CN112876710A - Biodegradable antibacterial graphene in-situ polymerization copolyester packaging film and preparation process thereof - Google Patents
Biodegradable antibacterial graphene in-situ polymerization copolyester packaging film and preparation process thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The application discloses a biodegradable antibacterial graphene in-situ polymerization copolyester packaging film and a preparation process thereof, wherein the antibacterial graphene in-situ polymerization copolyester packaging film comprises the following raw materials in parts by weight: 70-85 parts of graphene in-situ polymerization biodegradable copolyester, 5-20 parts of polylactic acid, 3-5 parts of inorganic filler, 0.1-1 part of antioxidant, 0.1-1 part of light stabilizer and 0.1-1 part of lubricant. According to the in-situ polymerization biodegradable copolyester of graphene, a graphene component is introduced in the polymerization process of a biodegradable polyester material, and the multi-layer gridding structure of graphene enables macromolecules of the biodegradable polyester material to be uniformly distributed, so that the molecular weight distribution is narrower, and due to the regularity of the molecular structure, many new properties which are not possessed originally, such as barrier property, antibacterial property, electric conductivity and the like, are expressed.
Description
Technical Field
The application belongs to the field of biodegradable materials, and particularly relates to a biodegradable antibacterial graphene in-situ polymerization copolyester packaging film and a preparation process thereof.
Background
With the use of disposable sanitary products such as paper towels, paper diapers and sanitary towels, the usage amount of sanitary material packages is also increasing year by year. It is anticipated that the problem of plastic contamination from sanitary packaging will certainly increase in the near future. Sanitary products have high requirements on sanitary material packaging due to the particularity of the sanitary products, and packaging materials are often required to have the characteristics of antibiosis, aging resistance, easiness in printing, high-speed automatic packaging and the like. The antibacterial property of the material is mainly achieved by adding metal ions into the material, and if the biodegradable packaging material is used for replacing the traditional plastic packaging, the problem that the metal ions directly enter the natural environment after the material is degraded to cause pollution can be caused. Therefore, the development of a novel biodegradable antibacterial packaging material which does not depend on the metal particle bacteriostasis principle is urgently needed.
Graphene is a two-dimensional crystal, and common graphite is formed by stacking planar carbon atoms which are orderly arranged in a honeycomb shape layer by layer, and the interlayer acting force of the graphite is weak, so that the graphite can be easily peeled off from each other to form a thin graphite sheet. When a graphite sheet is exfoliated into monolayers, such monolayers having only one carbon atom thick are graphene.
The graphite of 1 mm contains 300 ten thousand layers of single-layer graphene, the smallest bacterium known today is 0.2 mm, about 600 times as much as graphene, and the bacterium can be killed by cutting the cell wall immediately before it moves on the sharp nanoscale two-dimensional material.
The graphene bacteriostatic application can cut the cell membrane of bacteria by inserting the cell membrane of the bacteria and can destroy the cell membrane by directly extracting phospholipid molecules on the cell membrane in a large scale so as to kill the bacteria.
Disclosure of Invention
In order to solve the above problems, the present application provides a biodegradable in-situ polymerized copolyester packaging film of antibacterial graphene and a preparation process thereof, wherein the biodegradable in-situ polymerized copolyester packaging film of antibacterial graphene comprises the following raw materials in parts by weight: 70-85 parts of graphene in-situ polymerization biodegradable copolyester, 5-20 parts of polylactic acid, 3-5 parts of inorganic filler, 0.1-1 part of antioxidant, 0.1-1 part of light stabilizer and 0.1-1 part of lubricant.
Preferably, the thickness of the biodegradable antibacterial graphene in-situ polymerization copolyester packaging film product prepared by the method is 0.008-0.030mm, and the width of the product is 40-300 cm.
Preferably, the chemical structural formula of the graphene in-situ polymerization biodegradable copolyester is as follows:
preferably, the graphene in-situ polymerization biodegradable copolyester has the number average molecular weight of 100000-120000, the intrinsic viscosity of 0.6-1.2 dL/g and the acid value of 15-25.
Preferably, the graphene in-situ polymerization biodegradable copolyester is graphene in-situ polymerization PBAT
Preferably, the polylactic acid is one or more of Ingeo 4032D, Ingeo 4043D, Ingeo 4060D manufactured by Natureworks corporation, usa; the inorganic filler is one or more of talcum powder, calcium carbonate, titanium dioxide and white carbon black; the antioxidant is one or more of hindered phenol heat stabilizer and phosphite heat stabilizer; the light stabilizer is one or more of hindered amine light stabilizer and ultraviolet absorbent; the lubricant is one or more of erucamide, oleamide, stearic acid and calcium stearate.
Preferably, the filler has a particle size specification of 5000 mesh to 8000 mesh.
Preferably, the antioxidant is BASF Irganox 1010 or BASF Irganox 168; the stabilizer is BASF Chimassorb 944; the lubricant is erucamide.
The application also discloses a preparation process of the biodegradable antibacterial graphene in-situ polymerization copolyester packaging film, which comprises the following steps:
s1: uniformly mixing the graphene in-situ polymerization biodegradable copolyester, polylactic acid, inorganic filler, antioxidant, light stabilizer and lubricant, putting the mixture into a double-screw extruder, and carrying out melt blending at 140-180 ℃;
s2: extruding and granulating, and air-cooling and granulating to obtain the special material for the biodegradable antibacterial graphene in-situ polymerization copolyester packaging film;
s3: putting the special material for the biodegradable antibacterial graphene in-situ polymerization copolyester packaging film into a three-layer co-extrusion film blowing machine, and blowing the film to obtain a finished product of the biodegradable antibacterial graphene in-situ polymerization copolyester packaging film;
the preparation method of the graphene in-situ polymerization biodegradable copolyester sequentially comprises the steps of raw material preparation, esterification, polycondensation, chain extension and discharging, wherein the reaction raw materials comprise graphene, two dibasic acids and one dihydric alcohol, and the graphene accounts for 0.1-1 wt% of the copolyester; the dibasic acid is 2 of purified terephthalic acid, adipic acid and succinic acid, the dibasic alcohol is butanediol, and the molar ratio of the alkyd is (1.05-1.15): 1.
preferably, the diameter of the screw of the three-layer co-extrusion film blowing machine is 45-65mm, and the length-diameter ratio of the screw is 30: 1, cooling the die head internally, and controlling the film blowing temperature at 150-180 ℃.
Preferably, the graphene is hydroxyl graphene oxide; the particle size of the hydroxyl graphene oxide is 2-6 microns.
Preferably, in the preparation process of the graphene in-situ polymerization biodegradable copolyester, the reaction raw materials further comprise a reaction auxiliary agent, wherein the reaction auxiliary agent comprises 0.01-0.05 wt% of a catalyst, 0.05-0.2 wt% of an antioxidant, 0.05-0.2 wt% of a stabilizer and 0.05-0.2 wt% of a lubricant;
the catalyst is one or more of titanium catalysts and tin catalysts such as tetrabutyl titanate, stannous zincate and the like;
the antioxidant is a complex of a phosphite antioxidant and a hindered amine antioxidant, and the complex mass ratio is (0.9-1.2): 1;
the stabilizer is hindered phenol stabilizer;
the lubricant is an amide lubricant.
Preferably, the raw material preparation comprises the steps of graphene dispersion, auxiliary agent preparation and pulping, wherein,
the graphene dispersion comprises the steps of adding graphene into dihydric alcohol, and simultaneously performing pre-dispersion treatment by using a high-speed stirrer and an ultrasonic disperser to obtain graphene dispersion liquid, wherein the content of the graphene in the graphene dispersion liquid is 4-8 wt%, the power of the ultrasonic disperser is 10-15 KW, and the dispersion time is 10-40 min;
the preparation method of the auxiliary agent comprises the steps of adding a reaction auxiliary agent into dihydric alcohol, and performing pre-dispersion treatment by using a high-speed stirrer to obtain an auxiliary agent dispersion liquid, wherein the auxiliary agent content in the auxiliary agent dispersion liquid is 5-10 wt%;
the pulping comprises the steps of adding two dibasic acids and one dihydric alcohol in a certain ratio into a pulping kettle, maintaining the temperature of the pulping kettle at 65-75 ℃, enabling the rotating speed of a stirrer to be 100-120 r/min, pulping for 1 hour, adding a graphene dispersion liquid and an auxiliary dispersion liquid, and continuously pulping for 0.5-1 hour.
Preferably, the esterification step further comprises a pre-esterification step before, wherein the pre-esterification step comprises the steps of conveying the mixture slurry in the pulping kettle to a pre-esterification kettle through a screw pump, maintaining the temperature of the pre-esterification kettle at 165-175 ℃, and carrying out pre-esterification reaction for 1 hour;
the esterification comprises the steps of conveying materials in a pre-esterification kettle into a tower plate type continuous esterification reactor through a metering pump, maintaining the temperature of the reactor at 215-225 ℃, enabling the materials to flow downwards along a tower plate in sequence under the action of self gravity, keeping a high dispersion effect of graphene under the dispersion of ultrasonic waves built in the reactor, and enabling the materials to reach a high esterification degree when flowing to the bottom of the reactor by calculating the height and the distance of the tower plate.
The application also discloses a tower plate type continuous esterification reactor, which comprises a reactor body, a material inlet, a material outlet, a gas phase outlet, a tower plate and an ultrasonic dispersion part, wherein the material inlet is arranged at the upper end of the side wall of the reactor body; the material outlet is arranged at the lower end of the reactor body; the gas phase outlet is arranged at the upper end of the reactor body, the tower plate is arranged in the inner cavity of the reactor body, and the cross section of the tower plate is arranged in an inverted V shape; the ultrasonic dispersion part comprises ultrasonic dispersion probes, the ultrasonic dispersion probes are arranged on the inner side wall of the reactor body, the ultrasonic dispersion probes are matched with the tower plate to enable materials entering from the material inlet to fall on the center of the right upper side of the tower plate, and the materials flow downwards along the tower plate and are dispersed under the action of the ultrasonic dispersion probes.
This application can bring following beneficial effect:
1. according to the in-situ polymerization biodegradable copolyester of graphene, a graphene component is introduced in the polymerization process of a biodegradable polyester material, and the multi-layer gridding structure of graphene enables macromolecules of the biodegradable polyester material to be uniformly distributed, so that the molecular weight distribution is narrower, and due to the regularity of the molecular structure, many new properties which are not possessed originally, such as barrier property, antibacterial property, electric conductivity and the like, are expressed.
2. The graphene used in the invention is hydroxyl graphene oxide, and can be grafted to the molecular structure of the biodegradable polyester material through the end group functional group in the polymerization reaction, so that the in-situ polymerization effect is achieved, the reinforcing and toughening effect is achieved, the physical performance of the material is better, and the excellent anti-aging performance is shown.
3. The invention utilizes the chain extension technology of the reactive double-screw extruder to effectively improve the molecular weight of the graphene in-situ polymerized biodegradable copolyester, and simultaneously carries out end-capping treatment on the polyester molecules through chain extension reaction, thereby greatly reducing the number of active functional groups, enabling the material property to be more stable and obviously improving the weather resistance of the material.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the application and together with the description serve to explain the application and not to limit the application. In the drawings:
FIG. 1 is a schematic diagram of a plate-type continuous esterification reactor according to the present application;
fig. 2 is a schematic structural view of an ultrasonic dispersion probe according to the present application.
Detailed Description
Example 1
The embodiment discloses a tower plate type continuous esterification reactor, which comprises a reactor body 1, a material inlet 2, a material outlet 3, a tower plate 4 and an ultrasonic dispersion part, wherein the material inlet 2 is arranged at the upper end of the side wall of the reactor body 1; the material outlet 3 is arranged at the lower end of the reactor body 1; the gas phase outlet 8 is arranged at the upper end of the reactor body 1, the tower plate 4 is arranged in the inner cavity of the reactor body 1, and the cross section of the tower plate 4 is arranged in an inverted V shape; the ultrasonic dispersion portion comprises ultrasonic dispersion probes 5, the ultrasonic dispersion probes 5 are arranged on the inner side wall of the reactor body 1, the ultrasonic dispersion probes 5 are matched with the tower plate 4 to enable materials entering from the material inlet 2 to fall on the center of the position right above the tower plate 4, and the materials flow downwards along the tower plate 4 and are dispersed under the action of the ultrasonic dispersion probes 5.
It is understood that the ultrasonic dispersion portion further includes an ultrasonic generator 6, and the ultrasonic generator 6 is connected to the ultrasonic dispersion probe 5.
It can be understood that the ultrasonic dispersion probe 5 is uniformly disposed on the inner wall of the reactor body 1.
Still include heat conduction portion 7, heat conduction portion 7 sets up in the periphery of reactor body 1, and heat conduction oil inlet 71 is provided with to heat conduction portion 7 upper end, and heat conduction oil outlet 72 is provided with to heat conduction portion 7 lower extreme.
When the plate-type continuous esterification reactor in this embodiment is used, the material enters from material inlet 2, falls on column plate 4, and the material flows downwards and around along column plate 4, because the setting of ultrasonic dispersion portion, disperses the graphene in the material, effectively avoids the reunion of graphene for graphene keeps sufficient dispersion degree in reaction process always, makes molecular structure more even, and molecular weight distributes more narrowly.
Example 2: a preparation method of graphene in-situ polymerization biodegradable copolyester comprises the following steps:
s1, dispersing graphene: adding graphene into a proper amount of dihydric alcohol, and simultaneously performing pre-dispersion treatment by using a high-speed stirrer and an ultrasonic disperser to obtain a graphene dispersion liquid, wherein the graphene content in the graphene dispersion liquid is 4-8 wt%.
S2, auxiliary agent preparation: adding an auxiliary agent such as a catalyst, an antioxidant, a stabilizer, a lubricant and the like into a proper amount of dihydric alcohol, and performing pre-dispersion treatment by using a high-speed stirrer to obtain an auxiliary agent dispersion liquid, wherein the auxiliary agent content in the auxiliary agent dispersion liquid is 5-10 wt%.
S3, pulping: adding two dibasic acids and one dihydric alcohol in a certain ratio into a pulping kettle, maintaining the temperature of the pulping kettle at 65-75 ℃, rotating the stirrer at 100-120 r/min, pulping for 1 hour, adding the graphene dispersion liquid and the assistant dispersion liquid in the step (a) and the step (b), and continuously pulping for 0.5-1 hour.
S4, pre-esterification: and conveying the mixture slurry in the pulping kettle to the pre-esterification kettle through a screw pump, maintaining the temperature of the pre-esterification kettle at 165-175 ℃, and carrying out esterification reaction for 1 hour.
S5, esterification: the method comprises the steps of conveying materials in a pre-esterification kettle into a tower plate type continuous esterification reactor through a metering pump, maintaining the temperature of the reactor at 215-225 ℃, enabling the materials to flow downwards along a tower plate in sequence under the action of self gravity, keeping a high dispersion effect of graphene under the dispersion of ultrasonic waves built in the reactor, and enabling the materials to reach a high esterification degree when flowing to the bottom of the reactor by calculating the height and the distance of the tower plate.
S6, polycondensation: and (3) stably conveying the esterified substance in the tower plate type reactor to a horizontal polycondensation kettle through a metering pump, maintaining the temperature of the polycondensation kettle at 235-245 ℃, the rotating speed of a stirrer at 20-30 r/min and the pressure at 20-50 Pa, and discharging after the polycondensation reaction is carried out for 3-3.5 hours.
S7, chain extension: uniformly conveying the polycondensation-finished material into a reactive double-screw extruder through a melt pump, setting the temperature of the extruder to be 150-220 ℃, and setting the rotating speed of a screw to be 120-150 r/min; and simultaneously, uniformly feeding the chain extender into the double-screw extruder by using a weightless metering feeder, carrying out chain extension reaction on the materials in the double-screw extruder for about 4-5 min, and further reducing the melt index.
S8, cutting into granules: and (3) feeding the materials in the extruder into a water ring granulating device through a melt filter, granulating, then feeding the materials into a drying device, drying, packaging and warehousing to obtain the graphene in-situ polymerization biodegradable copolyester.
The specific implementation conditions are as follows:
characterization of
In this embodiment, the obtained graphene in-situ polymerization biodegradable copolyester is tested, wherein the testing method is as follows:
1. the biodegradation rate is tested by the following method: GB/T20197-
2. The surface resistance value is measured by the following method: GB/T1410-
3. The antibacterial performance is tested by the following steps: QB/T2591-
4. The water vapor transmission rate is measured by the following method: GB/T1037-
5. The tensile strength is measured by the following method: GB/T1040-2006
6. The elongation at break is measured by the following method: GB/T1040-2006
Table 1 performance test results of graphene in-situ polymerization biodegradable copolyester
From the data in table 1 above, it can be seen that: the in-situ polymerized biodegradable copolyester of graphene obtained by the method has the advantages of biodegradability of more than 95%, good conductivity, strong antibacterial property and high tensile strength.
Compared with example 1, the comparative example 1 shows that the copolyester does not contain graphene, has no antibacterial property, and has reduced tensile strength, poor barrier property and poor conductivity.
Comparative examples 2 to 5 compared with example 1, it can be seen that the in-situ polymerization biodegradable copolyester of graphene prepared by using only 1 kind of dibasic acid or using 3 kinds of dibasic acids has greatly reduced biodegradability, poor barrier property and poor physical properties.
Example 3: a preparation process of a biodegradable antibacterial graphene in-situ polymerization copolyester packaging film comprises the following steps:
s1: uniformly mixing 70-85 parts of graphene in-situ polymerization biodegradable copolyester obtained in the embodiment 2, 5-20 parts of polylactic acid, 3-5 parts of inorganic filler, 0.1-1 part of antioxidant, 0.1-1 part of light stabilizer and 0.1-1 part of lubricant, putting the mixture into a double-screw extruder, and carrying out melt blending at 140-180 ℃;
s2: extruding and granulating, and air-cooling and granulating to obtain the special material for the biodegradable antibacterial graphene in-situ polymerization copolyester packaging film;
s3: and putting the special material for the biodegradable antibacterial graphene in-situ polymerization copolyester packaging film into a three-layer co-extrusion film blowing machine, and blowing the film to obtain a finished product of the biodegradable antibacterial graphene in-situ polymerization copolyester packaging film.
The specific implementation conditions are as follows:
characterization of
The biodegradable antibacterial graphene in-situ polymerization copolyester packaging film obtained in example 3 is tested, wherein the test method comprises the following steps:
the antibacterial performance is tested by the following steps: QB/T2591-
Tensile strength GB/T1040-
Elongation at break GB/T1040-
Heat seal Strength QB/T2358-
Table 2 performance test results of biodegradable antibacterial graphene in-situ polymerization copolyester packaging film
From the data analysis in table 2 above, it can be seen that the biodegradable antibacterial graphene in-situ polymerization copolyester packaging film obtained in the present application has excellent antibacterial performance, tensile strength and heat sealing strength. And compared with the comparative example 1 and the example 1, and compared with the comparative example 2 and the example 2, the content of the graphene in-situ polymerization biodegradable copolyester has a large influence on the performance of the packaging film.
The embodiments in the present specification are described in a progressive manner, and the same and similar parts among the embodiments are referred to each other, and each embodiment focuses on the differences from the other embodiments. In particular, for the system embodiment, since it is substantially similar to the method embodiment, the description is simple, and for the relevant points, reference may be made to the partial description of the method embodiment.
The above description is only an example of the present application and is not intended to limit the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the scope of the claims of the present application.
Claims (10)
1. A biodegradable antibacterial graphene in-situ polymerization copolyester packaging film is characterized by comprising the following raw materials in parts by weight: 70-85 parts of graphene in-situ polymerization biodegradable copolyester, 5-20 parts of polylactic acid, 3-5 parts of inorganic filler, 0.1-1 part of antioxidant, 0.1-1 part of light stabilizer and 0.1-1 part of lubricant.
2. The biodegradable antimicrobial graphene in-situ polymerization copolyester packaging film according to claim 1, wherein: the graphene in-situ polymerization biodegradable copolyester has the following chemical structural formula:
3. the biodegradable antimicrobial graphene in-situ polymerization copolyester packaging film according to claim 1, wherein: the graphene in-situ polymerization biodegradable copolyester has the number average molecular weight of 100000-120000, the intrinsic viscosity of 0.6-1.2 dL/g and the acid value of 15-25.
4. The biodegradable antimicrobial graphene in-situ polymerization copolyester packaging film according to claim 1, wherein: the polylactic acid is one or more of Ingeo 4032D, Ingeo 4043D, Ingeo 4060D manufactured by Natureworks, USA; the inorganic filler is one or more of talcum powder, calcium carbonate, titanium dioxide and white carbon black; the antioxidant is one or more of hindered phenol heat stabilizer and phosphite heat stabilizer; the light stabilizer is one or more of hindered amine light stabilizer and ultraviolet absorbent; the lubricant is one or more of erucamide, oleamide, stearic acid and calcium stearate.
5. A preparation process of a biodegradable antibacterial graphene in-situ polymerization copolyester packaging film is characterized by comprising the following steps:
s1: uniformly mixing the graphene in-situ polymerization biodegradable copolyester, polylactic acid, inorganic filler, antioxidant, light stabilizer and lubricant, putting the mixture into a double-screw extruder, and carrying out melt blending at 140-180 ℃;
s2: extruding and granulating, and air-cooling and granulating to obtain the special material for the biodegradable antibacterial graphene in-situ polymerization copolyester packaging film;
s3: putting the special material for the biodegradable antibacterial graphene in-situ polymerization copolyester packaging film into a three-layer co-extrusion film blowing machine, and blowing the film to obtain a finished product of the biodegradable antibacterial graphene in-situ polymerization copolyester packaging film;
the preparation method of the graphene in-situ polymerization biodegradable copolyester sequentially comprises the steps of raw material preparation, esterification, polycondensation, chain extension and discharging, wherein the reaction raw materials comprise graphene, two dibasic acids and one dihydric alcohol, and the graphene accounts for 0.1-1 wt% of the copolyester; the dibasic acid is 2 of purified terephthalic acid, adipic acid and succinic acid, the dibasic alcohol is butanediol, and the molar ratio of the alkyd is (1.05-1.15): 1.
6. the process according to claim 5, characterized in that: the graphene is hydroxyl graphene oxide; the particle size of the hydroxyl graphene oxide is 2-6 microns.
7. The process according to claim 5, characterized in that: in the preparation process of the graphene in-situ polymerization biodegradable copolyester, reaction raw materials further comprise a reaction auxiliary agent, wherein the reaction auxiliary agent comprises 0.01-0.05 wt% of a catalyst, 0.05-0.2 wt% of an antioxidant, 0.05-0.2 wt% of a stabilizer and 0.05-0.2 wt% of a lubricant;
the catalyst is one or more of titanium catalysts and tin catalysts such as tetrabutyl titanate, stannous zincate and the like;
the antioxidant is a complex of a phosphite antioxidant and a hindered amine antioxidant, and the complex mass ratio is (0.9-1.2): 1;
the stabilizer is hindered phenol stabilizer;
the lubricant is an amide lubricant.
8. The process according to claim 5, characterized in that: the preparation of the raw materials comprises the steps of graphene dispersion, auxiliary agent preparation and pulping, wherein,
the graphene dispersion comprises the steps of adding graphene into dihydric alcohol, and simultaneously performing pre-dispersion treatment by using a high-speed stirrer and an ultrasonic disperser to obtain graphene dispersion liquid, wherein the content of the graphene in the graphene dispersion liquid is 4-8 wt%, the power of the ultrasonic disperser is 10-15 KW, and the dispersion time is 10-40 min;
the preparation method of the auxiliary agent comprises the steps of adding a reaction auxiliary agent into dihydric alcohol, and performing pre-dispersion treatment by using a high-speed stirrer to obtain an auxiliary agent dispersion liquid, wherein the auxiliary agent content in the auxiliary agent dispersion liquid is 5-10 wt%;
the pulping comprises the steps of adding two dibasic acids and one dihydric alcohol in a certain ratio into a pulping kettle, maintaining the temperature of the pulping kettle at 65-75 ℃, enabling the rotating speed of a stirrer to be 100-120 r/min, pulping for 1 hour, adding a graphene dispersion liquid and an auxiliary dispersion liquid, and continuously pulping for 0.5-1 hour.
9. The process according to claim 5, characterized in that: the esterification step also comprises a pre-esterification step, wherein the pre-esterification step comprises the step of conveying the mixture slurry in the pulping kettle to a pre-esterification kettle through a screw pump, maintaining the temperature of the pre-esterification kettle at 165-175 ℃, and carrying out pre-esterification reaction for 1 hour;
the esterification comprises the steps of conveying materials in a pre-esterification kettle into a tower plate type continuous esterification reactor through a metering pump, maintaining the temperature of the reactor at 215-225 ℃, enabling the materials to flow downwards along a tower plate in sequence under the action of self gravity, keeping a high dispersion effect of graphene under the dispersion of ultrasonic waves built in the reactor, and enabling the materials to reach a high esterification degree when flowing to the bottom of the reactor by calculating the height and the distance of the tower plate.
10. The process according to claim 9, characterized in that: the plate-type continuous esterification reactor comprises:
the reactor body is provided with a plurality of reaction chambers,
the material inlet is arranged at the upper end of the side wall of the reactor body;
the material outlet is arranged at the lower end of the reactor body;
a gas phase outlet provided at an upper end of the reactor body,
the tower plate is arranged in the inner cavity of the reactor body, and the cross section of the tower plate is arranged in an inverted V shape;
the ultrasonic dispersion part comprises ultrasonic dispersion probes, a plurality of ultrasonic dispersion probes are arranged on the inner side wall of the reactor body, the ultrasonic dispersion probes are matched with the tower plate to enable materials entering from the material inlet to fall on the center of the right upper side of the tower plate, and the materials flow downwards along the tower plate and are dispersed under the action of the ultrasonic dispersion probes.
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