CN110437595B - Antistatic biodegradable polymer composite material and preparation method thereof - Google Patents

Antistatic biodegradable polymer composite material and preparation method thereof Download PDF

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CN110437595B
CN110437595B CN201810416048.9A CN201810416048A CN110437595B CN 110437595 B CN110437595 B CN 110437595B CN 201810416048 A CN201810416048 A CN 201810416048A CN 110437595 B CN110437595 B CN 110437595B
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biodegradable polymer
graphene oxide
composite material
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reduced graphene
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CN110437595A (en
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解孝林
瞿昊
叶昀昇
周兴平
尹亮亮
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Huazhong University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
    • C08J3/215—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase at least one additive being also premixed with a liquid phase
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/14—Gas barrier composition

Abstract

The invention discloses an antistatic biodegradable polymer composite material and a preparation method thereof, wherein the composite material comprises a biodegradable polymer matrix and reduced graphene oxide, wherein the reduced graphene oxide is coated on the surface of a biodegradable polymer microsphere; in addition, the mass ratio of the biodegradable polymer matrix to the reduced graphene oxide is 100: 1-100: 30, and the biodegradable polymer matrix is polypropylene carbonate (PPC) or polybutylene adipate terephthalate (PBAT). Compared with the prior art, the invention can effectively solve the problem of difficult dispersion caused by stacking and agglomeration of graphene in the polymer and improve the glass transition temperature, the mechanical property and the antistatic property of the biodegradable polymer (such as polypropylene carbonate) by improving the content of the conductive filler in the composite material, the whole process flow of the corresponding composite material preparation method, the reaction conditions of each step and the like.

Description

Antistatic biodegradable polymer composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of biodegradable materials, and particularly relates to an antistatic biodegradable polymer composite material and a preparation method thereof.
Background
The high polymer material has the advantages of light weight, low price and the like, and is widely applied to scientific research and many aspects of people's life. But the vigorous development of the plastics industry brings about a great deal of white pollution, which seriously damages the ecosystem. Based on this, the research and application of biodegradable polymers is becoming more and more important. Biodegradable polymers include natural polymers including starch, cellulose, chitin, etc., and chemically synthesized biodegradable polymers such as polypropylene carbonate (PPC) polymerized from carbon dioxide and propylene oxide, polybutylene adipate/terephthalate (PBAT) copolymerized from terephthalic acid, adipic acid and 1, 4-butanediol, polylactic acid (PLA) polymerized from lactic acid as a raw material, etc.
Biodegradable polymers have certain disadvantages such as poor mechanical properties and low glass transition temperature, which limit the range of applications. The addition of nanofillers (such as graphene oxide and cellulose nanofibers) to biodegradable polymers can increase the mechanical strength and glass transition temperature of the material. However, the strong interaction of the nanofiller (such as pi-pi interaction between graphene oxides and hydrogen bonding between cellulose nanofibers) causes the filler to agglomerate in the biodegradable polymer, resulting in the decrease of the toughness of the composite material. In addition, the thermal properties of graphene oxide and cellulose nanofibers are poor, and the addition of the graphene oxide and cellulose nanofibers as fillers into a polymer matrix can cause the thermal decomposition temperature of the material to be reduced.
The polymer material is easy to generate static electricity in the using process, the static electricity is harmful to daily production and life, and particularly, the polymer material has obvious influence on electronic components, and the heat generated by the instant electric field or current can damage elements and influence the service life of electronic products. Therefore, the research on the antistatic biodegradable polymer composite material and the improvement of the glass transition temperature and the mechanical property of the composite material have important practical significance and economic significance for widening the application field of the composite material. The conductivity of the composite material is an important index for measuring the antistatic performance of the material, and the conductive polymer composite material is widely concerned due to low price, light weight, strong extensibility and simple preparation process.
Meanwhile, the biodegradable polymer composite material which has high glass transition temperature, good mechanical property and excellent antistatic property has good application prospect. However, the prior art lacks such a biodegradable polymer composite having an excellent balance of properties.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides an antistatic biodegradable polymer composite material and a preparation method thereof, and aims to prepare a graphene oxide coated biodegradable polymer microsphere, reduce graphene oxide, effectively compound reduced graphene oxide with the biodegradable polymer microsphere through a hydrogen bond, coat the reduced graphene oxide on the surface of the biodegradable polymer microsphere, effectively prevent the biodegradable polymer microsphere from stacking, and modify the biodegradable polymer by taking the reduced graphene oxide as a filler, so that the mechanical property and the antistatic property of the composite material can be obviously improved, and the technical problems of low vitrification temperature, poor mechanical property and poor antistatic property of the biodegradable polymer in the prior art are solved.
In order to achieve the above object, according to one aspect of the present invention, an antistatic biodegradable polymer composite is provided, which includes a biodegradable polymer matrix and reduced graphene oxide, wherein the biodegradable polymer matrix exists in a form of biodegradable polymer microspheres, and the reduced graphene oxide is coated on the surfaces of the biodegradable polymer microspheres, and a mass ratio of the biodegradable polymer matrix to the reduced graphene oxide is 100:1 to 100: 30.
Preferably, the antistatic biodegradable polymer composite has a conductivity of 1 × 10 at 25 ℃-6～35S/m。
Preferably, the mass ratio of the biodegradable polymer matrix to the reduced graphene oxide is 100: 10-100: 30.
Preferably, the conductivity of the antistatic biodegradable polymer composite material at 25 ℃ is 1-35S/m.
Preferably, the biodegradable polymer matrix is polypropylene carbonate or polybutylene adipate/terephthalate.
Preferably, the reduced graphene oxide is obtained by reducing graphene oxide with metal powder, and the metal is zinc or aluminum.
According to another aspect of the present invention, there is provided a method for preparing an antistatic biodegradable polymer composite, comprising the steps of:
(1) dispersing a biodegradable polymer in an organic solvent to obtain a biodegradable polymer dispersion liquid, wherein the concentration of the biodegradable polymer in the dispersion liquid is 1g/5 mL-1 g/50 mL; wherein the biodegradable polymer is polypropylene carbonate or polybutylene adipate/terephthalate;
(2) dispersing graphene oxide in deionized water to obtain a graphene oxide aqueous dispersion, wherein the concentration of the graphene oxide is 0.4-6 mg/ml, and the pH value of the graphene oxide aqueous dispersion is 2-5;
(3) dropwise adding the biodegradable polymer dispersion liquid obtained in the step (1) into the graphene oxide aqueous dispersion liquid obtained in the step (2), stirring, emulsifying, and removing the organic solvent to obtain a stably dispersed graphene oxide coated biodegradable polymer emulsion;
(4) reducing the graphene oxide in the graphene oxide coated biodegradable polymer emulsion obtained in the step (3) by using metal powder to obtain reduced graphene oxide coated biodegradable polymer microspheres; the mass ratio of the biodegradable polymer to the reduced graphene oxide is 100: 1-100: 30;
(5) and (4) removing unreacted metal powder in the step (4) by using hydrochloric acid, and then filtering, washing and drying to obtain the antistatic biodegradable polymer composite material.
Preferably, the organic solvent in step (1) is one or more of dichloromethane, ethyl acetate, toluene and chloroform.
Preferably, the volume of the graphene oxide aqueous dispersion in the step (2) is 5-10 times of the volume of the biodegradable polymer dispersion.
Preferably, in the step (2), a hydrochloric acid solution is adopted to adjust the pH value of the graphene oxide aqueous dispersion to 2-5.
Preferably, the stirring speed in the step (3) is 800-1000 r/min, and the stirring time is 1-3 hours.
Preferably, the mass ratio of the metal powder to the graphene oxide in the step (4) is (0.5-2): 1, and the metal is zinc or aluminum.
Preferably, in the step (4), the graphene oxide in the graphene oxide coated biodegradable polymer emulsion obtained in the step (3) is reduced by using metal powder under the ultrasonic dispersion condition.
Preferably, the preparation method further comprises the following steps:
(6) and carrying out thermal forming treatment on the antistatic biodegradable polymer composite material to obtain the antistatic biodegradable polymer composite material film.
In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
(1) according to the antistatic biodegradable polymer composite material provided by the invention, the biodegradable polymer matrix exists in a biodegradable polymer microsphere form, the reduced graphene oxide is coated on the surface of the biodegradable polymer microsphere to effectively prevent the reduced graphene oxide from stacking, and the reduced graphene oxide is used as a filler to modify the biodegradable polymer, so that the mechanical property and the antistatic property of the composite material can be obviously improved.
(2) According to the antistatic biodegradable polymer composite material provided by the invention, the coating of the graphene oxide on the degradable polymer microspheres is realized firstly, then the graphene oxide is reduced, the coating form is maintained, the mutually-lapped network structure of the reduced graphene oxide is formed after heat treatment, the biodegradable polymer plays a role of supporting the network structure, the graphene oxide is reduced in situ through the idea of coating the microspheres, the reduced graphene oxide network structure is constructed, the mechanical property and the antistatic property are enhanced, the antistatic biodegradable polymer composite material is different from the antistatic biodegradable polymer composite material which is formed by blending inorganic nano sheets after chemical modification with a polymer in the prior art, and the influence of an emulsifier on the environment does not exist.
(3) The preparation method of the antistatic biodegradable polymer composite material is simple and feasible, has mild conditions, and is suitable for industrial large-scale production. Compared with the prior art, the invention can effectively solve the problem of difficult dispersion caused by stacking and agglomeration of graphene in the polymer and improve the glass transition temperature, the mechanical property and the antistatic property of the biodegradable polymer (such as polypropylene carbonate) by improving the content of the conductive filler in the composite material, the whole process flow of the corresponding composite material preparation method, the reaction conditions of each step and the like.
(4) In the preparation process of the composite material, the metal powder is adopted to reduce the graphene oxide at room temperature under the weak acid condition, and compared with hydrazine hydrate, thermal reduction and other methods, the method has the advantages of energy conservation, environmental friendliness and the like.
(5) The high modulus and high conductivity of the reduced graphene oxide in the composite material provided by the invention enables the reduced graphene oxide/biodegradable polymer microsphere composite material to have good mechanical properties and antistatic properties.
(6) The reduced graphene oxide coated biodegradable polymer material provided by the invention has a good water vapor and oxygen blocking effect, is beneficial to storage of the material, and has a wide application prospect in the fields of electronic packaging and agricultural degradable plastics.
Drawings
FIG. 1 is a scanning electron microscope image of reduced graphene oxide coated polypropylene carbonate microspheres prepared in example 1;
FIG. 2 is a transmission electron microscope image of the reduced graphene oxide coated polypropylene carbonate microspheres prepared in example 1;
fig. 3 is a graph of conductivity of the polypropylene carbonate/reduced graphene oxide composite material in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides an antistatic biodegradable polymer composite material, which comprises a biodegradable polymer matrix and reduced graphene oxide, wherein the biodegradable polymer matrix exists in a biodegradable polymer microsphere form, and the reduced graphene oxide is coated on the biodegradable polymerThe mass ratio of the biodegradable polymer matrix to the reduced graphene oxide on the surface of the microsphere is 100: 1-100: 30, and the conductivity of the antistatic biodegradable polymer composite material at 25 ℃ is 1 × 10-635S/m, when the ratio of the preferred biodegradable polymer to the reduced graphene oxide is 100: 10-100: 30, the conductivity of the composite material is 1-35S/m, and the performance requirement of the high-antistatic material is met. The biodegradable polymer matrix is polypropylene carbonate (abbreviated as PPC) or poly adipic acid/butylene terephthalate (abbreviated as PBAT), which belongs to thermoplastic biodegradable plastics and is obtained by copolymerization of terephthalic acid, adipic acid and 1, 4-butanediol. The reduced graphene oxide is obtained by reducing graphene oxide with metal powder, wherein the metal is zinc or aluminum, and the surface of the graphene oxide is provided with an oxygen-containing group.
The invention provides a preparation method of the antistatic biodegradable polymer composite material, which comprises the following steps:
(1) dispersing a biodegradable polymer in an organic solvent to obtain a biodegradable polymer dispersion liquid, wherein the concentration of the biodegradable polymer in the dispersion liquid is 1g/5 mL-1 g/50 mL; wherein the biodegradable polymer is polypropylene carbonate or polybutylene adipate/terephthalate; the organic solvent is one of dichloromethane, ethyl acetate, toluene and chloroform.
(2) Dispersing graphene oxide in deionized water to obtain a graphene oxide aqueous dispersion, adjusting the concentration of the graphene oxide aqueous dispersion to 0.4-6 mg/ml, and adjusting the pH value of the graphene oxide aqueous dispersion to 2-5 by adopting an aqueous solution of hydrochloric acid; the purpose of adjusting the pH is to improve the lipophilicity of the graphene oxide so as to facilitate the coating of the degradable polymer by the graphene oxide when the graphene oxide is mixed to form emulsion in the next step; the volume of the graphene oxide aqueous solution is 5-10 times of that of the biodegradable polymer solution.
(3) Dropwise adding the biodegradable polymer dispersion liquid obtained in the step (1) into the graphene oxide aqueous dispersion liquid obtained in the step (2), stirring, emulsifying, and removing the organic solvent to obtain a stably dispersed graphene oxide coated biodegradable polymer emulsion; the stirring speed is 800-1000 r/min, the stirring time is 1-3 hours, and the organic solvent in the degradable polymer dispersion liquid is volatilized and separated out through continuous stirring with certain strength, so that the influence of the residual organic solvent on the subsequent reduction process and the stability of the coating structure is avoided.
(4) Adding metal powder into the graphene oxide-coated biodegradable polymer emulsion obtained in the step (3), and reducing graphene oxide in the graphene oxide-coated biodegradable polymer emulsion under the ultrasonic-assisted dispersion effect to obtain reduced graphene oxide-coated biodegradable polymer microspheres; the mass ratio of the biodegradable polymer to the reduced graphene oxide is 100: 1-100: 30; the mass ratio of the metal powder to the graphene oxide is 0.5-2, and the metal is one of zinc or aluminum.
(5) And (4) adding excessive hydrochloric acid into the biodegradable polymer composite dispersion liquid obtained in the step (4) to remove unreacted metal powder, and then filtering, washing and drying to obtain the antistatic biodegradable polymer composite.
(6) And carrying out thermal forming treatment on the antistatic biodegradable polymer composite material to obtain the antistatic biodegradable polymer composite material film.
In order to prepare antistatic biodegradable polymer composites while increasing their glass transition temperature and mechanical properties, it is necessary to select a suitable nanofiller. Graphene is a two-dimensional material composed of carbon atoms, and has the advantages of light weight, large specific surface area and the like due to the particularity of a two-dimensional structure. In addition, the nano-material has excellent electrical properties, thermal properties, high mechanical strength and other properties, and thus has application prospects. However, the graphene surface lacks functional groups, so that the dispersibility is poor, and the stacked graphene is easy to stack due to strong interaction between sheets, and the stacked graphene structure has poor stability, reduces the specific surface area of the graphene, and limits the efficient utilization of the interface, so that the performance of the graphene in the fields of energy storage, catalysis, composite materials, electronic devices and the like is influenced. In order to solve the problem of poor dispersibility of graphene in a degradable polymer, in the prior art, a surfactant is additionally added to improve the dispersion of graphene in the polymer, but once the surfactant is added, the surfactant is difficult to remove, and on the other hand, the environment is polluted.
Graphene oxide is a two-dimensional sheet material containing carboxyl, hydroxyl and epoxy groups obtained by chemically exfoliating graphite powder. The terminal thereof has a hydrophilic oxygen-containing group and a hydrophobic basal plane, and thus exhibits amphiphilicity. By adjusting the pH value of the solution, the graphene oxide can be adsorbed between interfaces and reduce the interfacial tension, thereby playing the role of a surfactant. By utilizing the characteristic, the graphene oxide is coated on the surface of the biodegradable polymer and then reduced, so that the stacking of the biodegradable polymer can be effectively prevented, and the reduced graphene oxide is used as a filler to modify the biodegradable polymer, so that the mechanical property and the antistatic property of the composite material are obviously improved.
According to the invention, the hydrophilicity and hydrophobicity of graphene oxide are firstly adjusted, then the dispersion liquid of the biodegradable polymer is dripped into the aqueous dispersion liquid of the graphene oxide to prepare the biodegradable polymer microsphere coated by the graphene oxide, and the reduced graphene oxide is lapped into a network through hot-pressing treatment by controlling various conditions in the preparation process, including stirring speed and stirring time, the concentration of the polymer dispersion liquid, the concentration of the graphene oxide dispersion liquid, subsequent graphene oxide reduction conditions and the like, so that the antistatic property and the strength of the composite material are further improved.
Aiming at the defects that inorganic nano sheets are easy to stack, poor in compatibility with polymers and easy to generate phase separation and material defects in the preparation method of the inorganic nano sheet/polymer composite material, the invention selects graphene oxide with amphipathy, coats the surface of the biodegradable polymer microsphere by adjusting the pH value, and further reduces the graphene oxide to prepare the biodegradable high polymer material with high antistatic property and high mechanical strength. The graphene oxide plays the role of a surfactant and is adsorbed on the surface of the biodegradable polymer pellet, and the reduced graphene oxide coated pellet is formed after the metal powder is reduced. By constructing the structure coated by the microspheres, the reduced graphene with the conductive effect is uniformly dispersed in the composite material, and a surfactant for dispersing the graphene is not required to be additionally added, so that the pollution of the surfactant to the environment and the complicated process of removing the surfactant in the material preparation process are avoided. The graphene oxide coated biodegradable polymer microspheres are saturated in an aqueous solution at a high concentration, and are uniform and stable. And then, reducing the metal powder under a weak acid condition, and freeze-drying to obtain the reduced graphene oxide coated biodegradable polymer microsphere with uniform size and controllable diameter. The tensile strength of the biodegradable high polymer material film with high antistatic property and high mechanical strength prepared by the thermal forming method is improved by 60 percent compared with that of a biodegradable polymer, the glass transition temperature is improved by 11 ℃, the thermal decomposition starting temperature is improved by 5 ℃, and the electrical conductivity of the material is improved by 35 times compared with that of a composite material directly blended with reduced graphene oxide when the content of the reduced graphene oxide is 30 percent. Different from the traditional method of blending the modified inorganic nano-material surface, the method only uses the emulsification effect of mechanical stirring to coat the graphene oxide on the surface of the biodegradable polymer microsphere, and then reduces the biodegradable polymer microsphere by using metal powder to fix the coating appearance, so that the method has remarkable advantages.
In the preparation process of the biodegradable polymer composite material, each step is cooperated, the step sequence cannot be changed, for example, in order to prepare the graphene oxide coated biodegradable polymer microsphere, the dispersion liquid of the polymer substrate material must be added into the graphene oxide aqueous dispersion liquid, and in order to realize good coating effect, the amphipathy of the graphene oxide must be adjusted firstly; considering that graphene oxide interacts with a biodegradable polymer through a hydrogen bond, in order to maintain the weak acting force, a relatively mild operation condition needs to be selected as much as possible in the treatment process after emulsification coating, for example, metal powder is selected to reduce graphene oxide, and reduction of graphene oxide can be realized at room temperature; hydrochloric acid is adopted to remove excessive metal powder, other methods are not adopted, the purpose is to ensure that the microspheres are always in an acidic environment, the microsphere system is maintained, the reduced graphene oxide is ensured to be coated on the surface of the biodegradable polymer, finally, the network structure of the reduced graphene oxide can be formed through hot pressing, the biodegradable polymer plays a role in supporting the network of the reduced graphene oxide, and the obtained biodegradable polymer composite material has excellent antistatic property, mechanical property and heat resistance.
The following are examples:
example 1
An antistatic biodegradable polymer composite material comprises reduced graphene oxide coated polypropylene carbonate microspheres, wherein after hot press molding, the reduced graphene oxide is lapped into a network and distributed on the interface of the polypropylene carbonate microspheres. Wherein the mass ratio of the polypropylene carbonate to the reduced graphene oxide is about 100: 30. the preparation process of the antistatic polymer composite material comprises the following steps:
3g of polypropylene carbonate was ultrasonically stirred with 30ml of methylene chloride for 2h until completely dissolved.
And dispersing graphene oxide in deionized water under the assistance of ultrasonic dispersion to obtain 150ml of graphene oxide aqueous dispersion with the concentration of 6 mg/ml. The pH of the graphene oxide aqueous dispersion was adjusted to 3 with hydrochloric acid and sonicated for 0.5 h.
And adding a dichloromethane solution of the polypropylene carbonate into the graphene oxide aqueous solution, controlling the stirring speed to be 800r/min, and continuously stirring for 1h to obtain the stable emulsion. 1.8g of zinc powder was added to the above emulsion and the mixture was sonicated for 10min with stirring, and then excess hydrochloric acid was added to remove the unreacted zinc powder. And (2) freeze-drying the solution to obtain the reduced graphene oxide coated polypropylene carbonate microspheres, observing a small amount of the reduced graphene oxide coated polypropylene carbonate microspheres by using a scanning electron microscope (as shown in figure 1), wherein the spherical structure of the reduced graphene oxide coated polypropylene carbonate microspheres can be obviously seen, and the transmission electron microscope image of the polypropylene carbonate microspheres is shown in figure 2, so that the reduced graphene oxide coated polypropylene carbonate microspheres can be seen.
The reduced graphene oxide/polypropylene carbonate composite material film is obtained by performing hot press molding on the material, the film material is cut into standard sample strips by a cutter to be subjected to tensile test, the maximum tensile strength is 31MPa (the maximum tensile strength of pure polypropylene carbonate is 23MPa), the glass transition temperature of the material is 36 ℃ (the glass transition temperature of pure polypropylene carbonate is 25 ℃) by Differential Scanning Calorimetry (DSC), the temperature for the thermal decomposition of the material to reach 5% is 276 ℃ (the thermal decomposition 5% temperature of pure polypropylene carbonate is 273 ℃) by a thermogravimetric analyzer (TGA), the conductivity of the material is 35S/m by a four-probe test, and the conductivity test result is shown in figure 3.
Example 2
An antistatic biodegradable polymer composite material comprises reduced graphene oxide coated polypropylene carbonate microspheres, wherein after hot press molding, the reduced graphene oxide is lapped into a network and distributed on the interface of the polypropylene carbonate microspheres. Wherein the mass ratio of the polypropylene carbonate to the reduced graphene oxide is about 100: 25.
the preparation process of the antistatic polymer composite material comprises the following steps:
1g of polypropylene carbonate is ultrasonically stirred with 50ml of ethyl acetate for 2h until completely dissolved.
And (3) dispersing graphene oxide in deionized water under the assistance of ultrasonic waves to obtain 250ml of graphene oxide aqueous dispersion with the concentration of 1 mg/ml. The pH of the graphene oxide aqueous dispersion was adjusted to 2 with hydrochloric acid and sonicated for 0.5 h.
And adding a dichloromethane solution of the polypropylene carbonate into the graphene oxide aqueous solution, controlling the stirring speed to be 900r/min, and continuously stirring for 1h to obtain the stable emulsion. Adding 0.3g of aluminum powder into the emulsion, stirring and carrying out ultrasonic treatment for 10min, and adding excessive hydrochloric acid to remove unreacted aluminum powder. And (3) freeze-drying the solution to obtain the reduced graphene oxide coated polypropylene carbonate microsphere powder.
The reduced graphene oxide/polypropylene carbonate composite material film is obtained by carrying out hot press molding on the materials, the film material is cut into a standard sample strip by a cutter to be subjected to tensile test to achieve the maximum tensile strength of 33MPa, Differential Scanning Calorimetry (DSC) is used to obtain the glass transition temperature of the material of 32 ℃, thermogravimetric analysis (TGA) is used to obtain the temperature at which the thermal decomposition of the material reaches 5% of 277 ℃, a four-probe is used to test the conductivity of the material of 27S/m, and the film material has excellent antistatic performance.
Example 3
An antistatic biodegradable polymer composite material comprises reduced graphene oxide coated polypropylene carbonate microspheres, wherein after hot press molding, the reduced graphene oxide is lapped into a network and distributed on the interface of the polypropylene carbonate microspheres. Wherein the mass ratio of the polypropylene carbonate to the reduced graphene oxide is about 100: 10.
the preparation process of the antistatic polymer composite material comprises the following steps:
2g of polypropylene carbonate was ultrasonically stirred with 10ml of chloroform for 2 hours until completely dissolved.
And dispersing graphene oxide in deionized water under the assistance of ultrasonic dispersion to obtain 100ml of graphene oxide aqueous dispersion with the concentration of 2 mg/ml. The pH of the graphene oxide aqueous dispersion was adjusted to 3 with hydrochloric acid and sonicated for 0.5 h.
And adding a dichloromethane solution of the polypropylene carbonate into the graphene oxide aqueous solution, controlling the stirring speed to be 1000r/min, and continuously stirring for 2h to obtain the stable emulsion. 0.1g of zinc powder is added into the emulsion, the mixture is stirred and ultrasonically treated for 10min, and then excessive hydrochloric acid is added to remove the unreacted zinc powder. And (3) freeze-drying the solution to obtain the reduced graphene oxide coated polypropylene carbonate microsphere powder.
And carrying out hot press molding on the materials to obtain the reduced graphene oxide/polypropylene carbonate composite material film. The film material is cut into standard sample strips by a cutter to be subjected to tensile test to achieve the maximum tensile strength of 37MPa, the glass transition temperature of the material is 29 ℃ by Differential Scanning Calorimetry (DSC), the temperature of 5 percent of thermal decomposition of the material is 278 ℃ by thermogravimetric analysis (TGA), and the conductivity of the material is 1.04S/m by a four-probe test, so that the film material has certain antistatic performance.
Example 4
An antistatic biodegradable polymer composite material comprises reduced graphene oxide coated polypropylene carbonate microspheres, wherein after hot press molding, the reduced graphene oxide is lapped into a network and distributed on the interface of the polypropylene carbonate microspheres. Wherein the mass ratio of the polypropylene carbonate to the reduced graphene oxide is about 100: 20.
the preparation process of the antistatic polymer composite material comprises the following steps:
2g of polypropylene carbonate was ultrasonically stirred with 50ml of toluene for 2h until completely dissolved.
And dispersing graphene oxide in deionized water under the assistance of ultrasonic waves to obtain 300ml of graphene oxide aqueous dispersion with the concentration of 1.3 mg/ml. The pH of the graphene oxide aqueous dispersion is adjusted to 5 by hydrochloric acid, and ultrasonic treatment is carried out for 0.5 h.
And adding a toluene solution of the polypropylene carbonate into the graphene oxide aqueous solution, controlling the stirring speed to be 800r/min, and continuously stirring for 3 hours to obtain the stable emulsion. Adding 0.6g of aluminum powder into the emulsion, stirring and carrying out ultrasonic treatment for 10min, and adding excessive hydrochloric acid to remove unreacted aluminum powder. And (3) freeze-drying the solution to obtain the reduced graphene oxide coated polypropylene carbonate microsphere powder.
And carrying out hot press molding on the materials to obtain the reduced graphene oxide/polypropylene carbonate composite material film. The film material is cut into standard sample strips by a cutter to be subjected to tensile test to achieve the maximum tensile strength of 35MPa, the glass transition temperature of the material is 31 ℃ by Differential Scanning Calorimetry (DSC), the temperature of 5% of thermal decomposition of the material is 277 ℃ by thermogravimetric analysis (TGA), the conductivity of the material is 7.2S/m by a four-probe test, and the film material has good antistatic performance.
Example 5
An antistatic biodegradable polymer composite material comprises reduced graphene oxide coated polypropylene carbonate microspheres, wherein after hot press molding, the reduced graphene oxide is lapped into a network and distributed on the interface of the polypropylene carbonate microspheres. Wherein the mass ratio of the polypropylene carbonate to the reduced graphene oxide is about 100: 1.
the preparation process of the antistatic polymer composite material comprises the following steps:
5g of polypropylene carbonate was ultrasonically stirred with 25ml of methylene chloride for 2h until completely dissolved.
And dispersing graphene oxide in deionized water under the assistance of ultrasonic waves to obtain 125ml of graphene oxide aqueous dispersion with the concentration of 0.4 mg/ml. The pH of the graphene oxide aqueous dispersion was adjusted to 4 with hydrochloric acid and sonicated for 0.5 h.
And adding a dichloromethane solution of the polypropylene carbonate into the graphene oxide aqueous solution, controlling the stirring speed to be 850r/min, and continuously stirring for 2h to obtain the stable emulsion. Adding 0.1g of aluminum powder into the emulsion, stirring and carrying out ultrasonic treatment for 10min, and adding excessive hydrochloric acid to remove unreacted aluminum powder. And (3) freeze-drying the solution to obtain the reduced graphene oxide coated polypropylene carbonate microsphere powder.
Cutting the film material into standard sample strips by a cutter, performing tensile test to obtain the maximum tensile strength of 27MPa, obtaining the glass transition temperature of 27 ℃ by Differential Scanning Calorimetry (DSC), obtaining the temperature of 275 ℃ when the thermal decomposition of the material reaches 5 percent by using a thermogravimetric analyzer (TGA), and testing the conductivity of the material to be 1.3 × 10 by using a four-probe-3S/m。
Comparative example 1
In order to compare the performance of the antistatic biodegradable polymer composite material, the pure polypropylene carbonate film is obtained by the same method in the embodiment, and the specific preparation method is as follows:
ultrasonically stirring 5g of polypropylene carbonate and 25ml of ethyl acetate for 2 hours until the polypropylene carbonate is completely dissolved, adjusting the pH value of 125ml of deionized water to 2 by using hydrochloric acid, ultrasonically stirring for 0.5 hour, adding the ethyl acetate solution of the polypropylene carbonate into the hydrochloric acid solution, controlling the stirring speed to be 1000r/min, continuously stirring for 3 hours, filtering, washing, drying and hot-press forming the obtained particles, cutting the hot-press formed polypropylene carbonate film into a standard sample strip by using a cutter, performing a tensile test to obtain the maximum tensile strength of 23MPa, obtaining the glass transition temperature of the material by using a Differential Scanning Calorimetry (DSC) of 25 ℃, obtaining the temperature of 273 ℃ when the thermal decomposition of the material reaches 5 percent by using a thermogravimetric analyzer (TGA), and testing the conductivity of the material to be 1 × 10 by using a four-probe-6S/m, no antistatic property.
Comparative example 2
In order to compare with the performance of the antistatic biodegradable polymer composite material, the embodiment includes graphene oxide-coated polypropylene carbonate microspheres, and the graphene oxide is distributed on the interface of the polypropylene carbonate microspheres after hot press molding, wherein the mass ratio of the polypropylene carbonate to the graphene oxide is about 100:20, and the specific preparation method is as follows:
the preparation method comprises the steps of ultrasonically stirring 2g of polypropylene carbonate and 50ml of toluene for 2 hours until the materials are completely dissolved, dispersing the graphene oxide in deionized water under the assistance of ultrasonic waves to obtain 300ml of graphene oxide aqueous dispersion with the concentration of 1.3mg/ml, adjusting the pH value of the graphene oxide aqueous dispersion to 3 by using hydrochloric acid, ultrasonically stirring for 0.5 hour, adding the toluene solution of the polypropylene carbonate into the graphene oxide aqueous solution, controlling the stirring speed to be 850r/min, continuously stirring for 3 hours to obtain stable emulsion, freeze-drying the solution to obtain graphene oxide coated polypropylene carbonate microsphere powder, carrying out hot press molding on the materials to obtain a graphene oxide/polypropylene carbonate composite material film, cutting the film into standard sample strips by using a cutter to carry out tensile test to reach the maximum tensile strength of 28MPa, obtaining the glass transition temperature of the material to be 29 ℃ by using Differential Scanning Calorimetry (DSC), measuring the thermal decomposition temperature of the material to be 5% by using a Thermal Gravimetric Analyzer (TGA) to be 270 ℃, and testing the electrical conductivity of the material to be 1 × 10 by using a four-probe to be 1-6S/m, no antistatic property.
Comparative example 3
In order to compare with the performance of the antistatic biodegradable polymer composite material, the embodiment includes graphene oxide-coated polypropylene carbonate microspheres, and the graphene oxide is distributed on the interface of the polypropylene carbonate microspheres after hot press molding, wherein the mass ratio of the polypropylene carbonate to the graphene oxide is about 100:1, and the specific preparation method is as follows:
5g of polypropylene carbonate was stirred with 25ml of methylene chloride ultrasonically for 2h until completely dissolved. And dispersing graphene oxide in deionized water under the assistance of ultrasonic waves to obtain 125ml of graphene oxide aqueous dispersion with the concentration of 0.4 mg/ml. The pH of the graphene oxide aqueous dispersion was adjusted to 2 with hydrochloric acid and sonicated for 0.5 h. And adding a toluene solution of the polypropylene carbonate into the graphene oxide aqueous solution, controlling the stirring speed to be 900r/min, and continuously stirring for 3 hours to obtain the stable emulsion. Freeze drying the solution to obtain the poly (alkene carbonate) coated by the graphene oxideCutting the film material into standard sample strips by a cutter, performing tensile test to obtain a maximum tensile strength of 37MPa, obtaining a material glass transition temperature of 33 ℃ by Differential Scanning Calorimetry (DSC), obtaining a temperature of 275 ℃ when thermal decomposition of the material reaches 5 percent by using a thermogravimetric analyzer (TGA), and testing the conductivity of the material to be 1 × 10 by using a four-probe-6S/m, no antistatic property.
Comparative example 4:
in order to compare the performance of the antistatic biodegradable polymer composite material, the embodiment includes a reduced graphene oxide and polypropylene carbonate blended composite material, and the reduced graphene oxide is randomly distributed in a polymer substrate after hot press molding, wherein the mass ratio of the polypropylene carbonate to the reduced graphene oxide is about 100:30, and the specific preparation method is as follows:
2g of polypropylene carbonate was stirred with 50ml of methylene chloride ultrasonically for 2h until completely dissolved. 600mg of reduced graphene oxide was dispersed in 100ml of deionized water. The pH of the reduced graphene oxide aqueous dispersion is adjusted to 2 by hydrochloric acid, and ultrasonic treatment is carried out for 0.5 h. And adding the toluene solution of the polypropylene carbonate into the graphene oxide aqueous solution, controlling the stirring speed to be 900r/min, and continuously stirring for 3 h. And filtering, washing, drying and hot-press forming the obtained particles to obtain the reduced graphene oxide/polypropylene carbonate composite material film. The above film material was cut into a standard sample strip with a cutter and subjected to a tensile test to a maximum tensile strength of 26MPa, a glass transition temperature of 29 ℃ with a Differential Scanning Calorimetry (DSC) method, a temperature of 5% thermal decomposition of the material with a thermogravimetric analyzer (TGA) method of 275 ℃ and a conductivity of 0.98S/m with a four-probe test, and had a certain antistatic property, but compared with example 1, the composite material prepared by the comparative example cannot obtain the polymer microspheres coated by the reduced graphene oxide because the reduced graphene oxide and the polymer have no interaction, under the same addition of the reduced graphene oxide, the reduced graphene oxide is randomly and disorderly distributed in the composite material, the polymer network was not effectively bridged and accordingly the conductivity of the composite material prepared in example 1 was more than 35 times that of the composite material obtained in this comparative example.
Comparative example 5:
in order to compare the performance of the antistatic biodegradable polymer composite material, the embodiment includes a reduced graphene oxide and polypropylene carbonate blended composite material, and the reduced graphene oxide is randomly distributed in a polymer substrate after hot press molding, wherein the mass ratio of the polypropylene carbonate to the reduced graphene oxide is about 100:10, and the specific preparation method is as follows:
2g of polypropylene carbonate was stirred with 50ml of methylene chloride ultrasonically for 2h until completely dissolved. 200mg of reduced graphene oxide was dispersed in 150ml of deionized water. The pH of the reduced graphene oxide aqueous dispersion is adjusted to 3 by hydrochloric acid, and ultrasonic treatment is carried out for 0.5 h. And adding a toluene solution of the polypropylene carbonate into the graphene oxide aqueous solution, controlling the stirring speed to be 800r/min, continuously stirring for 3h, filtering, washing, drying and carrying out hot press molding on the obtained particles to obtain the reduced graphene oxide/polypropylene carbonate composite material film. The film material is cut into a standard sample strip by a cutter to be subjected to tensile test to achieve the maximum tensile strength of 28MPa, the glass transition temperature of the material is 27 ℃ by Differential Scanning Calorimetry (DSC), the temperature of 5% of thermal decomposition of the material is 276 ℃ by thermogravimetric analysis (TGA), the conductivity of the material is 0.25S/m by a four-probe test, and the material has certain antistatic performance.
TABLE 1 mechanical Properties, thermal Properties and conductivity of the inventive Material
Figure BDA0001649401230000161
The biodegradable polymer matrix material polypropylene carbonate in the above embodiment can be completely replaced by PBAT (poly (butylene adipate terephthalate)), so as to obtain a PBAT-based composite material; correspondingly, in the preparation method, except that the type of the organic solvent for dissolving the biodegradable polymer matrix may need to be properly adjusted, other reaction conditions, such as the type and proportion of reactants, stirring time and the like, can be kept unchanged; wherein, the organic solvent suitable for the polypropylene carbonate matrix is preferably one of dichloromethane, ethyl acetate, toluene and chloroform; the organic solvent suitable for the PBAT matrix is preferably any one of dichloromethane, chloroform, benzene, toluene.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (8)

1. An antistatic biodegradable polymer composite material is characterized in that the composite material comprises a biodegradable polymer matrix and reduced graphene oxide, wherein the biodegradable polymer matrix exists in a biodegradable polymer microsphere form, and the reduced graphene oxide is coated on the surface of the biodegradable polymer microsphere; the preparation method of the antistatic biodegradable polymer composite material comprises the following steps:
(1) dispersing a biodegradable polymer in an organic solvent to obtain a biodegradable polymer dispersion liquid, wherein the concentration of the biodegradable polymer in the dispersion liquid is 1g/5 mL-1 g/50 mL; wherein the biodegradable polymer is polypropylene carbonate or polybutylene adipate/terephthalate;
(2) dispersing graphene oxide in deionized water to obtain a graphene oxide aqueous dispersion, wherein the concentration of the graphene oxide is 0.4-6 mg/ml, and the pH value of the graphene oxide aqueous dispersion is 2-5;
(3) dropwise adding the biodegradable polymer dispersion liquid obtained in the step (1) into the graphene oxide aqueous dispersion liquid obtained in the step (2), stirring, emulsifying, and removing the organic solvent to obtain a stably dispersed graphene oxide coated biodegradable polymer emulsion;
(4) reducing the graphene oxide in the graphene oxide coated biodegradable polymer emulsion obtained in the step (3) by using metal powder to obtain reduced graphene oxide coated biodegradable polymer microspheres; the mass ratio of the biodegradable polymer to the reduced graphene oxide is 100: 1-100: 30;
(5) removing unreacted metal powder in the step (4) by using hydrochloric acid, and then filtering, washing and drying to obtain the antistatic biodegradable polymer composite material;
(6) and carrying out thermal forming treatment on the antistatic biodegradable polymer composite material to obtain the antistatic biodegradable polymer composite material film.
2. The composite material of claim 1, wherein the antistatic biodegradable polymer composite has an electrical conductivity of 1 × 10 at 25 ℃-6~35 S/m。
3. The composite material of claim 1, wherein the reduced graphene oxide is obtained by reducing graphene oxide with a metal powder, wherein the metal is zinc or aluminum.
4. The preparation method of the antistatic biodegradable polymer composite material is characterized by comprising the following steps:
(1) dispersing a biodegradable polymer in an organic solvent to obtain a biodegradable polymer dispersion liquid, wherein the concentration of the biodegradable polymer in the dispersion liquid is 1g/5 mL-1 g/50 mL; wherein the biodegradable polymer is polypropylene carbonate or polybutylene adipate/terephthalate;
(2) dispersing graphene oxide in deionized water to obtain a graphene oxide aqueous dispersion, wherein the concentration of the graphene oxide is 0.4-6 mg/ml, and the pH value of the graphene oxide aqueous dispersion is 2-5;
(3) dropwise adding the biodegradable polymer dispersion liquid obtained in the step (1) into the graphene oxide aqueous dispersion liquid obtained in the step (2), stirring, emulsifying, and removing the organic solvent to obtain a stably dispersed graphene oxide coated biodegradable polymer emulsion;
(4) reducing the graphene oxide in the graphene oxide coated biodegradable polymer emulsion obtained in the step (3) by using metal powder to obtain reduced graphene oxide coated biodegradable polymer microspheres; the mass ratio of the biodegradable polymer to the reduced graphene oxide is 100: 1-100: 30;
(5) removing unreacted metal powder in the step (4) by using hydrochloric acid, and then filtering, washing and drying to obtain the antistatic biodegradable polymer composite material;
(6) and carrying out thermal forming treatment on the antistatic biodegradable polymer composite material to obtain the antistatic biodegradable polymer composite material film.
5. The method according to claim 4, wherein the organic solvent in step (1) is one or more of dichloromethane, ethyl acetate, toluene and chloroform.
6. The preparation method according to claim 4, wherein the volume of the graphene oxide aqueous dispersion in the step (2) is 5 to 10 times that of the biodegradable polymer dispersion.
7. The method according to claim 4, wherein the stirring speed in the step (3) is 800 to 1000r/min, and the stirring time is 1 to 3 hours.
8. The preparation method according to claim 4, wherein the mass ratio of the metal powder to the graphene oxide in the step (4) is (0.5-2): 1, and the metal is zinc or aluminum.
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