CN112574399B

CN112574399B - High-temperature-resistant polycyclic aromatic hydrocarbon polyester hollow container and preparation method thereof

Info

Publication number: CN112574399B
Application number: CN202110213178.4A
Authority: CN
Inventors: 王静刚; 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: 2021-05-07
Anticipated expiration: 2041-02-26
Also published as: CN112574399A

Abstract

The invention discloses a high-temperature-resistant polycyclic aromatic hydrocarbon polyester hollow container and a preparation method thereof. The preparation method comprises the following steps: inputting polycyclic aromatic hydrocarbon polyester into an injection molding machine for injection molding, wherein the working parameters of the injection molding machine comprise: the temperature of the charging barrel is 260-290 ℃, the temperature of the die head is 260-290 ℃, the temperature of the die is 25-60 ℃, and the injection pressure is 30-150 MPa, so that the high-temperature-resistant polycyclic aromatic hydrocarbon polyester hollow container is prepared. The polycyclic aromatic hydrocarbon polyester is prepared by copolymerizing dihydroxyethoxy polycyclic aromatic hydrocarbon, terephthalic acid or an esterified product thereof and dihydric alcohol. The high-temperature-resistant polycyclic aromatic hydrocarbon polyester hollow container prepared by the invention has the heat deformation temperature of 95-160 ℃, has excellent performances of high transparency, high toughness and the like, and can be widely applied to the fields of baby feeding bottle bodies, water cups, kitchen electrical products, hot-filling beverage bottles, medical containers and the like.

Description

High-temperature-resistant polycyclic aromatic hydrocarbon polyester hollow container and preparation method thereof

Technical Field

The invention relates to a product, in particular to a high-temperature-resistant polycyclic aromatic hydrocarbon polyester hollow container and a preparation method and application thereof, and belongs to the technical field of high polymer material products.

Background

Polyethylene terephthalate (PET) has excellent performances such as high transparency, solvent resistance and impact resistance, the glass transition temperature of a hollow container prepared from the polyethylene terephthalate (PET) is only 70 ℃ respectively, the heat-resistant temperature is low, and the hollow container is subjected to thermal deformation when encountering boiling water and cannot be used in the fields of hollow containers such as a baby feeding bottle cup body, a water cup, kitchen electrical products (a stirring cup cold cup of a wall-breaking food processor, a portable fruit juice mixer stirring cup, a juice extractor juicing barrel of a juice extractor, a noodle mixer stirring cup and the like), a hot-filling beverage bottle, medical appliances and the like.

Disclosure of Invention

The invention mainly aims to provide a high-temperature-resistant polycyclic aromatic hydrocarbon polyester hollow container to overcome the defect of insufficient heat resistance of the conventional polyester hollow container.

The invention also aims to provide a preparation method of the high-temperature-resistant polycyclic aromatic hydrocarbon polyester hollow container.

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

the embodiment of the invention provides a high-temperature-resistant polycyclic aromatic hydrocarbon polyester hollow container which has a hollow structure, is mainly prepared from polycyclic aromatic hydrocarbon polyester, and comprises the following components in parts by weight:

component (a) comprising a bishydroxyethoxy polycyclic aromatic hydrocarbon;

component (b), terephthalic acid or an esterified product thereof; and

component (c), a glycol comprising a cyclic glycol and/or an aliphatic glycol;

the dihydroxyethoxy polycyclic aromatic hydrocarbon has a structure as shown in any one of formula (1) to formula (4):

。

in some embodiments, the cyclic diol comprises any one or a combination of two or more of 1, 4-cyclohexanedimethanol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, tricyclodecanedimethanol, and the like.

Further, the heat distortion temperature of the high-temperature resistant polycyclic aromatic hydrocarbon polyester hollow container is 95-160 ℃.

Further, the visible light transmittance of the high-temperature-resistant polycyclic aromatic hydrocarbon polyester hollow container is 88-92% when the wavelength is cut off at 700 nm.

Further, the high-temperature-resistant polycyclic aromatic hydrocarbon polyester hollow container can be used for a feeding bottle body, a water cup, a kitchen electrical product, a hot-filling beverage bottle or a medical container and the like, but is not limited thereto.

The embodiment of the invention also provides a preparation method of the high-temperature-resistant polycyclic aromatic hydrocarbon polyester hollow container, which comprises the following steps:

inputting polycyclic aromatic hydrocarbon polyester into an injection molding machine for injection molding, wherein the working parameters of the injection molding machine comprise: the temperature of the charging barrel is 260-290 ℃, the temperature of the die head is 260-290 ℃, the temperature of the die is 25-60 ℃, and the injection pressure is 30-150 MPa, so that the high-temperature-resistant polycyclic aromatic hydrocarbon polyester hollow container is prepared.

In some embodiments, the method of making the high temperature resistant polycyclic aromatic hydrocarbon polyester comprises:

reacting a first mixed reaction system containing dihydroxyethoxy polycyclic aromatic hydrocarbon, terephthalic acid or an esterified product thereof, dihydric alcohol and an esterification or ester exchange catalyst at 160-240 ℃ to obtain an intermediate product;

reacting a second mixed reaction system containing the intermediate product, a polycondensation catalyst and a stabilizer at 260-290 ℃ under a vacuum condition to obtain high-temperature-resistant polycyclic aromatic hydrocarbon polyester;

。

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

1) according to the embodiment of the invention, the high-temperature resistant polycyclic aromatic hydrocarbon polyester hollow container is prepared by synthesizing novel dihydroxy ethoxy polycyclic aromatic hydrocarbon, terephthalic acid or esterified matters thereof and dihydric alcohol copolyester, and the heat-resistant temperature of the novel hollow container can reach 95-160 ℃;

2) in the resin of the novel high-temperature-resistant polycyclic aromatic hydrocarbon polyester hollow container provided by the embodiment of the invention, alicyclic diol is adopted to partially replace aliphatic diol, and the alicyclic diol is utilized to absorb energy through conformational transition when the copolyester is impacted by external force, so that the toughness of the copolyester is effectively improved, and the copolyester has excellent elongation at break when being stretched; meanwhile, the space non-planar structure of the alicyclic dihydric alcohol further prevents the crystallization of the copolyester and improves the transparency of the copolyester, so that the prepared hollow container has excellent performances of high transparency, high toughness and the like;

3) the high-temperature-resistant polycyclic aromatic hydrocarbon polyester hollow container provided by the embodiment of the invention is widely applied to the fields of baby feeding bottle bodies, water cups, kitchen electrical products (stirring cup cold cups of wall breaking machines, stirring cups of portable fruit juice machines, juice extracting barrels of juice extracting machines, stirring cups of noodle machines and the like), hot-filling beverage bottles, medical containers 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 (bis-hydroxyethoxy) polycyclic aromatic hydrocarbon ethylene glycol 1, 4-cyclohexanedimethanol copolyester prepared in example 1 of the present invention¹An H-NMR spectrum;

FIG. 2 is a DSC chart of poly (bis-hydroxyethoxy) polycyclic aromatic hydrocarbon ethylene glycol 1, 4-cyclohexanedimethanol copolyester prepared in example 1 of the present invention.

Detailed Description

As described above, in view of the defects of the prior art, the inventors of the present invention have made extensive studies and practice to provide a technical solution of the present invention, which is to prepare a high temperature resistant polycyclic aromatic hydrocarbon polyester hollow container by synthesizing a novel dihydroxy ethoxy polycyclic aromatic hydrocarbon, terephthalic acid or its esterified product, and a diol copolyester. 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.

An aspect of an embodiment of the present invention provides a high temperature resistant polycyclic aromatic hydrocarbon polyester hollow container, which has a hollow structure, and is mainly prepared from polycyclic aromatic hydrocarbon polyester, and a composition for synthesizing the polycyclic aromatic hydrocarbon polyester includes:

component (a) comprising a bishydroxyethoxy polycyclic aromatic hydrocarbon;

component (b), terephthalic acid or an esterified product thereof; and

component (c), a glycol comprising a cyclic glycol and/or an aliphatic glycol;

。

the structure of the dihydroxyethoxy polycyclic aromatic hydrocarbon adopted by the invention has a plurality of benzene rings, the structural rigidity is high, and meanwhile, the dihydroxyethyl polycyclic aromatic hydrocarbon has high-activity hydroxyethyl and freely-rotating oxygen-ether bonds. The rigid structure of the dihydroxyethoxy polycyclic aromatic hydrocarbon can obviously improve the glass transition temperature of the copolyester, the structural primary hydroxyl group of the dihydroxyethoxy polycyclic aromatic hydrocarbon has high reaction activity and can efficiently generate esterification or ester exchange reaction with terephthalic acid or an esterified product thereof, so that the copolyester with high molecular weight can be obtained, the free rotation of the oxyalkane bond can also increase the free activity of the terminal hydroxyl group, reduce the steric hindrance and be beneficial to improving the molecular weight of the copolyester; meanwhile, alicyclic dihydric alcohol such as cyclohexane dimethanol and the like which is added has higher rigidity and a spatial non-planar structure than ethylene glycol, so that the heat resistance of the copolyester is further improved, the conformational transition of the alicyclic dihydric alcohol provides better toughness of the copolyester, the efficient synergy on the copolyester structure is realized, and the copolyester achieves high molecular weight, high toughness and high transparency.

In some embodiments, the cyclic diol includes any one or a combination of two or more of 1, 4-cyclohexanedimethanol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, tricyclodecanedimethanol, and the like, but is not limited thereto.

In some embodiments, the aliphatic diol includes any one or a combination of two or more of ethylene glycol, propylene glycol, butylene glycol, and the like, but is not limited thereto.

In some embodiments, the molar ratio of component (a) to component (b) is from 5 to 80: 100.

Further, the molar ratio of the combination of component (a) and component (c) to component (b) is 120-300: 100.

Further, the terephthalate includes dimethyl terephthalate, but is not limited thereto.

That is, in another aspect, the resin for preparing the high temperature resistant polycyclic aromatic hydrocarbon polyester hollow container is polycyclic aromatic hydrocarbon polyester, and the composition for preparing polycyclic aromatic hydrocarbon polyester comprises the following components:

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

a component (b): terephthalic acid or an esterified product thereof; and

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

wherein, calculated as the molar amount of component (b);

the content of the component (a) is 5-80 mol%;

the content of the component (a) and the component (c) is 120-300 mol%.

In some embodiments, the high temperature resistant polycyclic aromatic hydrocarbon polyester hollow container is formed by compounding polycyclic aromatic hydrocarbon polyester and polymer, and other polymers compounded with polycyclic aromatic hydrocarbon polyester include any one or combination of more than two of polypropylene, polyether ether sulfone, polyether sulfone, polyamide and other polymers, but not limited thereto.

In some embodiments, the high temperature resistant polycyclic aromatic hydrocarbon polyester hollow container has a heat distortion temperature of 95 to 160 ℃.

Further, the visible light transmittance of the high-temperature-resistant polycyclic aromatic hydrocarbon polyester hollow container is 88-92% when the wavelength is cut off at 700 nm. And the hollow container is not broken when falling 1m away from the ground.

Furthermore, the high-temperature-resistant polycyclic aromatic hydrocarbon polyester hollow container has excellent performances such as high transparency and high toughness.

Further, the high temperature resistant polycyclic aromatic hydrocarbon polyester hollow container can be used for a baby feeding bottle body, a water cup, a kitchen electrical product (such as a stirring cup cold cup of a broken wall food processor, a stirring cup of a carry-on fruit juice extractor, a juice extracting barrel of a juice extractor, a stirring cup of a noodle maker and the like), a hot filling beverage bottle, a medical container and the like.

Another aspect of the embodiments of the present invention also provides a method for preparing a high temperature resistant polycyclic aromatic hydrocarbon polyester hollow container, including: at least adopting any one mode of injection molding and the like to prepare the polycyclic aromatic hydrocarbon polyester into a required hollow container product.

In some embodiments, a method of making the high temperature resistant polycyclic aromatic hydrocarbon polyester hollow container comprises:

In some embodiments, a method of making the high temperature resistant polycyclic aromatic hydrocarbon polyester comprises:

。

in some embodiments, the method of making comprises: bisphenol polycyclic aromatic hydrocarbon, ethylene carbonate and alkali metal carbonate are mixed according to the proportion of 1: 2.01-2.10: uniformly mixing the materials according to a molar ratio of 0.001-0.005 to form a mixture, and reacting the mixture at 150-250 ℃ for 1-5 hours to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon;

the bisphenol polycyclic aromatic hydrocarbon has a structure as shown in any one of a formula (5) to a formula (8):

。

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 1, 4-cyclohexanedimethanol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, tricyclodecanedimethanol, 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, and the like, but is not limited thereto.

In some embodiments, the method of making specifically comprises:

reacting the first mixed reaction system at 160-240 ℃ for 2.0-6.0 h under a protective atmosphere to obtain an intermediate product; and the number of the first and second groups,

and (3) reacting the second mixed reaction system for 1.5-6 h under the conditions that the temperature is 260-290 ℃ and the vacuum degree is less than 200Pa, so as to obtain the polycyclic aromatic hydrocarbon polyester.

In some embodiments, the method for preparing the high temperature resistant polycyclic aromatic hydrocarbon polyester resin specifically comprises: under a protective atmosphere, reacting dihydroxy ethoxy polycyclic aromatic hydrocarbon, terephthalic acid or an esterified product thereof, dihydric alcohol, an esterification or ester exchange catalyst for 2.0-6.0 h at 160-240 ℃ to obtain a first reaction mixture; and reacting the first reaction mixture for 1.5-6 hours under the action of a polycondensation catalyst and a stabilizer under the conditions that the temperature is 260-290 ℃ and the vacuum degree is below 200Pa, so as to obtain the polycyclic aromatic hydrocarbon polyester.

In some embodiments, the molar ratio of the bis-hydroxyethoxy polycyclic aromatic hydrocarbon to the terephthalic acid or the esterified product thereof is 5 to 80:100, i.e., in other words, the bis-hydroxyethoxy polycyclic aromatic hydrocarbon is 5 to 80mol% based on the molar amount of the terephthalic acid or the esterified product thereof.

In some embodiments, the molar ratio of the combination of the bishydroxyethoxy polycyclic aromatic hydrocarbon and the diol to the terephthalic acid or esterified product thereof is 120 to 300: 100; that is, in another aspect, the amount of the combination of the bis-hydroxyethoxy polycyclic aromatic hydrocarbon and the diol is 120mol% to 300mol% based on the molar amount of the terephthalic acid or the esterified product thereof.

In some embodiments, the molar ratio of the esterification or transesterification catalyst to the terephthalic acid or esterified product thereof is from 0.5 to 2.0: 1000.

In some embodiments, the molar ratio of the polycondensation catalyst to the terephthalic acid or its esterified product is 0.5 to 2.0: 1000.

In some embodiments, the molar ratio of the stabilizer to the terephthalic acid or its esters is 0.4 to 3.0: 1000.

That is, in terms of the molar amount of terephthalic acid or an esterified product thereof, the content of the esterification or transesterification catalyst is 0.5 mol% to 2.0 mol%, the content of the polycondensation catalyst is 0.5 mol% to 2.0 mol%, and the content of the stabilizer is 0.4 mol% to 3.0 mol%.

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, a tin-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 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.

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 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.

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.

In some embodiments, the method of making further comprises: the polycyclic aromatic hydrocarbon polyester is dried for 4-12 hours at the temperature of 80-130 ℃, and then the dried polycyclic aromatic hydrocarbon polyester is input into an injection molding machine for injection molding.

In some embodiments, the method of making further comprises: compounding polycyclic aromatic hydrocarbon polyester with polymer, inputting the obtained mixture into an injection molding machine for injection molding, wherein the other polymer compounded with the polycyclic aromatic hydrocarbon polyester comprises any one or combination of more than two of polymers such as polypropylene, polyether ether sulfone, polyether sulfone, polyamide and the like, but is not limited to the above.

In some more preferred embodiments, the processing method of the high-temperature resistant polycyclic aromatic hydrocarbon polyester hollow container specifically comprises the following steps:

(1) drying the high-temperature-resistant polycyclic aromatic hydrocarbon polyester resin by hot air at the temperature of 80-130 ℃ for 4-12 h;

(2) and adding the dried high-temperature-resistant polycyclic aromatic hydrocarbon polyester resin into an injection molding machine, wherein the temperature of a charging barrel of the injection molding machine is 260-290 ℃, the temperature of a die head of the injection molding machine is 260-290 ℃, the temperature of a die is 25-60 ℃, and the injection pressure is 30-150 MPa, and performing injection molding to obtain the high-temperature-resistant polycyclic aromatic hydrocarbon polyester hollow container.

Therefore, compared with the existing PET polyester, the dihydroxy ethoxy polycyclic aromatic hydrocarbon modified copolyester has excellent performances of high glass transition temperature, high transparency and elongation at break, and the high-temperature-resistant polycyclic aromatic hydrocarbon polyester hollow container prepared by the invention can be widely applied to the bodies of baby feeding bottles, water cups, kitchen electrical products (cold cups of stirring cups of wall breaking machines, stirring cups of portable fruit juice machines, juice extracting barrels of juice extracting machines, stirring cups of noodle machines and the like), hot-filling beverage bottles, medical containers and the like.

For another example, another aspect of the embodiments of the present invention also provides a container, a container wall of which has a multilayer composite film structure, the multilayer composite film structure includes a first structural layer and a second structural layer which are sequentially stacked, the first structural layer and the second structural layer are bonded, and the first structural layer is a film made of a polycyclic aromatic hydrocarbon polyester, and a composition for synthesizing the polycyclic aromatic hydrocarbon polyester includes:

component (a) comprising a bishydroxyethoxy polycyclic aromatic hydrocarbon;

component (b), terephthalic acid or an esterified product thereof; and

component (c), a glycol comprising a cyclic glycol and/or an aliphatic glycol;

。

the structures of the terephthalic acid or the esterified product thereof and the dihydric alcohol are as described above, and are not described herein again.

The second structural layer can be formed by inorganic materials, organic materials or composite materials thereof. The multilayer composite film can be applied to a body of a baby bottle, a water cup, a kitchen appliance, a hot-fill beverage bottle, a medical container and the like, but is not limited thereto.

By the technical scheme, in the resin of the novel high-temperature-resistant polycyclic aromatic hydrocarbon polyester hollow container provided by the embodiment of the invention, alicyclic diol is adopted to partially replace aliphatic diol, and the alicyclic diol is utilized to absorb energy by conformational transition when the copolyester is impacted by external force, so that the toughness of the copolyester is effectively improved, and the copolyester has excellent elongation at break when stretched; meanwhile, the space non-planar structure of the alicyclic dihydric alcohol further prevents the crystallization of the copolyester and improves the transparency of the copolyester, so that the prepared hollow container has excellent performances of high transparency, high toughness and the like; the prepared high-temperature-resistant polycyclic aromatic hydrocarbon polyester hollow container has the heat deformation temperature of 95-160 ℃, has excellent performances of high transparency, high toughness and the like, and can be widely applied to the fields of baby feeding bottle bodies, water cups, kitchen electrical products, hot-filling beverage bottles, medical containers 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 ℃. 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 ℃.

In the following embodiments, the bishydroxyethoxy polycyclic aromatic hydrocarbon can be prepared by the following steps:

bisphenol polycyclic aromatic hydrocarbon (formula (5) - (formula (8)), ethylene carbonate and alkali metal carbonate are mixed according to the proportion of 1: 2.01-2.10: 0.001-0.005, and reacting the mixture at 150-250 ℃ for 1-5 hours to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon.

Example 1

The method comprises the following steps of (1) drying the polyhydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 4-cyclohexanedimethanol copolyester of the poly (terephthalic acid) at 90 ℃ for 8 hours by hot air; and adding the dried resin into an injection molding machine, wherein the temperature of a first zone of a screw of the injection molding machine is 278 ℃, the temperature of a second zone is 278 ℃, the temperature of a third zone is 278 ℃, the temperature of a fourth zone is 280 ℃, the temperature of a die head is 280 ℃, the temperature of a die is 30 ℃, the injection pressure is 50MPa, and the hollow cup body with the diameter of 70mm, the height of 168mm and the thickness of 2.5mm is obtained by injection molding. The hollow cup body has the cut-off of 700nm, the visible light transmittance is 89%, and the hollow cup body does not crack when falling 1m away from the ground.

Wherein x, y and z are integers from 1 to 10, and m is an integer from 10 to 100.

The formula and the synthesis method of the poly (p-phenylene terephthalate) bis-hydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 4-cyclohexanedimethanol resin are as follows: dimethyl terephthalate, dihydroxy ethoxy polycyclic aromatic hydrocarbon (2), ethylene glycol and 1, 4-cyclohexaneAdding dimethyl alkane into a reactor according to the molar ratio of 1:0.30:2.4:0.30, then adding anhydrous zinc acetate of an ester exchange catalyst with the molar weight of dimethyl terephthalate of 0.8 per thousand, gradually heating to 180 ℃ under the protection of nitrogen for esterification, reacting for 4.0 hours, then adding a polycondensation catalyst antimony trioxide with the molar weight of dimethyl terephthalate of 1.0 per thousand, adding a stabilizer trimethyl phosphate of 1.0 per thousand, gradually heating to 280 ℃, gradually reducing the vacuum degree to 40Pa, and reacting for 3.0 hours to obtain the dihydroxy ethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 4-cyclohexanedimethanol copolyester with the intrinsic viscosity of 0.76dL/g and nuclear magnetism of the copolyester¹H-NMR is shown in FIG. 1, DSC curve is shown in FIG. 2, and glass transition temperature is 124 ℃.

Example 2

The method comprises the following steps of (1) drying the polyhydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 3-cyclohexanedimethanol copolyester of the poly (terephthalic acid) by hot air for 6 hours at 120 ℃, wherein the structure is shown as a formula (10); and then adding the dried resin into an injection molding machine, wherein the temperature of a first region of a screw is 278 ℃, the temperature of a second region of the screw is 280 ℃, the temperature of a third region of the screw is 280 ℃, the temperature of a fourth region of the screw is 280 ℃, the temperature of a die head of the screw is 40 ℃, the injection pressure of the screw is 40MPa, and the hollow cup body with the diameter of 70mm, the height of 168mm and the thickness of 2.5mm is obtained through injection molding. The hollow cup body is cut off at 700nm, the visible light transmittance is 90%, and the hollow cup body does not crack when falling 1m away from the ground.

The synthesis method of the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 3-cyclohexanedimethanol copolyester of the terephthalic acid comprises the following steps: adding dimethyl terephthalate, dihydroxyethoxy polycyclic aromatic hydrocarbon (2), ethylene glycol and 1, 3-cyclohexanedimethanol into a reactor according to the molar ratio of 1:0.40:2.1:0.2, then adding an ester exchange catalyst of 0.7 thousandth of the molar weight of the dimethyl terephthalate, gradually heating to 190 ℃ under the protection of nitrogen for esterification, reacting for 3.0h, then adding a polycondensation catalyst of 0.8 thousandth of the molar weight of the dimethyl terephthalate, antimony trioxide and 2.0 thousandth of stabilizer trimethyl phosphate, gradually heating to 282 ℃, gradually reducing the vacuum degree to 20Pa, and reacting for 2.5h to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 3-cyclohexanedimethanol copolyester of the polyethylene terephthalate, wherein the intrinsic viscosity of the copolyester is 0.81dL/g, and the glass transition temperature is 130 ℃.

Example 3

The method comprises the following steps of (1) drying the polyhydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 2-cyclohexanedimethanol copolyester of the poly (terephthalic acid) at 100 ℃ for 7 hours by hot air; and then adding the dried resin into an injection molding machine, wherein the temperature of a screw rod of the injection molding machine in a first area is 276 ℃, the temperature of a screw rod of the injection molding machine in a second area is 278 ℃, the temperature of a screw rod of the injection molding machine in a third area is 278 ℃, the temperature of a die head of the injection molding machine in a fourth area is 280 ℃, the temperature of a die head of the injection molding machine is 278 ℃, the temperature of a die is 60 ℃. The hollow cup body has a cut-off of 700nm, a visible light transmittance of 92 percent, and no fracture when falling 1m away from the ground.

The formula and the synthesis method of the poly (p-phenylene terephthalate) dihydroxy ethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 2-cyclohexanedimethanol resin are as follows: adding terephthalic acid, dihydroxyethoxy polycyclic aromatic hydrocarbon (2), ethylene glycol and 1, 2-cyclohexanedimethanol into a reactor according to the molar ratio of 1:0.30:2.1:0.20, then adding an ester exchange catalyst of 0.6 thousandth of the molar weight of dimethyl terephthalate, gradually heating to 240 ℃ under the protection of nitrogen for esterification, reacting for 6.0h, then adding a polycondensation catalyst of 0.6 thousandth of the molar weight of dimethyl terephthalate, antimony trioxide and 1.5 thousandth of stabilizer trimethyl phosphate, gradually heating to 290 ℃, gradually reducing the vacuum degree to 10Pa, and reacting for 1.5h to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 2-cyclohexanedimethanol copolyester of the polyethylene terephthalate, wherein the intrinsic viscosity of the copolyester is 0.70dL/g, and the glass transition temperature of the copolyester is 120 ℃.

Example 4

The method comprises the following steps of (1) drying the poly (p-phenylenetereoxy) polycyclic aromatic hydrocarbon ethylene glycol tricyclodecane dimethanol copolyester with the structure as formula (12) by hot air at 95 ℃ for 6.5 h; and then adding the dried resin into an injection molding machine, wherein the temperature of a screw rod of the injection molding machine in a first area is 284 ℃, the temperature of a screw rod of the injection molding machine in a second area is 285 ℃, the temperature of a screw rod of the injection molding machine in a third area is 285 ℃, the temperature of a die head of the injection molding machine in a fourth area is 285 ℃, the temperature of the die head of the injection molding machine is 284 ℃, the temperature of the die is 50 ℃. The hollow cup body is cut off at 700nm, the visible light transmittance is 89%, and the hollow cup body does not crack when falling 1m away from the ground.

The formula and the synthesis method of the dihydroxy ethoxy polycyclic aromatic hydrocarbon ethylene glycol tricyclodecane dimethanol polyterephthalate resin are as follows: adding dimethyl terephthalate, dihydroxyethoxy polycyclic aromatic hydrocarbon (2), ethylene glycol and tricyclodecane dimethanol into a reactor according to the molar ratio of 1:0.30:2.1:0.3, then adding an ester exchange catalyst of 1.2 thousandth of the molar weight of dimethyl terephthalate, gradually heating to 195 ℃ under the protection of nitrogen for esterification, reacting for 2.0h, then adding a polycondensation catalyst of ethylene glycol antimony of 1.8 thousandth of the molar weight of dimethyl terephthalate and stabilizer dimethyl phosphate of 2.5 thousandth, gradually heating to 285 ℃, gradually reducing the vacuum degree to 100Pa, and reacting for 6.0h to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 4-cyclohexanedimethanol copolyester, wherein the intrinsic viscosity of the copolyester is 0.78dL/g, and the glass transition temperature is 128 ℃.

Example 5

Mixing poly (p-phenyleneterephthalate) dihydroxy ethoxy polycyclic aromatic hydrocarbon ethylene glycol tricyclodecane dimethanol copolyester with polypropylene according to the mass ratio of 80:20, and drying the mixed resin by hot air at 90 ℃ for 6.0 h; and then adding the dried mixed resin into an injection molding machine, wherein the temperature of a screw rod of the injection molding machine in a first area is 285 ℃, the temperature of a screw rod of the injection molding machine in a second area is 285 ℃, the temperature of a screw rod of the injection molding machine in a third area is 285 ℃, the temperature of a die head of the injection molding machine in a fourth area is 285 ℃, the temperature of a die head of the injection molding machine is 284 ℃, the temperature of the die is 45 ℃, and the. The cut-off of the hollow container is 700nm, the visible light transmittance is 91%, and the hollow container does not crack when falling 1m away from the ground.

The formula and the synthesis method of the dihydroxy ethoxy polycyclic aromatic hydrocarbon ethylene glycol tricyclodecane dimethanol polyterephthalate resin are as follows: adding dimethyl terephthalate, dihydroxyethoxy polycyclic aromatic hydrocarbon (2), ethylene glycol and tricyclodecane dimethanol into a reactor according to the molar ratio of 1:0.05:2.1:0.4, then adding an ester exchange catalyst of 1.0 thousandth of the molar weight of dimethyl terephthalate, anhydrous manganese acetate, gradually heating to 180 ℃ under the protection of nitrogen for esterification, reacting for 4.0h, then adding a polycondensation catalyst of ethylene glycol antimony of 1.5 thousandth of the molar weight of dimethyl terephthalate and a stabilizer of dimethyl phosphate of 1.5 thousandth, gradually heating to 280 ℃, and gradually reducing the vacuum degree to 50Pa, reacting for 3.5h to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 4-cyclohexanedimethanol copolyester, wherein the intrinsic viscosity of the copolyester is 0.94dL/g, and the glass transition temperature is 96 ℃.

Example 6

The method comprises the following steps of (1) drying the polyhydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 4-cyclohexanedimethanol copolyester of the poly (terephthalic acid) by hot air for 10 hours at the temperature of 80 ℃, wherein the structure is shown as a formula (13); and then adding the dried resin into an injection molding machine, wherein the temperature of a screw rod of the injection molding machine in a first area is 282 ℃, the temperature of a screw rod of the injection molding machine in a second area is 282 ℃, the temperature of a screw rod of the injection molding machine in a third area is 282 ℃, the temperature of a die head of the injection molding machine in a fourth area is 282 ℃, the temperature of the die head of the injection molding machine is 35 ℃, and the injection pressure. The hollow cup body is cut off at 700nm, the visible light transmittance is 90%, and the hollow cup body does not crack when falling 1m away from the ground.

The formula and the synthesis method of the dihydroxy ethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 4-cyclohexanedimethanol resin are as follows: adding dimethyl terephthalate, dihydroxyethoxy polycyclic aromatic hydrocarbon (1), ethylene glycol and 1, 4-cyclohexanedimethanol into a reactor according to the molar ratio of 1:0.80:2.1:0.20, then adding anhydrous zinc acetate of an ester exchange catalyst with the molar weight of 1.5 thousandth of dimethyl terephthalate, gradually heating to 185 ℃ under the protection of nitrogen for esterification for 5 hours, then adding a polycondensation catalyst antimony acetate with the molar weight of 2.0 thousandth of dimethyl terephthalate and 3.0 thousandth of stabilizer trimethyl phosphate, gradually heating to 286 ℃, gradually reducing the vacuum degree to 15Pa, and reacting for 4.5 hours to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 4-cyclohexanedimethanol copolyester, wherein the intrinsic viscosity of the copolyester is 0.63dL/g, and the glass transition temperature is 121 ℃.

Example 7

The method comprises the following steps of (1) drying the polyhydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 4-cyclohexanedimethanol copolyester of the poly (terephthalic acid) at 85 ℃ for 9 hours by hot air; and then adding the dried resin into an injection molding machine, wherein the temperature of a screw rod of the injection molding machine in a first area is 282 ℃, the temperature of a screw rod of the injection molding machine in a second area is 282 ℃, the temperature of a screw rod of the injection molding machine in a third area is 284 ℃, the temperature of a die head of the injection molding machine in a fourth area is 284 ℃, the temperature of the die head of the injection molding machine is 283 ℃, the temperature of the die is 30 ℃. The hollow cup body has the cut-off of 700nm, the visible light transmittance of 88 percent, and no crack when falling 1m away from the ground.

The formula and the synthesis method of the dihydroxy ethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 4-cyclohexanedimethanol resin are as follows: adding dimethyl terephthalate, dihydroxyethoxy polycyclic aromatic hydrocarbon (3), ethylene glycol and 1, 4-cyclohexanedimethanol into a reactor according to the molar ratio of 1:0.40:0.6:0.20, then adding anhydrous zinc acetate of an ester exchange catalyst with the molar weight of 0.5 thousandth of dimethyl terephthalate, gradually heating to 180 ℃ under the protection of nitrogen for esterification for 4 hours, then adding a polycondensation catalyst antimony acetate with the molar weight of 1.0 thousandth of dimethyl terephthalate and 2.2 thousandth of stabilizer trimethyl phosphate, gradually heating to 282 ℃, gradually reducing the vacuum degree to 12Pa, and reacting for 4.0 hours to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 4-cyclohexanedimethanol copolyester, wherein the intrinsic viscosity of the copolyester is 0.75dL/g, and the glass transition temperature is 106 ℃.

Example 8

The method comprises the following steps of (1) drying the polyhydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 4-cyclohexanedimethanol copolyester with the structure shown in the formula (15) by hot air at 88 ℃ for 10 hours; and then adding the dried resin into an injection molding machine, wherein the temperature of a screw rod of the injection molding machine in a first area is 282 ℃, the temperature of a screw rod of the injection molding machine in a second area is 282 ℃, the temperature of a screw rod of the injection molding machine in a third area is 282 ℃, the temperature of a die head of the injection molding machine in a fourth area is 282 ℃, the temperature of the die head of the injection molding machine is 45 ℃, and the injection pressure. The hollow cup body has the cut-off of 700nm, the visible light transmittance of 91 percent, and no fracture when falling 1m away from the ground.

The formula and the synthesis method of the dihydroxy ethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 4-cyclohexanedimethanol resin are as follows: adding dimethyl terephthalate, dihydroxyethoxy polycyclic aromatic hydrocarbon (4), ethylene glycol and 1, 4-cyclohexanedimethanol into a reactor according to the molar ratio of 1:0.50:2.1:0.10, then adding anhydrous zinc acetate as a catalyst with the molar weight of 0.8 thousandth of dimethyl terephthalate, gradually heating to 182 ℃ under the protection of nitrogen for esterification, reacting for 3.3 hours, then adding antimony trioxide with the molar weight of 0.7 thousandth of dimethyl terephthalate, dibutyltin oxide with the molar weight of 0.5 thousandth of dimethyl terephthalate and triphenyl phosphate as a stabilizer with the molar weight of 1.0 thousandth of 1.282 ℃, gradually heating to 282 ℃ and gradually reducing the vacuum degree to 20Pa, and reacting for 4.0 hours to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 4-cyclohexanedimethanol copolyester with the intrinsic viscosity of 0.70/g and the glass transition temperature of 111 dL.

Example 9

The method comprises the following steps of (1) drying the polyhydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol copolyester with the structure shown in the formula (16) by hot air at 130 ℃ for 4 hours; and then adding the dried resin into an injection molding machine, wherein the temperature of a screw rod of the injection molding machine in a first area is 288 ℃, the temperature of a screw rod of the injection molding machine in a second area is 290 ℃, the temperature of a screw rod of the injection molding machine in a third area is 290 ℃, the temperature of a die head of the injection molding machine in a fourth area is 290 ℃, the temperature of the die head of the injection molding machine is 60 ℃, and the injection pressure of the injection molding. The hollow cup body has the cut-off of 700nm, the visible light transmittance is 89%, and the hollow cup body does not crack when falling 1m away from the ground.

Wherein x and y are integers from 1 to 10, and m is an integer from 10 to 100.

The formula and the synthesis method of the dihydroxy ethoxy polycyclic aromatic hydrocarbon glycol resin of the poly (terephthalic acid) are as follows: adding dimethyl terephthalate, dihydroxyethoxy polycyclic aromatic hydrocarbon (2) and ethylene glycol into a reactor according to the molar ratio of 1:0.70:2.1, then adding anhydrous zinc acetate with the molar weight of 0.8 thousandth of that of dimethyl terephthalate, gradually heating to 200 ℃ under the protection of nitrogen for esterification, reacting for 3.0h, then adding antimony trioxide with the molar weight of 0.8 thousandth of that of dimethyl terephthalate and stabilizer diphenyl phosphate with the molar weight of 1.5 thousandth of that of diphenyl phosphate, gradually heating to 288 ℃, gradually reducing the vacuum degree to 25Pa, and reacting for 3.0h to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol terephthalate, wherein the intrinsic viscosity of the copolyester is 0.60dL/g, and the glass transition temperature is 146 ℃.

Example 10

The method comprises the following steps of (1) drying the polyhydroxyethoxy polycyclic aromatic hydrocarbon butanediol copolyester of the poly (terephthalic acid) for 7 hours by hot air at the temperature of 80 ℃, wherein the structure of the butanediol copolyester is shown as a formula (17); and then adding the dried resin into an injection molding machine, wherein the temperature of a screw rod of the injection molding machine in a first area is 260 ℃, the temperature of a screw rod of the injection molding machine in a second area is 262 ℃, the temperature of a screw rod of the injection molding machine in a third area is 262 ℃, the temperature of a die head of the injection molding machine in a fourth area is 262 ℃, the temperature of the die head of the injection molding machine is 260 ℃, the temperature of the die is 25 ℃. The hollow cup body is cut off by 700nm, the visible light transmittance is 88 percent, and the hollow cup body does not crack when falling 1m away from the ground.

Formula (17), wherein x and y are integers of 1 to 10, and m is an integer of 10 to 100.

The formula and the synthesis method of the poly (p-phenyleneterephthalate) dihydroxy ethoxy polycyclic aromatic hydrocarbon butanediol resin are as follows: adding dimethyl terephthalate, dihydroxyethoxy polycyclic aromatic hydrocarbon (2), butanediol and 1, 4-cyclohexanedimethanol into a reactor according to the molar ratio of 1:0.40:2.1:0.4, then adding tetrabutyl titanate with the molar amount of 0.8 per thousand of dimethyl terephthalate, gradually heating to 160 ℃ under the protection of nitrogen for esterification for 4.5 hours, then adding diphenyl phosphate as a stabilizer with the molar amount of 1.3 per thousand of dimethyl terephthalate, gradually heating to 260 ℃, gradually reducing the vacuum degree to 32Pa, and reacting for 3.5 hours to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon butanediol 1, 4-cyclohexanedimethanol copolyester of the poly (terephthalic acid), wherein the intrinsic viscosity of the copolyester is 0.78dL/g, and the glass transition temperature is 112 ℃.

Example 11

The method comprises the following steps of (1) drying the polyhydroxyethoxy polycyclic aromatic hydrocarbon propylene glycol copolyester of the poly (terephthalic acid) for 12 hours by hot air at 85 ℃, wherein the structure of the copolyester is as shown in a formula (18); and then adding the dried resin into an injection molding machine, wherein the temperature of a screw rod of the injection molding machine in a first area is 270 ℃, the temperature of a screw rod of the injection molding machine in a second area is 272 ℃, the temperature of a screw rod of the injection molding machine in a third area is 272 ℃, the temperature of a die head of the injection molding machine in a fourth area is 272 ℃, the temperature of the die head of the injection molding machine is 30 ℃, and the injection pressure of the injection molding. The hollow cup body is cut off by 700nm, the visible light transmittance is 90%, and the hollow cup body does not crack when falling 1m away from the ground.

Wherein x and y are integers from 1 to 10, and m is an integer from 10 to 100.

The formula and the synthesis method of the dihydroxyethoxy polycyclic aromatic hydrocarbon-propylene glycol terephthalate resin are as follows: adding dimethyl terephthalate, dihydroxyethoxy polycyclic aromatic hydrocarbon (2), propylene glycol and 1, 4-cyclohexanedimethanol into a reactor according to the molar ratio of 1:0.40:2.1:0.4, then adding anhydrous manganese acetate with the molar weight of 2.0 thousandth of dimethyl terephthalate, gradually heating to 175 ℃ under the protection of nitrogen for esterification for 5.0h, then adding antimony trioxide with the molar weight of 0.5 thousandth of dimethyl terephthalate and 0.4 thousandth of stabilizer dimethyl phosphate, gradually heating to 275 ℃, gradually reducing the vacuum degree to 30Pa, and reacting for 3.5h to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon propylene glycol 1, 4-cyclohexanedimethanol copolyester, wherein the intrinsic viscosity of the copolyester is 0.77dL/g, and the glass transition temperature is 117 ℃.

The hollow cup body obtained by injection molding in the above embodiment of the invention can be a baby feeding bottle cup body, a water cup, a kitchen electrical product, such as a stirring cup cold cup of a broken wall cooking machine, a stirring cup of a portable fruit juice machine, a juice extracting barrel of a juice extracting machine, a stirring cup of a noodle maker, a hot filling beverage bottle, a medical container and the like, but is not limited thereto.

Example 12

In this example, the polyhydroxyethoxy polycyclic aromatic hydrocarbon ethylene glycol 1, 4-cyclohexanedimethanol terephthalate obtained in example 1 is first formed into a structural layer, and then the structural layer can be combined with an inorganic material, an organic material or a composite material thereof through an adhesive to form a multilayer composite film having a composite layered structure, wherein the multilayer composite film can be used for preparing container walls of various containers such as baby bottle bodies, water cups, kitchen electrical products, hot-filled beverage bottles, medical containers and the like.

Comparative example 1

This comparative example differs from example 1 in that: the poly (1, 4-cyclohexanedimethanol) copolyester with the structure shown as the formula (9) of the poly (dihydroxyethoxy) polycyclic aromatic hydrocarbon ethylene glycol is replaced by the polyethylene terephthalate (PET) in the prior art and added into an injection molding machine, the heat-resistant temperature of the obtained cup body is 71 ℃, the cup body is crystallized in the processing process, and the transparency is 86%.

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 high temperature resistant polycyclic aromatic hydrocarbon polyester hollow container, characterized in that, the high temperature resistant polycyclic aromatic hydrocarbon polyester hollow container has a hollow structure, and the high temperature resistant polycyclic aromatic hydrocarbon polyester hollow container is mainly prepared from polycyclic aromatic hydrocarbon polyester, and the composition for synthesizing the polycyclic aromatic hydrocarbon polyester comprises:

component (a) comprising a bishydroxyethoxy polycyclic aromatic hydrocarbon;

component (b), terephthalic acid or an esterified product thereof; and

a component (c), a dihydric alcohol, wherein the dihydric alcohol is a combination of a cyclic dihydric alcohol and an aliphatic dihydric alcohol, the cyclic dihydric alcohol is selected from any one or a combination of more than two of 1, 4-cyclohexanedimethanol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol and tricyclodecane dimethanol, and the aliphatic dihydric alcohol is selected from any one or a combination of more than two of ethylene glycol, propylene glycol and butanediol;

the dihydroxyethoxy polycyclic aromatic hydrocarbon has a structure shown in a formula (2) or a formula (4):

；

the heat deformation temperature of the high-temperature resistant polycyclic aromatic hydrocarbon polyester hollow container is 95-160 ℃; the wavelength of the light is cut off at 700nm, and the visible light transmittance is 88-92%.

2. The high temperature resistant polycyclic aromatic hydrocarbon polyester hollow container of claim 1, wherein: the molar ratio of the component (a) to the component (b) is 5-80: 100.

3. The high temperature resistant polycyclic aromatic hydrocarbon polyester hollow container of claim 1, wherein: the molar ratio of the combination of the component (a) and the component (c) to the component (b) is 120-300: 100.

4. The high temperature resistant polycyclic aromatic hydrocarbon polyester hollow container of claim 1, wherein: the terephthalic acid ester is dimethyl terephthalate.

5. The high temperature resistant polycyclic aromatic hydrocarbon polyester hollow container of claim 1, wherein: the high-temperature-resistant polycyclic aromatic hydrocarbon polyester hollow container is prepared by compounding polycyclic aromatic hydrocarbon polyester and a polymer, wherein the polymer is selected from any one or the combination of more than two of polypropylene, polyether ether sulfone, polyether sulfone and polyamide.

6. The high temperature resistant polycyclic aromatic hydrocarbon polyester hollow container of claim 1, wherein: the high-temperature-resistant polycyclic aromatic hydrocarbon polyester hollow container can be used for a feeding bottle body, a water cup, a kitchen electrical product, a hot-filling beverage bottle or a medical container.

7. A preparation method of a high-temperature-resistant polycyclic aromatic hydrocarbon polyester hollow container is characterized by comprising 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 at 160-240 ℃ for 2.0-6.0 h under a protective atmosphere to obtain an intermediate product; the dihydric alcohol is a combination of a cyclic dihydric alcohol and an aliphatic dihydric alcohol, the cyclic dihydric alcohol is selected from any one or a combination of more than two of 1, 4-cyclohexanedimethanol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol and tricyclodecanedimethanol, and the aliphatic dihydric alcohol is selected from any one or a combination of more than two of ethylene glycol, propylene glycol and butanediol;

reacting a second mixed reaction system containing the intermediate product, a polycondensation catalyst and a stabilizer for 1.5-6 hours at the temperature of 260-290 ℃ and the vacuum degree of below 200Pa to obtain polycyclic aromatic hydrocarbon polyester;

；

inputting polycyclic aromatic hydrocarbon polyester into an injection molding machine for injection molding, wherein the working parameters of the injection molding machine comprise: the cylinder temperature is 260-290 ℃, the die head temperature is 260-290 ℃, the die temperature is 25-60 ℃, and the injection pressure is 30-150 MPa, so that the high-temperature-resistant polycyclic aromatic hydrocarbon polyester hollow container as claimed in any one of claims 1-6 is prepared.

8. The production method according to claim 7, characterized by comprising: bisphenol polycyclic aromatic hydrocarbon, ethylene carbonate and alkali metal carbonate are mixed according to the proportion of 1: 2.01-2.10: uniformly mixing the materials according to a molar ratio of 0.001-0.005 to form a mixture, and reacting the mixture at 150-250 ℃ for 1-5 hours to obtain the dihydroxyethoxy polycyclic aromatic hydrocarbon;

the bisphenol polycyclic aromatic hydrocarbon has a structure shown as a formula (6) or a formula (8):

；

the alkali metal carbonate is selected from any one or the combination of more than two of potassium carbonate, sodium carbonate, lithium carbonate and cesium carbonate.

9. The method of claim 7, wherein: the terephthalic acid ester is dimethyl terephthalate.

10. The method of claim 7, wherein: the molar ratio of the dihydroxy ethoxy polycyclic aromatic hydrocarbon to the terephthalic acid or the esterified product thereof is 5-80: 100.

11. The method of claim 7, wherein: the mole ratio of the combination of the dihydroxyethoxy polycyclic aromatic hydrocarbon and the dihydric alcohol to the terephthalic acid or the esterified product thereof is 120-300: 100.

12. The method of claim 7, wherein: the molar ratio of the esterification or ester exchange catalyst to the terephthalic acid or the esterified product thereof is 0.5-2.0: 1000.

13. The method of claim 7, wherein: the molar ratio of the polycondensation catalyst to the terephthalic acid or the esterified product thereof is 0.5-2.0: 1000.

14. The method of claim 7, wherein: the molar ratio of the stabilizer to the terephthalic acid or the ester thereof is 0.4-3.0: 1000.

15. The method of claim 7, wherein: the esterification or ester exchange catalyst is selected from any one or the combination of more than two of zinc catalyst, manganese catalyst, titanium catalyst and tin catalyst;

and/or the polycondensation catalyst is any one or the combination of more than two of titanium catalyst, tin catalyst, antimony catalyst and germanium catalyst.

16. The method of claim 7, wherein: the stabilizer is a phosphorus stabilizer, and the phosphorus stabilizer is selected from one or the 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.

17. The method of claim 15, wherein: the zinc catalyst is zinc acetate.

18. The method of claim 15, wherein: the manganese catalyst is manganese acetate.

19. The method of claim 15, wherein: the titanium catalyst is selected from one or the combination of more than two of tetrabutyl titanate, isopropyl titanate, titanium dioxide and inorganic supported titanium catalyst.

20. The method of claim 15, wherein: the antimony catalyst is selected from any one or combination of more than two of antimony trioxide, ethylene glycol antimony, antimony acetate and polyethylene glycol antimony.

21. The method of claim 15, wherein: the tin catalyst is selected from any one or combination of more than two of dibutyltin oxide, stannous isooctanoate, monobutyl triisooctanoate tin and dioctyltin oxide.

22. The method of claim 15, wherein: the germanium-based catalyst is selected from germanium dioxide and/or germanium oxide.

23. The method of claim 7, further comprising: the polycyclic aromatic hydrocarbon polyester is dried for 4-12 hours at the temperature of 80-130 ℃, and then the dried polycyclic aromatic hydrocarbon polyester is input into an injection molding machine for injection molding.

24. The method of claim 7, further comprising: compounding polycyclic aromatic hydrocarbon polyester with a polymer, and inputting the obtained mixture into an injection molding machine for injection molding, wherein the polymer is any one or the combination of more than two of polypropylene, polyether ether sulfone, polyether sulfone and polyamide.

25. A container having a wall of a multilayer composite film structure comprising a first structural layer and a second structural layer stacked in this order, the first structural layer being adhesively bonded to the second structural layer, and the first structural layer being a film formed from a polycyclic aromatic hydrocarbon polyester, wherein a composition for synthesizing the polycyclic aromatic hydrocarbon polyester comprises:

component (a) comprising a bishydroxyethoxy polycyclic aromatic hydrocarbon;

component (b), terephthalic acid or an esterified product thereof; and

。