CN113968962B - 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 from 2 to 2.2 ten thousand yuan/ton to 2.4 to 2.6 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 ester exchange reaction on a first mixed reaction system containing carbonic diester, 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 the temperature of 200-295 ℃ to obtain a high-strength high-modulus polyester-polycarbonate copolymer;
alternatively, the preparation method comprises:
(i) Carrying out ester exchange reaction on a first mixed reaction system containing carbonic diester, 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 keeping 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 the temperature of 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 high modulus polyester-polycarbonate copolymer synthesized by the foregoing preparation method.
In some embodiments, the high strength, high modulus polyester-polycarbonate copolymer has a tensile strength of no less than 17.0MPa and a tensile modulus of no less than 95.0MPa.
Some embodiments of the present invention also provide a composition for synthesizing a high strength, 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 the cyclic dihydric alcohol, the second dihydric alcohol comprises a combination of an aliphatic dihydric alcohol and the cyclic dihydric alcohol, the aliphatic dihydric alcohol comprises 1, 4-butanediol, and the cyclic dihydric alcohol comprises any one of 2, 8-quinoline diol and tricyclodecane dimethanol or a combination of two thereof.
Some embodiments of the present invention also provide uses of the high strength and high modulus polyester-polycarbonate copolymer, for example, in the field of preparing packaging materials (such as packaging bags, packaging films, etc.), 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 has low price, 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;
(3) According to the invention, a carbonate bond (-OCOO-) is introduced into the polyester-polycarbonate copolymer, so that the content of a fatty 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 may 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 ester exchange reaction on a first mixed reaction system containing carbonic diester, 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 under a vacuum condition at the temperature of 200-295 ℃ 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 ester exchange reaction on a first mixed reaction system containing carbonic diester, 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 keeping the reaction system in the protective atmosphere to obtain a third intermediate product;
(iii) And (3) carrying out polycondensation reaction on the fifth mixed reaction system containing the third intermediate product, the polycondensation catalyst and the stabilizer under the vacuum condition at the temperature of 200-295 ℃ 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 of 2, 8-quinoline diol, tricyclodecane dimethanol, or a combination of two thereof, but is not limited thereto, and the specific structure may be as shown in the following formula:
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 a 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 carbonate and 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 from 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 added mass of the polycondensation catalyst is 0.01 to 0.5% of the theoretical mass of the high-strength high-modulus polyester-polycarbonate copolymer, and the added mass of the stabilizer 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 under a protective atmosphere, reducing the temperature to room temperature at a cooling rate of 1-50 ℃/min after the reaction is finished, and then maintaining the temperature for 1.0-5.0 h under 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 to 6.0 hours at the temperature of between 150 and 240 ℃ in a protective atmosphere, the temperature is reduced to room temperature at the cooling rate of between 1 and 50 ℃/min after the reaction is finished, and then the reaction is maintained for 1.0 to 5.0 hours 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 to 6.0 hours at the temperature of between 150 and 240 ℃ in a protective atmosphere, the temperature is reduced to room temperature at the cooling rate of between 1 and 50 ℃/min after the reaction is finished, and then the reaction is maintained for 1.0 to 5.0 hours 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 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. Compared with the traditional process without a cooling step and high-temperature vacuumizing, the preparation method disclosed by the invention has the advantages that the cooling rate is 1-50 ℃/min to reduce the temperature to the room temperature, the slower the cooling rate is, the more perfect the crystallization of the product can be realized, 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 diester, first dihydric alcohol and 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, and 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 the 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 the rate of 1-50 ℃/min after finishing, and keeping 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 ℃ to perform polycondensation for 2.0-10.0 hours to obtain the high-strength 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, 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, tetraethoxy germanium, 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, 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 one or a combination of 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 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, in combination with one or more thereof, but is not limited thereto.
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 high-strength high-modulus polyester-polycarbonate copolymer has the tensile strength of not less than 17.0MPa and the tensile modulus of not less than 95.0MPa.
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 making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention. Experimental procedures without specific conditions noted in the following examples, generally according to conventional conditions, or according to conditions recommended by the manufacturer.
In the following examples, thermal transition performance tests were carried out using a differential scanning calorimeter (Mettler Toledo DSC), N 2 Atmosphere, temperature range is-70-280 ℃, and heating rate is 10 ℃/min.
In the following examples, the mechanical properties were measured in an Instron model 5567 universal material tester, with sample dimensions of 20.0mm in length, 2.0mm in width and 1.0mm in thickness and a tensile speed of 20mm/min.
In the following examples, labthink VAC-V2 was used to determine the oxygen and carbon dioxide barrier properties as CO respectively 2 And O 2 As a gas source, the sample size of phi =97mm and the permeation area of 38.5cm, measured at 23 ℃ and 50% RH 2 。
Example 1
Adding 90.1g (1.0 mol) of dimethyl carbonate, 53.0g (0.588 mol) of 1, 4-butanediol, 1.9g (0.012 mol) of 2, 8-quinoline diol and 0.4g of germanium dioxide into a reactor, gradually heating to 90 ℃ under the protection of nitrogen, reacting for 36.0 hours, then closing heating, cooling 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-quinoline diol oligomer.
21.8g (0.1125 mol) of dimethyl terephthalate, 24.0g (0.1375 mol) of dimethyl adipate, 39.4g (0.4375 mol) of 1, 4-butanediol, 2.0g (0.0125 mol) of 2, 8-quinolinediol, 7g of polybutylene carbonate 2, 8-quinolinediol oligomer and 0.105g of isopropyl titanate are put into a reactor, gradually heated to 220 ℃ under the condition of nitrogen protection, reacted for 6.0 hours, then the heating is closed, the temperature is reduced to room temperature at the cooling 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 maintained to be lower than 25Pa by continuous vacuum pumping, 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 from 1 to 10, and m is an integer from 15 to 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 added 2 The permeability coefficient is 3.44barrer 2 The permeability coefficient was 5.98barrer.
Method for preparing high-strength high-modulus polyester-polycarbonate copolymer obtained in the example 1 On the H-NMR spectrum, the peak at 7.91ppm was H (4H) on the benzene ring, the peak at 6.77 to 7.73ppm was H (5H) on the quinoline ring in 2, 8-quinolinediol, the peak at 4.00 to 4.31ppm was H (4H) on the methylene group near the hydroxyl group in 1, 4-butanediol, the peak at 2.24ppm was H (4H) on the methylene group near the carbonyl group in adipic acid, the peak at 1.56 to 1.84ppm was H (4H) on the middle two methylene groups of 1, 4-butanediol, and the peak at 1.48ppm was H (4H) on the middle two methylene groups of adipic acid.
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 modulus polyester-polycarbonate copolymer obtained in this example is shown in FIG. 2.
Example 2
118.1g (1.0 mol) of diethyl carbonate, 53.0g (0.588 mol) of 1, 4-butanediol, 2.4g (0.012 mol) 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 (0.1125 mol) of dimethyl terephthalate, 24.0g (0.1375 mol) of dimethyl adipate, 39.4g (0.4375 mol) of 1, 4-butanediol, 2.5g (0.0125 mol) 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 kept to be lower than 20Pa by continuous vacuumization, 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 from 1 to 10, and m is an integer from 15 to 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 3 2 The permeability coefficient is 1.65barrer 2 The permeability coefficient was 3.07barrer.
Example 3
Putting 118.1g (1.0 mol) of diethyl carbonate, 48.4g (0.3 mol) 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 to heat, 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 polycarbonate oligomer.
21.8g (0.1125 mol) of dimethyl terephthalate, 24.0g (0.1375 mol) of dimethyl adipate, 26.0g (0.288 mol) of 1, 4-butanediol, 1.9g (0.012 mol) 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 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 shown in formula (III).
Wherein x, y, z, u and v are integers from 1 to 10, and m is an integer from 15 to 150.
The detection proves that the high-strength high-modulus polyester-polycarbonate copolymer obtained in the embodiment is white, the tensile strength is 21.6MPa, the tensile modulus is 133.1MPa, the elongation at break is 717%, the glass transition temperature is-5.2 ℃, and the temperature of CO is higher than that of the conventional method 2 The permeability coefficient is 2.78barrer 2 The permeability coefficient was 4.62barrer.
Example 4
214.2g (1.0 mol) of diphenyl carbonate, 196.3g (1.0 mol) 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 (0.1125 mol) of dimethyl terephthalate, 24.0g (0.1375 mol) of dimethyl adipate, 39.4g (0.4375 mol) of 1, 4-butanediol, 12.3g (0.0625 mol) 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 from 1 to 10, and m is an integer from 15 to 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%, the glass transition temperature is 28.1 ℃, and the temperature of CO is higher than that of the conventional polyester-polycarbonate copolymer 2 The permeability coefficient is 1.15barrer 2 The permeability coefficient was 2.34barrer.
Example 5
85.7g (0.4 mol) of diphenyl carbonate, 96.7g (0.6 mol) of 2, 8-quinolinediol, 117.8g (0.6 mol) of tricyclodecanedimethanol and 0.022g of tetraethoxygermanium are put into a reactor, gradually heated to 220 ℃ under the protection of nitrogen, reacted for 4.0 hours, then the reactor is closed to heat, cooled to room temperature at the cooling rate of 30 ℃/min under the protection of nitrogen, and kept for 5.0 hours, thus obtaining the 2, 8-quinolinediol tricyclodecanedimethanol oligomer.
21.8g (0.1125 mol) of dimethyl terephthalate, 24.0g (0.1375 mol) of dimethyl adipate, 39.4g (0.4375 mol) of 1, 4-butanediol, 4.0g (0.025 mol) of 2, 8-quinolinediol, 2.5g (0.0125 mol) 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.
1g of poly (2, 8-quinolinediol tricyclodecanedimethanol) oligomer, 99g of poly (terephthalic acid adipic acid butanediol tricyclodecanedimethanol ester oligomer, 0.01g of germanium acetate and 0.5g of phosphorous acid are put into a reactor, the reactor is vacuumized to 25Pa, the temperature is gradually increased to 250 ℃, the reaction is finished after the vacuum degree of the reaction system is kept lower than 30Pa by continuous vacuum pumping for 8.0 hours, and the high-strength and high-modulus polyester-polycarbonate copolymer is obtained, wherein the structure is shown in the formula (V).
Wherein x, y, z, u, v, w, a and b are integers from 1 to 10, and m is an integer from 15 to 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, the elongation at break is 853%, the glass transition temperature is 10.7 ℃, and the temperature of CO is higher than that of the polycarbonate copolymer 2 The permeability coefficient is 3.94barrer 2 The permeability coefficient was 6.48barrer.
Example 6
Putting 59.1g (0.5 mol) of diethyl carbonate, 196.3g (1.0 mol) of tricyclodecanedimethanol and 1.0g of titanium dioxide into a reactor, gradually heating to 120 ℃ under the protection of nitrogen, reacting for 20.0 hours, then closing heating, cooling to room temperature at a cooling rate of 50 ℃/min under the protection of nitrogen, and keeping for 2.0 hours to obtain the poly-tricyclodecanedimethanol oligomer.
21.8g (0.1125 mol) of dimethyl terephthalate, 24.0g (0.1375 mol) of dimethyl adipate, 60.8g (0.675 mol) of 1, 4-butanediol, 10.1g (0.0625 mol) of 2, 8-quinoline diol, 2.5g (0.0125 mol) 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.
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 are put into a reactor, the reactor is vacuumized to 25Pa, then the temperature is gradually increased to 200 ℃, the reaction is finished after the vacuum degree of the reaction system is kept lower than 20Pa by continuous vacuum pumping, and the reaction is finished after 10.0 hours, so that the high-strength and high-modulus polyester-polycarbonate copolymer is obtained, and the structure of the copolymer is shown as the formula (VI).
Wherein x, y, z, u, v, w and a are integers from 1 to 10, and m is an integer from 15 to 150.
Through detection, the high-strength 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%, the glass transition temperature is 22.5 ℃, and the CO temperature is higher than that of the polycarbonate copolymer 2 The permeability coefficient is 2.57barrer 2 The permeability coefficient was 3.36barrer.
Comparative example 1
Putting 43.7g (0.225 mol) of dimethyl terephthalate, 47.9g (0.275 mol) of dimethyl adipate, 81.1g (0.9 mol) 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 and heating, 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 polybutylene terephthalate obtained by the comparative example is detected to be white, the tensile strength is 16.6MPa, the tensile modulus is 93.5MPa, and the fracture degree is detectedElongation 917%, glass transition temperature-25.2 deg.C, O 2 The permeability coefficient is 4.33barrer 2 The permeability coefficient was 6.73barrer.
Comparative example 2
Putting 43.7g (0.225 mol) of dimethyl terephthalate, 47.9g (0.275 mol) of dimethyl adipate, 81.1g (0.9 mol) 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 O 2 The permeability coefficient is 4.52barrer 2 The permeability coefficient was 6.61barrer.
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) Under a protective atmosphere, carrying out transesterification reaction on a first mixed reaction system containing a carbonic diester, a first dihydric alcohol and a first transesterification catalyst at 90-220 ℃ for 4.0-36.0 h, and after the end, carrying out transesterification reaction at 1-50 o Reducing the temperature to room temperature at the cooling rate of C/min, and then keeping the temperature for 1.0-5.0 h in a protective atmosphere to form a first intermediate product;
(2) Under the protective atmosphere, a second mixed reaction system containing terephthalic acid and/or an esterified product thereof, adipic acid and/or an esterified product thereof, a second dihydric alcohol and a second esterification or ester exchange catalyst is subjected to esterification or ester exchange reaction for 1.5 to 6.0 hours at the temperature of 150 to 240 ℃, and after the reaction is finished, the reaction is carried out for 1 to 50 hours o Reducing the temperature to room temperature at the cooling rate of C/min, and then keeping the temperature for 1.0-5.0 h in a protective atmosphere to obtain a second intermediate product;
(3) 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 for 2.0 to 10.0 hours under the vacuum condition at the temperature of 200 to 295 ℃ to obtain a high-strength and high-modulus polyester-polycarbonate copolymer;
alternatively, the preparation method comprises:
under a protective atmosphere, the method comprises the following stepsThe first mixed reaction system containing carbonic diester, first dihydric alcohol and first ester exchange catalyst is used for carrying out ester exchange reaction for 4.0 to 36.0 hours at the temperature of 90 to 220 ℃, and after the ester exchange reaction is finished, the reaction time is 1 to 50 o The temperature is reduced to room temperature at the cooling rate of C/min, and then the temperature is kept for 1.0 to 5.0 hours in a protective atmosphere to form a first intermediate product;
(ii) under a protective atmosphere, 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 to 240 ℃ for 1.5 to 6.0h, and then carrying out esterification or ester exchange reaction at 1 to 50 h o Reducing the temperature to room temperature at the cooling rate of C/min, and then keeping the temperature for 1.0-5.0 h in a protective atmosphere to obtain a third intermediate product;
(iii) carrying out polycondensation reaction on a fifth mixed reaction system containing a third intermediate product, a polycondensation catalyst and a stabilizer for 2.0 to 10.0 hours under a vacuum condition at the temperature of 200 to 295 ℃ to obtain a high-strength high-modulus polyester-polycarbonate copolymer;
the first dihydric alcohol is cyclic dihydric alcohol or a combination of aliphatic dihydric alcohol and cyclic dihydric alcohol, the second dihydric alcohol is a combination of aliphatic dihydric alcohol and cyclic dihydric alcohol, the aliphatic dihydric alcohol is 1, 4-butanediol, and the cyclic dihydric alcohol is any one or a combination of two of 2, 8-quinoline diol and tricyclodecane dimethanol;
in step (1) or step (i), the molar ratio of the carbonic acid diester to the first glycol is 1; the addition amount of the first transesterification catalyst is 0.01 to 0.5 percent of the theoretical mass of the first intermediate product;
in the step (2) or the step (ii), the molar ratio of the combination of the terephthalic acid and/or the ester thereof and the adipic acid and/or the ester thereof to the second glycol is 1.2 to 3.0; the addition amount of the second esterification or ester exchange catalyst is 0.01 to 0.5 percent of the theoretical mass of the second intermediate product or the third intermediate product; 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 diol reacted in the polymer is 1 to 99 to 1;
in the step (3), the mass ratio of the first intermediate product to the second intermediate product is 1 to 99.
2. The method of claim 1, wherein: the carbonic diester comprises any one of dimethyl carbonate, diethyl carbonate and diphenyl carbonate or the combination of more than two of the dimethyl carbonate, the diethyl carbonate and the diphenyl carbonate.
3. The method of claim 1, wherein: in the step (3) or (iii), the mass of the polycondensation catalyst is 0.01 to 0.5 percent of the theoretical mass of the high-strength high-modulus polyester-polycarbonate copolymer, and the mass of the stabilizer is 0.01 to 0.5 percent of the theoretical mass of the high-strength high-modulus polyester-polycarbonate copolymer.
4. The method of claim 1, wherein: in the step (3) or (iii), vacuumizing to below 100Pa at room temperature, gradually heating to 200 to 295 ℃, and continuously vacuumizing to keep the vacuum not to exceed 100Pa in the whole polycondensation process.
5. The method of claim 1, wherein: the first transesterification catalyst includes any one of a titanium-based catalyst, a tin-based catalyst, and a germanium-based catalyst, or a combination of two or more thereof.
6. The method of claim 1, wherein: the second esterification or transesterification catalyst includes any one or a combination of two or more of a titanium-based catalyst, a tin-based catalyst, and a germanium-based catalyst.
7. The method of claim 1, wherein: the polycondensation catalyst comprises any one or a combination of more than two of a titanium catalyst, a tin catalyst and a germanium catalyst.
8. The method of claim 1, wherein: the stabilizer comprises 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.
9. A high strength, high modulus polyester-polycarbonate copolymer prepared by the process of any one of claims 1-8, having a tensile strength of not less than 17.0MPa and a tensile modulus of not less than 95.0MPa.
10. Use of the high strength and high modulus polyester-polycarbonate copolymer of claim 9 in the field of making packaging materials, containers or geomembranes.
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| CN109705323B (en) * | 2019-01-15 | 2020-12-15 | 南通龙达生物新材料科技有限公司 | Preparation method of high-barrier aliphatic-aromatic copolyester containing aliphatic carbonate chain segments |
| CN110407991B (en) * | 2019-06-25 | 2020-07-17 | 浙江大学 | Multi-block copolymer based on 2, 5-furandicarboxylic acid polyester and aliphatic polycarbonate and preparation method thereof |
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| CN102093544A (en) * | 2009-12-14 | 2011-06-15 | 上海杰事杰新材料(集团)股份有限公司 | 1, 2-propanediol copolyester polyterephthalate with high 1, 2-propanediol content and preparation method thereof |
| CN106800643A (en) * | 2017-02-09 | 2017-06-06 | 中国科学院化学研究所 | A kind of preparation method of high-fire resistance isobide type atactic polyester |
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