CN112876660A - Graphene in-situ polymerization biodegradable copolyester and preparation method and application thereof - Google Patents
Graphene in-situ polymerization biodegradable copolyester and preparation method and application thereof Download PDFInfo
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Abstract
The graphene in-situ polymerization biodegradable copolyester is characterized in that a graphene component is introduced in the polymerization process of a biodegradable polyester material, and macromolecules of the biodegradable polyester material are uniformly distributed through a multi-layer gridding structure of graphene, so that the molecular weight distribution is narrower, and many new properties which are not possessed originally are expressed due to the regularity of the molecular structure, such as barrier property, antibacterial property, electric conductivity and the like.
Description
Technical Field
The application belongs to the field of biodegradable materials, and particularly relates to graphene in-situ polymerization biodegradable copolyester and a preparation method and application thereof.
Background
Plastics bring great convenience to people's life, but the environmental problem that brings because of improper processing after a large amount of plastic products use the abandonment has become the focus of present global concern. Along with the coming of the policy of forbidding import of waste plastic garbage in China, the enhancement of garbage classification, waste plastic recycling, organic garbage biochemical treatment and the like gradually become social consensus, and biodegradable plastics are also paid attention because the biodegradable plastics are beneficial to compost biochemical treatment. The world has seen a banning policy for disposable products which are not easy to be recovered and are easy to be polluted, and the application of biodegradable materials is promoted.
At present, the most widely and mature biodegradable materials are PBAT (polybutylene terephthalate-adipate terephthalate) and PLA (polylactic acid), wherein the PBAT raw material source is a petrochemical product, the supply is stable, the yield is high, and the PBAT biodegradable material can be applied to the fields of shopping bags, garbage bags, agricultural mulching films, sanitary products and the like. However, due to the characteristics of the PBAT material, the PBAT material has the problems of short shelf life, poor barrier property, difficult degradation regulation and control and the like, so that the PBAT material is difficult to further apply and can only be used as a disposable product with a low added value. Therefore, the development of the PBAT copolymer material with adjustable degradation period, high barrier and high weather resistance has very important significance for the biodegradation industry in China.
Graphene (Graphene) is sp2The hybridized and connected carbon atoms are tightly packed into a new material with a single-layer two-dimensional honeycomb lattice structure. The graphene has excellent optical, electrical and mechanical properties, has important application prospects in the aspects of materials science, micro-nano processing, energy, biomedicine, drug delivery and the like, and is considered to be a revolutionary material in the future.
Chinese patent CN201811069121.6 discloses a preparation method and a special device of a functional graphene in-situ polymerized polyester terpolymer composite material, and the prepared graphene terpolymer composite material is obviously improved in antistatic performance, antibacterial performance, barrier performance and aging resistance compared with the traditional material. However, the polyester fiber biodegradable material mainly aims at the non-degradable polyester fiber, has a certain application value in the textile field, and is not suitable for the biodegradation field of other materials.
Disclosure of Invention
In order to solve the problems, the application provides graphene in-situ polymerization biodegradable copolyester which is characterized by comprising the following chemical structural formula: .
The application also provides a preparation method of the graphene in-situ polymerization biodegradable copolyester, which sequentially comprises the steps of raw material preparation, esterification, polycondensation, chain extension and discharging, wherein the reaction raw materials comprise graphene, two kinds of dibasic acids and one kind of 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 molar ratio of alkyds is 1.1: 1.
preferably, the graphene is hydroxyl graphene oxide; the particle size of the hydroxyl graphene oxide is 2-6 microns.
Preferably, the catalyst also comprises a reaction auxiliary agent, wherein the reaction auxiliary agent comprises 0.01-0.05 wt% of catalyst, 0.05-0.2 wt% of antioxidant, 0.05-0.2 wt% of stabilizer and 0.05-0.2 wt% of 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 antioxidant is BASF Irganox 1010 and BASF Irganox 168, and the compounding mass ratio is 1: 1; the stabilizer is BASF Chimassorb 944; the lubricant is erucamide.
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 graphene content 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 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.
Preferably, the polycondensation step comprises the steps of conveying the esterified substance obtained in the plate-type continuous esterification reactor to a horizontal polycondensation kettle stably 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; 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 uniformly feeding the chain extender into a double-screw extruder, and carrying out chain extension reaction on the materials in the double-screw extruder for about 4-5 min, wherein the chain extender is one of isocyanate chain extenders or multi-epoxy chain extenders. The length-diameter ratio of the reactive double-screw extruder is 54: 1, the diameter of the screw is 40-95 mm.
Preferably, the structure of the plate type continuous esterification reactor comprises a reactor body, a material inlet, a material 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.
Preferably, the reactor further comprises a heat conduction part, the heat conduction part is arranged on the periphery of the reactor body, a heat conduction oil inlet is formed in the upper end of the heat conduction part, and a heat conduction oil outlet is formed in the lower end of the heat conduction part.
The graphene in-situ polymerization biodegradable copolyester obtained by the method can be used in the fields of antistatic protective films, agricultural mulching films, antibacterial packages, composite packages, barrier materials, industrial packages, electronic packaging materials, disposable tableware, hygienic products and the like.
The graphene in-situ polymerization biodegradable copolyester obtained by the method has the number average molecular weight of 80000-160000, the intrinsic viscosity of 0.6-1.2 dL/g and the molecular weight distribution of 1.4-1.8.
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 by virtue of a multi-layer gridding structure of graphene, macromolecules of the biodegradable polyester material are uniformly distributed, the molecular weight distribution is narrower, and due to the regularity of the molecular structure, a plurality of new characteristics 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 biodegradability of the in-situ polymerized and biodegradable copolyester of the graphene can be influenced to a certain extent by controlling the amount and granularity of the introduced graphene, so that the purpose of adjustable biodegradation time is achieved;
4. in the aspect of the preparation method, a special ultrasonic dispersion tower plate type reactor is utilized, continuous reaction is realized, and simultaneously, graphene in materials is dispersed through a built-in ultrasonic dispersion device, so that the agglomeration of the graphene is effectively avoided, the graphene can always keep enough dispersion degree in the reaction process, the molecular structure is more uniform, and the molecular weight distribution is narrower;
5. according to the invention, a reactive double-screw extruder chain extension technology is utilized, the molecular weight of the graphene in-situ polymerization biodegradable copolyester is effectively improved, and meanwhile, the polyester molecules are subjected to end-capping treatment through a chain extension reaction, so that the number of active functional groups is greatly reduced, the material property is more stable, and the weather resistance of the material can be obviously improved;
6. the preparation method of the graphene in-situ polymerization biodegradable copolyester provided by the invention is simple in process, strong in operability and higher in practical value.
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:
example 3: characterization of
In this example, the graphene in-situ polymerization biodegradable copolyester obtained in example 1 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.
The embodiments in the specification are all described in a progressive mode, the same and similar parts among the embodiments are referred to each other, and each embodiment focuses on the difference between 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. The graphene in-situ polymerization biodegradable copolyester is characterized by having the following chemical structural formula:
2. the preparation method of the graphene in-situ polymerization biodegradable copolyester is characterized by sequentially comprising the steps of raw material preparation, esterification, polycondensation, chain extension and discharging, wherein the reaction raw materials comprise graphene, two dibasic acids and a 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.
3. the preparation method of the graphene in-situ polymerization biodegradable copolyester as claimed in claim 2, wherein the preparation method comprises the following steps: the graphene is hydroxyl graphene oxide; the particle size of the hydroxyl graphene oxide is 2-6 microns.
4. The preparation method of the graphene in-situ polymerization biodegradable copolyester as claimed in claim 2, wherein the preparation method comprises the following steps: the catalyst also comprises a reaction auxiliary agent, wherein the reaction auxiliary agent comprises 0.01-0.05 wt% of catalyst, 0.05-0.2 wt% of antioxidant, 0.05-0.2 wt% of stabilizer and 0.05-0.2 wt% of 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.
5. The preparation method of the graphene in-situ polymerization biodegradable copolyester as claimed in claim 4, wherein the preparation method comprises the following steps: the antioxidant is BASF Irganox 1010 and BASF Irganox 168, and the compounding mass ratio is 1: 1;
the stabilizer is BASF Chimassorb 944;
the lubricant is erucamide.
6. The preparation method of graphene in-situ polymerization biodegradable copolyester according to claim 2, characterized by comprising the following steps: 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 content of the reaction auxiliary agent 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.
7. The preparation method of graphene in-situ polymerization biodegradable copolyester according to claim 6, characterized by comprising the following steps: 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.
8. The preparation method of graphene in-situ polymerization biodegradable copolyester according to claim 7, characterized by comprising the following steps: the polycondensation step comprises the steps of conveying the esterified substance obtained in the tower plate type continuous esterification reactor to a horizontal polycondensation kettle stably 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;
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 uniformly feeding the chain extender into a double-screw extruder, and carrying out chain extension reaction on the materials in the double-screw extruder for about 4-5 min, wherein the chain extender is one of isocyanate chain extenders or multi-epoxy chain extenders.
9. The preparation method of graphene in-situ polymerization biodegradable copolyester according to claim 8, characterized by comprising the following steps: 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.
10. The graphene in-situ polymerization biodegradable copolyester of claim 1 or the graphene in-situ polymerization biodegradable copolyester obtained by the preparation method of claims 2 to 9, characterized in that: can be used in the fields of antistatic protective films, agricultural mulching films, antibacterial packages, composite packages, barrier materials, industrial packages, electronic packaging materials, disposable tableware, sanitary products and the like.
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