CN113968962A - High-strength high-modulus polyester-polycarbonate copolymer, and preparation method and application thereof - Google Patents
High-strength high-modulus polyester-polycarbonate copolymer, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a high-strength high-modulus polyester-polycarbonate copolymer, and a preparation method and application thereof. The preparation method comprises the following steps: the high-strength high-modulus polyester-polycarbonate copolymer is prepared by copolymerizing carbonic diester, terephthalic acid and/or esterified substances thereof, adipic acid and/or esterified substances thereof and dihydric alcohol. According to the invention, the carbonate bond is introduced into the polyester-polycarbonate copolymer, so that the content of the fatty chain in the copolymer is reduced, and the tensile strength, tensile modulus and gas barrier property of the copolymer are improved. In addition, the introduction of the carbonate bond improves the ester bond density of the molecular chain segment, thereby improving the degradation performance of the molecular chain segment. Under the dual action of the carbonate and the cyclic diol, the heat resistance of the polyester-polycarbonate copolymer is improved compared with that of PBAT.
Description
Technical Field
The invention relates to a polyester-polycarbonate copolymer, in particular to a high-strength high-modulus polyester-polycarbonate copolymer, a preparation method and application thereof, and belongs to the technical field of high polymer materials.
Background
Polybutylene terephthalate adipate (PBAT) is a commercialized thermoplastic degradable polyester plastic, consists of a flexible aliphatic chain segment and a rigid aromatic chain segment, integrates the excellent degradation performance of aliphatic polyester and the good mechanical property of aromatic polyester, and has wide application in the fields of agricultural mulching films, express packaging, take-out packaging, disposable plastic packaging such as shopping bags and garbage bags, disposable tableware, 3D printing and the like. Under the situation that the global plastic prohibition is increasingly strict, the advantage of PBAT degradation is increasingly highlighted, but the price of PBAT is also increased rapidly. Since the policy of global plastic limit and plastic prohibition is continuously released in 2020, the price of PBAT has risen to 2.4-2.6 ten thousand yuan/ton from 2-2.2 ten thousand yuan/ton. Therefore, it is necessary to adopt an effective method for reducing the cost thereof. Furthermore, the tensile strength and tensile modulus of PBAT are low, and can be improved while reducing costs.
Disclosure of Invention
The invention mainly aims to provide a high-strength high-modulus polyester-polycarbonate copolymer, a preparation method and application thereof, so as to reduce the cost of PBAT and overcome the defects of lower strength and modulus of the conventional PBAT.
In order to achieve the purpose, the invention adopts the following technical scheme:
some embodiments of the present invention provide a method for preparing a high strength and high modulus polyester-polycarbonate copolymer, comprising:
(1) carrying out an ester exchange reaction on a first mixed reaction system containing a carbonic diester, a first dihydric alcohol and a first ester exchange catalyst at 90-220 ℃ in a protective atmosphere, reducing the temperature to room temperature after the ester exchange reaction is finished, and then maintaining the reaction system in the protective atmosphere to form a first intermediate product;
(2) carrying out esterification or ester exchange reaction on a second mixed reaction system containing terephthalic acid and/or an ester thereof, adipic acid and/or an ester thereof, a second diol and a second esterification or ester exchange catalyst at 150-240 ℃ in a protective atmosphere, reducing the temperature to room temperature after the esterification or ester exchange reaction is finished, and then keeping the reaction system in the protective atmosphere to obtain a second intermediate product;
(3) performing polycondensation reaction on a third mixed reaction system containing the first intermediate product, the second intermediate product, a polycondensation catalyst and a stabilizer under a vacuum condition at 200-295 ℃ to obtain a high-strength high-modulus polyester-polycarbonate copolymer;
alternatively, the preparation method comprises:
(i) carrying out an ester exchange reaction on a first mixed reaction system containing a carbonic diester, a first dihydric alcohol and a first ester exchange catalyst at 90-220 ℃ in a protective atmosphere, reducing the temperature to room temperature after the ester exchange reaction is finished, and then maintaining the reaction system in the protective atmosphere to form a first intermediate product;
(ii) carrying out esterification or ester exchange reaction on a fourth mixed reaction system containing terephthalic acid and/or an ester thereof, adipic acid and/or an ester thereof, a second diol, a first intermediate product and a second esterification or ester exchange catalyst at 150-240 ℃ in a protective atmosphere, reducing the temperature to room temperature after the esterification or ester exchange reaction is finished, and then maintaining the reaction system in the protective atmosphere to obtain a third intermediate product;
(iii) performing polycondensation reaction on a fifth mixed reaction system containing a third intermediate product, a polycondensation catalyst and a stabilizer at 200-295 ℃ under a vacuum condition to obtain a high-strength high-modulus polyester-polycarbonate copolymer;
wherein the first dihydric alcohol comprises a cyclic dihydric alcohol or a combination of an aliphatic dihydric alcohol and a cyclic dihydric alcohol, the second dihydric alcohol comprises a combination of an aliphatic dihydric alcohol and a cyclic dihydric alcohol, the aliphatic dihydric alcohol comprises 1, 4-butanediol, and the cyclic dihydric alcohol comprises any one or a combination of two of 2, 8-quinoline diol and tricyclodecane dimethanol.
Some embodiments of the present invention also provide a high strength and modulus polyester-polycarbonate copolymer synthesized by the foregoing preparation method.
In some embodiments, the high strength and high modulus polyester-polycarbonate copolymer has a tensile strength of not less than 17.0MPa and a tensile modulus of not less than 95.0 MPa.
Some embodiments of the present invention also provide a composition for synthesizing a high strength and high modulus polyester-polycarbonate copolymer, comprising:
a component (a) comprising terephthalic acid and/or an esterified product thereof;
component (b) comprising adipic acid and/or an esterified product thereof;
component (c), comprising a carbonic acid diester;
component (d) comprising a first glycol, and
component (e) comprising a second glycol;
wherein the first dihydric alcohol comprises a cyclic dihydric alcohol or a combination of an aliphatic dihydric alcohol and a cyclic dihydric alcohol, the second dihydric alcohol comprises a combination of an aliphatic dihydric alcohol and a cyclic dihydric alcohol, the aliphatic dihydric alcohol comprises 1, 4-butanediol, and the cyclic dihydric alcohol comprises any one or a combination of two of 2, 8-quinoline diol and tricyclodecane dimethanol.
Some embodiments of the invention also provide uses of the high-strength high-modulus polyester-polycarbonate copolymer, for example, in the fields of preparing packaging materials (such as packaging bags, packaging films and the like), containers (such as shopping bags), mulching films and the like.
Compared with the prior art, the invention has the beneficial effects that:
(1) after the esterification or ester exchange reaction is finished, the temperature is reduced to room temperature under the action of protective atmosphere and is kept for a period of time, before the polycondensation reaction is started, the vacuum pumping is started to be higher in vacuum degree under the room temperature condition and then is heated to the polycondensation temperature, compared with the traditional process which does not contain a cooling step and starts the vacuum pumping under the high temperature condition, the side reactions such as high-temperature oxidation and the like of the product can be avoided, and the colorless or white high-quality product is obtained;
(2) the carbonic acid diester selected by the invention is low in price, and can be introduced into the structure of the polyester-polycarbonate copolymer in a copolymerization mode, so that the production cost can be obviously reduced;
(3) according to the invention, a carbonate bond (-OCOO-) is introduced into the polyester-polycarbonate copolymer, so that the content of the aliphatic chain in the copolymer is reduced, the tensile strength, the tensile modulus and the gas barrier property of the copolymer are improved, but the elongation at break is reduced. The 2, 8-quinoline diol structure adopted by the invention contains two benzene rings, has high structural rigidity, and is very beneficial to improving the tensile modulus, tensile strength and heat resistance of the polymer; the tricyclodecane dimethanol contains three five-membered ring structures, has higher rigidity, also plays a better role in improving tensile modulus, tensile strength and heat resistance, and can damage the crystallization of the polymer and improve the transparency of the polymer. In addition, the introduction of the carbonate bond improves the ester bond density of the molecular chain segment, thereby improving the degradation performance of the molecular chain segment. Under the dual action of the carbonate and the cyclic diol, the heat resistance of the polyester-polycarbonate copolymer is improved compared with that of PBAT.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be 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 application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a stress-strain plot of a high strength and high modulus polyester-polycarbonate copolymer prepared in example 1 of the present invention;
FIG. 2 is a DSC plot of the high strength and high modulus polyester-polycarbonate copolymer prepared in example 1 of the present invention.
Detailed Description
As described above, in view of the defects of the prior art, the present inventors have made extensive studies and extensive practices to provide a technical solution of the present invention, which is to obtain a polyester-polycarbonate copolymer having more excellent tensile strength, tensile modulus, gas barrier property and degradation property than PBAT, mainly by copolymerizing a polyester oligomer and a polycarbonate oligomer. The present invention will be more fully understood from the following detailed description, which should be read in conjunction with the accompanying drawings. Detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention, which can be embodied in various forms. Therefore, specific functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed embodiment.
The technical solution, its implementation and principles, etc. will be further explained as follows.
One aspect of the embodiments of the present invention provides a method for preparing a high-strength high-modulus polyester-polycarbonate copolymer, comprising:
(1) carrying out an ester exchange reaction on a first mixed reaction system containing a carbonic diester, a first dihydric alcohol and a first ester exchange catalyst at 90-220 ℃ in a protective atmosphere, reducing the temperature to room temperature after the ester exchange reaction is finished, and then maintaining the reaction system in the protective atmosphere to form a first intermediate product;
(2) carrying out esterification or ester exchange reaction on a second mixed reaction system containing terephthalic acid and/or an ester thereof, adipic acid and/or an ester thereof, a second diol and a second esterification or ester exchange catalyst at 150-240 ℃ in a protective atmosphere, reducing the temperature to room temperature after the esterification or ester exchange reaction is finished, and then keeping the reaction system in the protective atmosphere to obtain a second intermediate product;
(3) and carrying out polycondensation reaction on a third mixed reaction system containing the first intermediate product, the second intermediate product, a polycondensation catalyst and a stabilizer at 200-295 ℃ under a vacuum condition to obtain the high-strength high-modulus polyester-polycarbonate copolymer.
Another aspect of the embodiments of the present invention provides a method for preparing the high strength and high modulus polyester-polycarbonate copolymer, comprising:
(i) carrying out an ester exchange reaction on a first mixed reaction system containing a carbonic diester, a first dihydric alcohol and a first ester exchange catalyst at 90-220 ℃ in a protective atmosphere, reducing the temperature to room temperature after the ester exchange reaction is finished, and then maintaining the reaction system in the protective atmosphere to form a first intermediate product;
(ii) carrying out esterification or ester exchange reaction on a fourth mixed reaction system containing terephthalic acid and/or an ester thereof, adipic acid and/or an ester thereof, a second diol, a first intermediate product and a second esterification or ester exchange catalyst at 150-240 ℃ in a protective atmosphere, reducing the temperature to room temperature after the esterification or ester exchange reaction is finished, and then maintaining the reaction system in the protective atmosphere to obtain a third intermediate product;
(iii) and carrying out polycondensation reaction on a fifth mixed reaction system containing the third intermediate product, a polycondensation catalyst and a stabilizer at the temperature of 200-295 ℃ under a vacuum condition to obtain the high-strength high-modulus polyester-polycarbonate copolymer.
In some embodiments, the first glycol comprises a cyclic glycol, or a combination of a fatty glycol and a cyclic glycol, and the second glycol comprises a combination of a fatty glycol and a cyclic glycol.
Further, the aliphatic diol includes 1, 4-butanediol, but is not limited thereto.
In some embodiments, the cyclic diol includes any one or a combination of two of 2, 8-quinoline diol and tricyclodecane dimethanol, but is not limited thereto, and the specific structure can be shown as follows:
the 2, 8-quinoline diol structure adopted by the invention contains two benzene rings, has high structural rigidity, and is very beneficial to improving the tensile modulus, tensile strength and heat resistance of the polymer; the tricyclodecane dimethanol contains three five-membered ring structures, has higher rigidity, also plays a better role in improving tensile modulus, tensile strength and heat resistance, and can damage the crystallization of the polymer and improve the transparency of the polymer.
Further, the invention adopts the tricyclodecane dimethanol or the combination of the tricyclodecane dimethanol and 1, 4-butanediol, and the performances such as heat resistance, strength and modulus can be improved greatly.
In some embodiments, the carbonic acid diester includes any one or a combination of two or more of dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and the like, but is not limited thereto. The carbonic acid diester selected by the invention is cheap, and can obviously reduce the production cost by introducing the carbonic acid diester into the structure of the polyester-polycarbonate copolymer in a copolymerization mode. In addition, the introduction of the carbonate bond improves the ester bond density of the molecular chain segment, thereby improving the degradation performance of the molecular chain segment. Under the dual action of the carbonate and the cyclic diol, the heat resistance of the polyester-polycarbonate copolymer is improved compared with that of PBAT.
In some embodiments, in step (1) or step (i), the molar ratio of the carbonic acid diester to the first glycol is 1: 0.3 to 3.0.
In some embodiments, the first transesterification catalyst is added in an amount of 0.01 to 0.5% of the theoretical mass of the first intermediate product.
In some embodiments, in step (2) or step (ii), the molar ratio of the combined total moles of terephthalic acid and/or its esters and adipic acid and/or its esters to the second glycol is 1: 1.2 to 3.0.
In some embodiments, the second esterification or transesterification catalyst is added in an amount of 0.01 to 0.5% of the theoretical mass of the second intermediate product or the third intermediate product.
Further, in the step (ii), the mass ratio of the first intermediate product to the total mass of the phthalic acid and/or the esterified product thereof, the adipic acid and/or the esterified product thereof and the second diol reacted into the polymer is 1-99: 99-1.
In some embodiments, in step (3), the mass ratio of the first intermediate product to the second intermediate product is 1-99: 99-1.
In some embodiments, in step (3) or step (iii), the mass of the polycondensation catalyst added is 0.01 to 0.5% of the theoretical mass of the high-strength high-modulus polyester-polycarbonate copolymer, and the mass of the stabilizer added is 0.01 to 0.5% of the theoretical mass of the high-strength high-modulus polyester-polycarbonate copolymer.
In some embodiments, the method of making comprises: and carrying out ester exchange reaction on the first mixed reaction system at 90-220 ℃ for 4.0-36.0 h in a protective atmosphere, reducing the temperature to room temperature at a cooling rate of 1-50 ℃/min after the ester exchange reaction is finished, and then keeping the temperature for 1.0-5.0 h in the protective atmosphere to form a first intermediate product.
In some embodiments, the method of making comprises: in the step (2), the second mixed reaction system is subjected to esterification or ester exchange reaction for 1.5-6.0 h at 150-240 ℃ in a protective atmosphere, the temperature is reduced to room temperature at a cooling rate of 1-50 ℃/min after the esterification or ester exchange reaction is finished, and then the temperature is maintained for 1.0-5.0 h in the protective atmosphere to form a second intermediate product.
In some embodiments, the method of making comprises: in the step (3), the third mixed reaction system is vacuumized to be below 100Pa, and then gradually heated to 200-295 ℃ for polycondensation reaction for 2.0-10.0 h, so as to obtain the high-strength and high-modulus polyester-polycarbonate copolymer.
In some embodiments, the method of making comprises: in the step (ii), the fourth mixed reaction system is subjected to esterification or ester exchange reaction for 1.5-6.0 h at 150-240 ℃ in a protective atmosphere, the temperature is reduced to room temperature at a cooling rate of 1-50 ℃/min after the esterification or ester exchange reaction is finished, and then the fourth mixed reaction system is kept for 1.0-5.0 h in the protective atmosphere to form a third intermediate product.
In some embodiments, the method of making comprises: in the step (iii), the fifth mixed reaction system is vacuumized to be below 100Pa, and then gradually heated to 200-295 ℃ for polycondensation reaction for 2.0-10.0 h, so as to obtain the high-strength and high-modulus polyester-polycarbonate copolymer.
Further, in the step (3) or the step (iii), the vacuum is pumped to below 100Pa at room temperature, the temperature is gradually increased to 200-295 ℃, and the vacuum is continuously pumped to keep the vacuum not to exceed (less than or equal to) 100Pa in the whole polycondensation process. According to the preparation method, after the esterification or ester exchange reaction is finished, the temperature is reduced to room temperature under the action of protective atmosphere and is kept for a period of time, and the room temperature is vacuumized to be below 100Pa and then is heated to the polycondensation temperature, compared with the traditional process without a cooling step and high-temperature vacuumization, the cooling rate is 1-50 ℃/min to be reduced to the room temperature, the lower the cooling rate is, the more perfect the crystallization of the product can be, in addition, the side reactions of high-temperature oxidation and the like of the product can be avoided, and the colorless or white high-quality product can be obtained.
In some more specific embodiments, the preparation method of the high-strength high-modulus polyester-polycarbonate copolymer specifically comprises the following steps:
(1) under the protection of nitrogen or inert atmosphere, uniformly mixing carbonic acid diester, first dihydric alcohol and a first ester exchange catalyst, carrying out ester exchange reaction for 4.0-36.0 hours at 90-220 ℃, reducing the temperature to room temperature at a cooling rate of 1-50 ℃/min after the reaction is finished, and keeping the temperature for 1.0-5.0 hours under the protection of nitrogen or inert atmosphere to obtain a first intermediate product;
(2) under the protection of nitrogen or inert atmosphere, uniformly mixing terephthalic acid or an esterified product thereof, adipic acid or an esterified product thereof, a second dihydric alcohol and a second esterification or ester exchange catalyst, carrying out esterification or ester exchange reaction for 1.5-6.0 hours at 150-240 ℃, reducing the temperature to room temperature at a cooling rate of 1-50 ℃/min after the reaction is finished, and keeping the temperature for 1.0-5.0 hours under the protection of nitrogen or inert atmosphere to obtain a second intermediate product;
(3) uniformly mixing the first intermediate product, the second intermediate product, a polycondensation catalyst and a stabilizer, vacuumizing to be below 100Pa, gradually heating to 200-295 ℃ to perform polycondensation for 2.0-10.0 hours to obtain the high-strength high-modulus polyester-polycarbonate copolymer;
alternatively, the preparation method comprises the following steps:
(i) under the protection of nitrogen or inert atmosphere, uniformly mixing carbonic acid diester, first dihydric alcohol and a first ester exchange catalyst, carrying out ester exchange reaction for 4.0-36.0 hours at 90-220 ℃, reducing the temperature to room temperature at a cooling rate of 1-50 ℃/min after the reaction is finished, and keeping the temperature for 1.0-5.0 hours under the protection of nitrogen or inert atmosphere to obtain a first intermediate product;
(ii) under the protection of nitrogen or inert atmosphere, uniformly mixing terephthalic acid or an esterified product thereof, adipic acid or an esterified product thereof, a second dihydric alcohol, a first intermediate product and a second esterification or ester exchange catalyst, carrying out esterification or ester exchange reaction for 1.5-6.0 hours at 150-240 ℃, reducing the temperature to room temperature at a cooling rate of 1-50 ℃/min after the reaction is finished, and keeping the temperature for 1.0-5.0 hours under the protection of nitrogen or inert atmosphere to obtain a third intermediate product;
(iii) and uniformly mixing the third intermediate product, the polycondensation catalyst and the stabilizer, vacuumizing to below 100Pa, gradually heating to 200-295 ℃ for polycondensation reaction for 2.0-10.0 hours, and obtaining the high-strength and high-modulus polyester-polycarbonate copolymer.
In some embodiments, the first transesterification catalyst is selected from a combination of one or more of a titanium-based catalyst, a tin-based catalyst, a germanium-based catalyst, and the like, but is not limited thereto.
Further, the titanium-based catalyst includes any one or a combination of two or more of tetrabutyl titanate, isopropyl titanate, titanium dioxide, an inorganic supported titanium catalyst, and the like, but is not limited thereto.
Further, the tin-based catalyst includes any one or a combination of two or more of dibutyltin oxide, stannous isooctanoate, monobutyl triisooctanoate, dioctyltin oxide, and the like, but is not limited thereto.
Further, the germanium-based catalyst includes any one or a combination of two or more of germanium dioxide, germanium acetate, germanium tetraethoxide, and the like, but is not limited thereto.
In some embodiments, the second esterification or transesterification catalyst is selected from a combination of one or more of a titanium-based catalyst, a tin-based catalyst, a germanium-based catalyst, and the like, but is not limited thereto.
Further, the titanium-based catalyst includes any one or a combination of two or more of tetrabutyl titanate, isopropyl titanate, titanium dioxide, an inorganic supported titanium catalyst, and the like, but is not limited thereto.
Further, the tin-based catalyst includes any one or a combination of two or more of dibutyltin oxide, stannous isooctanoate, monobutyl triisooctanoate, dioctyltin oxide, and the like, but is not limited thereto.
Further, the germanium-based catalyst includes any one or a combination of two or more of germanium dioxide, germanium acetate, germanium tetraethoxide, and the like, but is not limited thereto.
In some embodiments, the polycondensation catalyst is selected from the group consisting of one or more combinations of titanium-based catalysts, tin-based catalysts, germanium-based catalysts, and the like, but is not limited thereto.
Further, the titanium-based catalyst includes any one or a combination of two or more of tetrabutyl titanate, isopropyl titanate, titanium dioxide, an inorganic supported titanium catalyst, and the like, but is not limited thereto.
Further, the tin-based catalyst includes any one or a combination of two or more of dibutyltin oxide, stannous isooctanoate, monobutyl triisooctanoate, dioctyltin oxide, and the like, but is not limited thereto.
Further, the germanium-based catalyst includes any one or a combination of two or more of germanium dioxide, germanium acetate, germanium tetraethoxide, and the like, but is not limited thereto.
In some embodiments, the stabilizer is selected from the group consisting 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, without limitation.
The preparation mechanism of the invention is as follows: the carbonate bond (-OCOO-) is introduced into the polyester-polycarbonate copolymer, which is beneficial to reducing the content of the fatty chain in the copolymer, thereby improving the tensile strength, the tensile modulus and the gas barrier property of the copolymer, but the elongation at break can be reduced. In addition, the introduction of the carbonate bond improves the ester bond density of the molecular chain segment, thereby improving the degradation performance of the molecular chain segment. Under the dual action of the carbonate and the cyclic diol, the heat resistance of the polyester-polycarbonate copolymer is improved compared with that of PBAT.
Another aspect of an embodiment of the present invention provides a high strength and high modulus polyester-polycarbonate copolymer, which can be prepared by any of the methods of the preceding embodiments.
Further, the tensile strength and the tensile modulus of the high-strength high-modulus polyester-polycarbonate copolymer are not lower than 17.0MPa and not lower than 95.0 MPa.
Yet another aspect of an embodiment of the present invention provides a composition for preparing the high strength and high modulus polyester-polycarbonate copolymer of the previous embodiment, comprising:
a component (a) comprising terephthalic acid and/or an esterified product thereof;
component (b) comprising adipic acid and/or an esterified product thereof;
component (c), comprising a carbonic acid diester;
component (d) comprising a first glycol, and
component (e), comprising a second glycol.
In some embodiments, the first glycol comprises a cyclic glycol, or a combination of a fatty glycol and a cyclic glycol, and the second glycol comprises a combination of a fatty glycol and a cyclic glycol.
Further, the aliphatic diol includes 1, 4-butanediol, but is not limited thereto.
In some embodiments, the cyclic diol comprises any one of 2, 8-quinoline diol, tricyclodecane dimethanol, or a combination of both.
In some embodiments, the carbonic acid diester includes any one or a combination of two or more of dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and the like, but is not limited thereto.
Further, the terephthalate may be dimethyl terephthalate, but is not limited thereto.
Further, the adipate may be dimethyl adipate, but is not limited thereto.
The embodiment of the invention also provides the application of the high-strength high-modulus polyester-polycarbonate copolymer, such as the application in the production of packaging materials (such as packaging bags, packaging films and the like), containers (such as shopping bags), mulching films 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, thermal transition performance tests were carried out using a differential scanning calorimeter (Mettler Toledo DSC), N2The temperature range of the atmosphere is-70-280 ℃, and the heating rate is 10 ℃/min.
In the following examples, the mechanical properties were measured in an Instron model 5567 Universal Material testing machine with sample bar dimensions of 20.0mm in length, 2.0mm in width and 1.0mm in thickness and a tensile speed of 20 mm/min.
In the following examples, Labthink VAC-V2 was used to determine the barrier properties for oxygen and carbon dioxide, respectively as CO2And O2Is used as air source, and is tested under the conditions of 23 deg.C and 50% RH, sample size phi is 97mm, and permeation area is 38.5cm2。
Example 1
Putting 90.1g (1.0mol) of dimethyl carbonate, 53.0g (0.588mol) of 1, 4-butanediol, 1.9g (0.012mol) of 2, 8-quinolinediol and 0.4g of germanium dioxide into a reactor, gradually raising the temperature to 90 ℃ under the protection of nitrogen, reacting for 36.0 hours, then closing the reactor, reducing the temperature to room temperature at the cooling rate of 10 ℃/min under the protection of nitrogen, and keeping for 2.0 hours to obtain the polytetramethylene glycol 2, 8-quinolinediol oligomer.
21.8g (0.1125mol) of dimethyl terephthalate, 24.0g (0.1375mol) of dimethyl adipate, 39.4g (0.4375mol) of 1, 4-butanediol, 2.0g (0.0125mol) of 2, 8-quinolinediol, 7g of polybutylene carbonate 2, 8-quinolinediol oligomer and 0.105g of isopropyl titanate are put into a reactor, the temperature is gradually increased to 220 ℃ under the condition of nitrogen protection, the reaction is carried out for 6.0 hours, then the heating is closed, the temperature is reduced to room temperature at the temperature reduction rate of 10 ℃/min under the condition of nitrogen protection, and the temperature is maintained for 4.0 hours, so that the polyester-polycarbonate oligomer is obtained.
100g of polyester-polycarbonate oligomer, 0.3g of dioctyltin oxide and 0.01g of diphenyl phosphate are put into a reactor, the reactor is vacuumized to 25Pa, then the temperature is gradually raised to 280 ℃, the vacuum degree of the reaction system is continuously vacuumized to be lower than 25Pa, and the reaction is finished after 7.0 hours, so that the high-strength and high-modulus polyester-polycarbonate copolymer is obtained, wherein the structure is shown as the formula (I).
Wherein x, y, z, u, v and w are integers of 1-10, and m is an integer of 15-150.
Through detection, the high-strength high-modulus polyester-polycarbonate copolymer obtained in the embodiment is white, the tensile strength is 17.9MPa, the tensile modulus is 115.4MPa, the elongation at break is 879%, the glass transition temperature is-7.9 ℃, and CO is added2Permeability coefficient of 3.44barrer, O2The permeability coefficient was 5.98 barrer.
Method for preparing high-strength high-modulus polyester-polycarbonate copolymer obtained in the example1An H peak (4H) on a benzene ring at 7.91ppm on an H-NMR spectrum, an H peak (5H) on a quinoline ring in 2, 8-quinolinediol at 6.77-7.73 ppm, and an H peak on a methylene group close to a hydroxyl group in 1, 4-butanediol at 4.00-4.31 ppmThe H peak (4H) of (1) is 2.24ppm of the H peak (4H) of a methylene group close to a carbonyl group in adipic acid, the H peaks (4H) of two methylene groups in the middle of 1, 4-butanediol are 1.56-1.84 ppm of the H peak (4H) of two methylene groups in the middle of adipic acid are 1.48ppm of the H peak.
The stress-strain curve of the high strength and modulus polyester-polycarbonate copolymer obtained in this example is shown in FIG. 1.
The DSC curve of the high strength and high modulus polyester-polycarbonate copolymer obtained in this example is shown in FIG. 2.
Example 2
118.1g (1.0mol) of diethyl carbonate, 53.0g (0.588mol) of 1, 4-butanediol, 2.4g (0.012mol) of tricyclodecanedimethanol and 0.4g of germanium dioxide are put into a reactor, the temperature is gradually increased to 115 ℃ under the protection of nitrogen, the reaction is carried out for 24.0 hours, then the heating is closed, the temperature is reduced to room temperature at the temperature reduction rate of 15 ℃/min under the protection of nitrogen, and the temperature is maintained for 2.0 hours, thus obtaining the polytetramethylene glycol tricyclodecanedimethanol oligomer.
21.8g (0.1125mol) of dimethyl terephthalate, 24.0g (0.1375mol) of dimethyl adipate, 39.4g (0.4375mol) of 1, 4-butanediol, 2.5g (0.0125mol) of tricyclodecanedimethanol, 46g of polytetramethylene glycol tricyclodecanedimethanol oligomer and 0.105g of isopropyl titanate are put into a reactor, gradually heated to 220 ℃ under the protection of nitrogen, reacted for 6.0 hours, then the heating is closed, the temperature is reduced to room temperature at the temperature reduction rate of 15 ℃/min under the protection of nitrogen, and the temperature is maintained for 4.0 hours, so that the polyester-polycarbonate oligomer is obtained.
100g of polyester-polycarbonate oligomer, 0.3g of germanium acetate and 0.1g of diphenyl phosphate are put into a reactor, the reactor is vacuumized to 20Pa, then the temperature is gradually increased to 270 ℃, the vacuum degree of the reaction system is continuously vacuumized to maintain lower than 20Pa, and the reaction is finished after 2.0 hours, so that the high-strength and high-modulus polyester-polycarbonate copolymer is obtained, wherein the structure is shown as the formula (II).
Wherein x, y, z, u, v and w are integers of 1-10, and m is an integer of 15-150.
Through detection, the high-strength high-modulus polyester-polycarbonate copolymer obtained in the embodiment is white, the tensile strength is 32.3MPa, the tensile modulus is 157.9MPa, the elongation at break is 675%, the glass transition temperature is 3.6 ℃, and the temperature of CO is 32Permeability coefficient of 1.65barrer, O2The permeability coefficient was 3.07 barrer.
Example 3
Putting 118.1g (1.0mol) of diethyl carbonate, 48.4g (0.3mol) of 2, 8-quinoline diol and 0.5g of stannous isooctanoate into a reactor, gradually heating to 125 ℃ under the protection of nitrogen, reacting for 18.0 hours, then closing the reactor for heating, cooling to room temperature at the cooling rate of 20 ℃/min under the protection of nitrogen, and keeping for 3.0 hours to obtain the 2, 8-quinoline diol oligomer of the polycarbonate.
21.8g (0.1125mol) of dimethyl terephthalate, 24.0g (0.1375mol) of dimethyl adipate, 26.0g (0.288mol) of 1, 4-butanediol, 1.9g (0.012mol) of 2, 8-quinolinediol, 24g of polycarbonate 2, 8-quinolinediol oligomer and 0.12g of titanium dioxide are put into a reactor, gradually heated to 240 ℃ under the protection of nitrogen, reacted for 1.5 hours, then the heating is closed, the temperature is reduced to room temperature at the cooling rate of 20 ℃/min under the protection of nitrogen, and the temperature is maintained for 3.0 hours, so that the polyester-polycarbonate oligomer is obtained.
Putting 100g of polyester-polycarbonate oligomer, 0.5g of stannous isooctanoate and 0.1g of triphenyl phosphite into a reactor, vacuumizing to 25Pa, gradually heating to 280 ℃, continuously vacuumizing to maintain the vacuum degree of a reaction system to be lower than 40Pa, and finishing the reaction after 5.0 hours to obtain the high-strength and high-modulus polyester-polycarbonate copolymer with the structure as shown in formula (III).
Wherein x, y, z, u and v are integers of 1-10, and m is an integer of 15-150.
The high-strength high-modulus polyester-polycarbonate copolymer obtained in the example is detected to be white, and the tensile strength is 21.6MPa, tensile modulus 133.1MPa, elongation at break 717%, glass transition temperature-5.2 ℃ and CO2Permeability coefficient of 2.78barrer, O2The permeability coefficient was 4.62 barrer.
Example 4
214.2g (1.0mol) of diphenyl carbonate, 196.3g (1.0mol) of tricyclodecane dimethanol and 0.25g of tetrabutyl titanate are put into a reactor, gradually heated to 220 ℃ under the protection of nitrogen, reacted for 6.0 hours, then the heating is closed, and the temperature is reduced to room temperature at the cooling rate of 1 ℃/min under the protection of nitrogen and kept for 1.0 hour to obtain the poly-tricyclodecane dimethanol carbonate oligomer.
21.8g (0.1125mol) of dimethyl terephthalate, 24.0g (0.1375mol) of dimethyl adipate, 39.4g (0.4375mol) of 1, 4-butanediol, 12.3g (0.0625mol) of tricyclodecane dimethanol and 0.295g of monobutyl triisooctanoic acid tin are put into a reactor, gradually heated to 200 ℃ under the protection of nitrogen, reacted for 4.0 hours, then the heating is closed, the temperature is reduced to room temperature at the temperature reduction rate of 5 ℃/min under the protection of nitrogen, and kept for 4.0 hours, thus obtaining the tricyclodecane dimethanol ester oligomer of the polybutylene terephthalate.
Putting 80g of poly-tricyclodecane dimethanol oligomer, 20g of poly-butanediol adipate tricyclodecane dimethanol oligomer, 0.1g of monobutyl triisooctanoic acid tin and 0.3g of trimethyl phosphate into a reactor, vacuumizing to 25Pa, gradually heating to 295 ℃, continuously vacuumizing to maintain the vacuum degree of a reaction system to be lower than 50Pa, and finishing the reaction after 2.0 hours to obtain the high-strength and high-modulus polyester-polycarbonate copolymer, wherein the structure is shown as a formula (IV).
Wherein x, y, z, u and v are integers of 1-10, and m is an integer of 15-150.
Through detection, the high-strength high-modulus polyester-polycarbonate copolymer obtained in the embodiment is white, the tensile strength is 55.6MPa, the tensile modulus is 270.4MPa, the elongation at break is 351%, and the glass transition is realizedChanging the temperature to 28.1 ℃ and CO2Permeability coefficient of 1.15barrer, O2The permeability coefficient was 2.34 barrer.
Example 5
85.7g (0.4mol) of diphenyl carbonate, 96.7g (0.6mol) of 2, 8-quinolinediol, 117.8g (0.6mol) of tricyclodecanedimethanol and 0.022g of tetraethoxygermanium are put into a reactor, the temperature is gradually increased to 220 ℃ under the protection of nitrogen, the reaction is carried out for 4.0 hours, then the heating is closed, the temperature is reduced to room temperature at the temperature reduction rate of 30 ℃/min under the protection of nitrogen, and the reaction is kept for 5.0 hours, so that the poly (2, 8-quinolinediol-tricyclodecanedimethanol) oligomer is obtained.
21.8g (0.1125mol) of dimethyl terephthalate, 24.0g (0.1375mol) of dimethyl adipate, 39.4g (0.4375mol) of 1, 4-butanediol, 4.0g (0.025mol) of 2, 8-quinolinediol, 2.5g (0.0125mol) of tricyclodecanedimethanol and 0.14g of tetraethoxygermanium are put into a reactor, the temperature is gradually increased to 150 ℃ under the condition of nitrogen protection, the reaction is carried out for 6.0 hours, then the heating is closed, the temperature is decreased to the room temperature at the temperature decreasing rate of 5 ℃/min under the condition of nitrogen protection, and the temperature is maintained for 5.0 hours, thus obtaining the poly (butylene glycol adipate) tricyclodecanedimethanol ester oligomer.
Putting 1g of poly (2, 8-quinolinediol tricyclodecanedimethanol) oligomer, 99g of poly (butanediol adipate), tricyclodecanedimethanol ester oligomer, 0.01g of germanium acetate and 0.5g of phosphorous acid into a reactor, vacuumizing to 25Pa, gradually heating to 250 ℃, continuously vacuumizing to maintain the vacuum degree of a reaction system to be lower than 30Pa, and finishing the reaction after 8.0 hours to obtain the high-strength and high-modulus polyester-polycarbonate copolymer, wherein the structure is shown as a formula (V).
Wherein x, y, z, u, v, w, a and b are integers of 1-10, and m is an integer of 15-150.
Through detection, the high-strength high-modulus polyester-polycarbonate copolymer obtained in the embodiment is white, the tensile strength is 17.1MPa, the tensile modulus is 105.4MPa, and the elongation at break is 853 percentGlass transition temperature of 10.7 ℃ and CO2Permeability coefficient of 3.94barrer, O2The permeability coefficient was 6.48 barrer.
Example 6
59.1g (0.5mol) of diethyl carbonate, 196.3g (1.0mol) of tricyclodecanedimethanol and 1.0g of titanium dioxide are put into a reactor, the temperature is gradually increased to 120 ℃ under the protection of nitrogen, the reaction is carried out for 20.0 hours, then the heating is closed, the temperature is reduced to room temperature at the temperature reduction rate of 50 ℃/min under the protection of nitrogen, and the temperature is maintained for 2.0 hours, thus obtaining the poly-tricyclodecanedimethanol carbonate oligomer.
21.8g (0.1125mol) of dimethyl terephthalate, 24.0g (0.1375mol) of dimethyl adipate, 60.8g (0.675mol) of 1, 4-butanediol, 10.1g (0.0625mol) of 2, 8-quinoline diol, 2.5g (0.0125mol) of tricyclodecane dimethanol, 42g of poly-tricyclodecane dimethanol carbonate oligomer and 0.15g of dioctyltin oxide are put into a reactor, the temperature is gradually increased to 220 ℃ under the protection of nitrogen, the reaction is carried out for 5.0 hours, then the heating is closed, the temperature is reduced to room temperature at the temperature reduction rate of 30 ℃/min under the protection of nitrogen, and the reaction is kept for 1.0 hour, thus obtaining the poly-butylene glycol tricyclodecane dimethanol adipate oligomer.
Putting 99g of poly-tricyclodecane dimethanol oligomer, 1g of poly-butanediol adipate tricyclodecane dimethanol ester oligomer, 0.5g of isopropyl titanate and 0.01g of ammonium phosphite into a reactor, vacuumizing to 25Pa, gradually heating to 200 ℃, continuously vacuumizing to maintain the vacuum degree of a reaction system to be lower than 20Pa, and finishing the reaction after 10.0 hours to obtain the high-strength high-modulus polyester-polycarbonate copolymer with the structure as shown in formula (VI).
Wherein x, y, z, u, v, w and a are integers of 1-10, and m is an integer of 15-150.
Through detection, the high-strength and high-modulus polyester-polycarbonate copolymer obtained in the embodiment is white, the tensile strength is 67.4MPa, the tensile modulus is 295.6MPa, the elongation at break is 308 percent,the glass transition temperature is 22.5 ℃ and CO2Permeability coefficient of 2.57barrer, O2The permeability coefficient was 3.36 barrer.
Comparative example 1
Putting 43.7g (0.225mol) of dimethyl terephthalate, 47.9g (0.275mol) of dimethyl adipate, 81.1g (0.9mol) of 1, 4-butanediol and 0.3g of tetrabutyl titanate into a reactor, gradually heating to 180 ℃ under the protection of nitrogen, reacting for 4.0 hours, then closing the reactor, cooling to room temperature under the protection of nitrogen, keeping for 3.0 hours, then vacuumizing to 30Pa, gradually heating to 230 ℃, continuously vacuumizing to keep the vacuum degree of the reaction system lower than 30Pa, and finishing the reaction after 4.0 hours to obtain the polybutylene terephthalate adipate.
The detection proves that the polybutylene terephthalate adipate obtained by the comparative example is white, the tensile strength is 16.6MPa, the tensile modulus is 93.5MPa, the elongation at break is 917 percent, the glass transition temperature is-25.2 ℃, and O2Permeability coefficient of 4.33barrer, CO2The permeability coefficient was 6.73 barrer.
Comparative example 2
Putting 43.7g (0.225mol) of dimethyl terephthalate, 47.9g (0.275mol) of dimethyl adipate, 81.1g (0.9mol) of 1, 4-butanediol and 0.3g of tetrabutyl titanate into a reactor, gradually heating to 180 ℃ under the protection of nitrogen, reacting for 4.0 hours, then vacuumizing to 30Pa, gradually heating to 230 ℃, continuously vacuumizing to maintain the vacuum degree of the reaction system to be lower than 30Pa, and finishing the reaction after 4.0 hours to obtain the polybutylene terephthalate adipate.
The polybutylene terephthalate adipate obtained in the comparative example is detected to be orange, the tensile strength is 15.9MPa, the tensile modulus is 90.6MPa, the elongation at break is 955 percent, the glass transition temperature is-24.8 ℃, and O2Permeability coefficient of 4.52barrer, CO2The permeability coefficient was 6.61 barrer.
Comparative example 3
This comparative example differs from example 1 in that: after the transesterification reaction, the temperature was not lowered to room temperature, and the reaction was not maintained under nitrogen. Adding dioctyltin oxide and diphenyl phosphate at 220 deg.C, directly vacuumizing, and gradually heating to 280 deg.C.
The comparative example adopts the traditional process without temperature reduction step and high-temperature vacuum pumping, the obtained product can generate side reactions such as high-temperature oxidation and the like, and the obtained product is yellow in color.
Example 7
Some embodiments of the invention also provide uses of the high strength and high modulus polyester-polycarbonate copolymer, such as for making packaging bags, packaging films, shopping bags, mulching films, and the like.
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.
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 (10)
1. A preparation method of a high-strength high-modulus polyester-polycarbonate copolymer is characterized by comprising the following steps:
(1) carrying out an ester exchange reaction on a first mixed reaction system containing a carbonic diester, a first dihydric alcohol and a first ester exchange catalyst at 90-220 ℃ in a protective atmosphere, reducing the temperature to room temperature after the ester exchange reaction is finished, and then maintaining the reaction system in the protective atmosphere to form a first intermediate product;
(2) carrying out esterification or ester exchange reaction on a second mixed reaction system containing terephthalic acid and/or an ester thereof, adipic acid and/or an ester thereof, a second diol and a second esterification or ester exchange catalyst at 150-240 ℃ in a protective atmosphere, reducing the temperature to room temperature after the esterification or ester exchange reaction is finished, and then keeping the reaction system in the protective atmosphere to obtain a second intermediate product;
(3) performing polycondensation reaction on a third mixed reaction system containing the first intermediate product, the second intermediate product, a polycondensation catalyst and a stabilizer under a vacuum condition at 200-295 ℃ to obtain a high-strength high-modulus polyester-polycarbonate copolymer;
alternatively, the preparation method comprises:
(i) carrying out an ester exchange reaction on a first mixed reaction system containing a carbonic diester, a first dihydric alcohol and a first ester exchange catalyst at 90-220 ℃ in a protective atmosphere, reducing the temperature to room temperature after the ester exchange reaction is finished, and then maintaining the reaction system in the protective atmosphere to form a first intermediate product;
(ii) carrying out esterification or ester exchange reaction on a fourth mixed reaction system containing terephthalic acid and/or an ester thereof, adipic acid and/or an ester thereof, a second diol, a first intermediate product and a second esterification or ester exchange catalyst at 150-240 ℃ in a protective atmosphere, reducing the temperature to room temperature after the esterification or ester exchange reaction is finished, and then maintaining the reaction system in the protective atmosphere to obtain a third intermediate product;
(iii) performing polycondensation reaction on a fifth mixed reaction system containing a third intermediate product, a polycondensation catalyst and a stabilizer at 200-295 ℃ under a vacuum condition to obtain a high-strength high-modulus polyester-polycarbonate copolymer;
wherein the first dihydric alcohol comprises a cyclic dihydric alcohol or a combination of an aliphatic dihydric alcohol and a cyclic dihydric alcohol, the second dihydric alcohol comprises a combination of an aliphatic dihydric alcohol and a cyclic dihydric alcohol, the aliphatic dihydric alcohol comprises 1, 4-butanediol, and the cyclic dihydric alcohol comprises any one or a combination of two of 2, 8-quinoline diol and tricyclodecane dimethanol.
2. The method of claim 1, wherein: the carbonic diester comprises any one or the combination of more than two of dimethyl carbonate, diethyl carbonate and diphenyl carbonate; and/or in the step (1) or the step (i), the molar ratio of the carbonic diester to the first dihydric alcohol is 1: 0.3-3.0; and/or the addition amount of the first transesterification catalyst is 0.01-0.5% of the theoretical mass of the first intermediate product.
3. The method of claim 1, wherein: in the step (2) or the step (ii), the molar ratio of the combination of the terephthalic acid and/or the esterified product thereof and the adipic acid and/or the esterified product thereof to the second glycol is 1: 1.2-3.0; and/or the addition amount of the second esterification or ester exchange catalyst is 0.01-0.5% of the theoretical mass of the second intermediate product or the third intermediate product; and/or in the step (ii), the mass ratio of the first intermediate product to the total mass of the terephthalic acid and/or the esterified product thereof, the adipic acid and/or the esterified product thereof and the second dihydric alcohol reacted into the polymer is 1-99: 99-1.
4. The method of claim 1, wherein: in the step (3), the mass ratio of the first intermediate product to the second intermediate product is 1-99: 99-1; and/or in the step (3) or the step (iii), the mass of the polycondensation catalyst is 0.01-0.5% of the theoretical mass of the high-strength high-modulus polyester-polycarbonate copolymer, and the mass of the stabilizer is 0.01-0.5% of the theoretical mass of the high-strength high-modulus polyester-polycarbonate copolymer.
5. The production method according to claim 1, characterized by comprising: carrying out ester exchange reaction on the first mixed reaction system at 90-220 ℃ for 4.0-36.0 h in a protective atmosphere, reducing the temperature to room temperature at a cooling rate of 1-50 ℃/min after the ester exchange reaction is finished, and then keeping the temperature for 1.0-5.0 h in the protective atmosphere to form a first intermediate product;
and/or in the step (2), carrying out esterification or ester exchange reaction on the second mixed reaction system at 150-240 ℃ for 1.5-6.0 h in a protective atmosphere, reducing the temperature to room temperature at a cooling rate of 1-50 ℃/min after the reaction is finished, and then keeping the temperature in the protective atmosphere for 1.0-5.0 h to form a second intermediate product;
and/or in the step (3), vacuumizing the third mixed reaction system to be less than 100Pa, gradually heating to 200-295 ℃ for polycondensation reaction for 2.0-10.0 h, and obtaining the high-strength and high-modulus polyester-polycarbonate copolymer;
and/or in the step (ii), carrying out esterification or ester exchange reaction on the fourth mixed reaction system at 150-240 ℃ for 1.5-6.0 h in a protective atmosphere, reducing the temperature to room temperature at a cooling rate of 1-50 ℃/min after the reaction is finished, and then keeping the temperature in the protective atmosphere for 1.0-5.0 h to form a third intermediate product;
and/or in the step (iii), vacuumizing the fifth mixed reaction system to be less than 100Pa, gradually heating to 200-295 ℃ for polycondensation reaction for 2.0-10.0 h, and obtaining the high-strength and high-modulus polyester-polycarbonate copolymer;
and/or in the step (3) or the step (iii), vacuumizing to be below 100Pa at room temperature, gradually heating to 200-295 ℃, and continuously vacuumizing to keep the vacuum not to exceed 100Pa in the whole polycondensation process.
6. The method of claim 1, wherein: the first transesterification catalyst comprises any one or a combination of more than two of a titanium catalyst, a tin catalyst and a germanium catalyst; and/or the second esterification or ester exchange catalyst comprises any one or the combination of more than two of titanium catalyst, tin catalyst and germanium catalyst;
and/or the polycondensation catalyst comprises any one or the combination of more than two of a titanium catalyst, a tin catalyst and a germanium catalyst;
and/or the stabilizer comprises any 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.
7. A high strength and high modulus polyester-polycarbonate copolymer prepared by the process of any of claims 1-6, preferably wherein the high strength and high modulus polyester-polycarbonate copolymer has a tensile strength of not less than 17.0MPa and a tensile modulus of not less than 95.0 MPa.
8. A composition for synthesizing a high strength and high modulus polyester-polycarbonate copolymer, comprising:
a component (a) comprising terephthalic acid and/or an esterified product thereof;
component (b) comprising adipic acid and/or an esterified product thereof;
component (c), comprising a carbonic acid diester;
component (d) comprising a first glycol, and
component (e) comprising a second glycol;
wherein the first dihydric alcohol comprises a cyclic dihydric alcohol or a combination of an aliphatic dihydric alcohol and a cyclic dihydric alcohol, the second dihydric alcohol comprises a combination of an aliphatic dihydric alcohol and a cyclic dihydric alcohol, the aliphatic dihydric alcohol comprises 1, 4-butanediol, and the cyclic dihydric alcohol comprises any one or a combination of two of 2, 8-quinoline diol and tricyclodecane dimethanol.
9. The composition of claim 8, wherein: the carbonic diester comprises any one or the combination of more than two of dimethyl carbonate, diethyl carbonate and diphenyl carbonate.
10. Use of the high strength and high modulus polyester-polycarbonate copolymer of claim 7 in the field of manufacturing packaging materials, containers, and mulching films.
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