high transparency polyester of claim 1.