CN110437595A - A kind of antistatic biodegradable polymers composite material and preparation method - Google Patents
A kind of antistatic biodegradable polymers composite material and preparation method Download PDFInfo
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- CN110437595A CN110437595A CN201810416048.9A CN201810416048A CN110437595A CN 110437595 A CN110437595 A CN 110437595A CN 201810416048 A CN201810416048 A CN 201810416048A CN 110437595 A CN110437595 A CN 110437595A
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Abstract
The invention discloses a kind of antistatic biodegradable polymers composite material and preparation methods, and wherein the composite material includes biodegradable polymer matrix and redox graphene, and redox graphene is coated on biodegradable polymers microsphere surface；In addition, the mass ratio of both biodegradable polymer matrix and redox graphene is 100:1~100:30, biodegradable polymer matrix is poly (propylene carbonate) (PPC) or polyadipate/butylene terephthalate (PBAT).The present invention is improved by the integrated artistic process of content and corresponding composite material and preparation method thereof to conductive filler in composite material, reaction condition of each step etc., it can effectively solve the problem that difficult the dispersion caused by graphene stacks in the polymer, reunites compared with prior art, and improve the glass transition temperature, mechanical property and antistatic property of biodegradable polymers (such as poly (propylene carbonate)).
Description
Technical field
The invention belongs to Biodegradable material technical fields, more particularly, to a kind of antistatic biodegradable poly-
Compound composite material and preparation method thereof.
Background technique
High molecular material has many advantages, such as light weight, cheap, is widely used in scientific research and people's life
Many aspects.But the booming of plastics industry brings a large amount of white pollution, seriously compromises the ecosystem.It is based on
This, the research and application of biodegradable polymers become more and more important.Biodegradable polymers are divided into natural polymer
It is such as poly- with carbon dioxide and propylene oxide including starch, cellulose, chitin etc. and chemically synthesized Biodegradable high-molecular
Poly (propylene carbonate) made of conjunction (PPC), and gather oneself two by what terephthalic acid (TPA), adipic acid and 1,4-butanediol were copolymerized
Acid/butylene terephthalate (PBAT), polylactic acid obtained using lactic acid as polymerizable raw material (PLA) etc..
Biodegradable polymers have some disadvantages itself, and if poor mechanical property, glass transition temperature are low, these are insufficient
Limit its use scope.Nanofiller (such as graphene oxide and cellulose Nanowire are added into biodegradable polymers
Dimension) mechanical strength and glass transition temperature of material can be improved.But because of strong interaction (such as graphite oxide of nanofiller itself
Between alkene π-π effect, it is cellulose nano-fibrous between hydrogen bond action) filler is occurred in biodegradable polymers
Reunite, composite material toughness is caused to decline.In addition because graphene oxide and cellulose nano-fibrous thermal property are bad, as filling out
The thermal decomposition temperature decline that will lead to material is added in polymeric matrix in material.
Polymer material is easy to produce static electricity in use, and the harm of electrostatic in daily production and life is big, especially right
Electronic component influences significantly, because of the heat meeting lesion element that its moment electric field or electric current generate, to influence the service life of electronic product.Cause
This, studies a kind of antistatic biodegradable polymers composite material, at the same improve its glass transition temperature and mechanical performance for
Widening its application field has important realistic meaning and economic significance.The electric conductivity of composite material is to measure the antistatic property of material
Can important indicator, conducting polymer composite material is because its price is low, and light weight, ductility is strong, preparation process it is simple and
By extensive concern.
It is compound to meet the biodegradable polymers that glass transition temperature is high, good mechanical property and antistatic property are excellent simultaneously
Material has a good application prospect.But the biodegradable polymers that the prior art lacks this excellent combination property are multiple
Condensation material.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of antistatic biodegradable polymerics
Object composite material and preparation method, its object is to the biodegradable polymers by preparing graphene oxide cladding first
Then microballoon restores graphene oxide, so that redox graphene has by hydrogen bond and biodegradable polymers microballoon
To imitate compound, redox graphene is coated on biodegradable polymers microsphere surface, it can be effectively prevent the stacking of its own, and
And redox graphene is as filler modified biodegradable polymers, can significantly improve composite material mechanical performance and
Thus it is bad to solve low prior art biodegradable polymers glass transition temperature, bad mechanical property, antistatic property for antistatic property
The technical issues of.
To achieve the above object, according to one aspect of the present invention, a kind of antistatic biodegradable polymers are provided
Composite material, the composite material include biodegradable polymer matrix and redox graphene, described biodegradable poly-
It closes object matrix to exist in the form of biodegradable polymers microballoon, and the redox graphene is coated on and described biological can drop
Depolymerize object microsphere surface, the mass ratio of the biodegradable polymer matrix and redox graphene be 100:1~
100:30。
Preferably, conductivity of the antistatic biodegradable polymers composite material at 25 DEG C is 1 × 10-6~
35S/m。
Preferably, the mass ratio of the biodegradable polymer matrix and redox graphene is 100:10~100:
30。
Preferably, conductivity of the antistatic biodegradable polymers composite material at 25 DEG C is 1~35S/m.
Preferably, the biodegradable polymer matrix is poly (propylene carbonate) or polyadipate/terephthalic acid (TPA) fourth
Diester.
Preferably, the redox graphene is to be obtained by graphene oxide through metal powder reduction, and the metal is
Zinc or aluminium.
Other side according to the invention provides a kind of preparation of antistatic biodegradable polymers composite material
Method includes the following steps:
(1) it disperses biodegradable polymers in organic solvent and obtains biodegradable polymers dispersion liquid, it is described
Concentration of the biodegradable polymers in the dispersion liquid is 1g/5mL~1g/50mL；Wherein, the biodegradable polymeric
Object is poly (propylene carbonate) or polyadipate/butylene terephthalate；
(2) in deionized water by graphene oxide dispersion, graphene oxide aqueous dispersions are obtained, wherein the oxidation stone
The concentration of black alkene is 0.4mg/ml~6mg/ml, and the pH value of the graphene oxide aqueous dispersions is 2~5；
(3) the biodegradable polymers dispersion liquid that step (1) obtains is added to the oxidation stone of step (2) acquisition
In black alkene aqueous dispersions, stirring, emulsification remove the organic solvent, obtain giving birth to for the graphene oxide cladding of stable dispersion
Object degradation polymer lotion；
(4) in the biodegradable polymers lotion for the graphene oxide cladding for being obtained step (3) using metal powder
Graphene oxide reduction, obtain redox graphene cladding biodegradable polymers microballoon；It is described biodegradable
Polymer and the redox graphene mass ratio are 100:1~100:30；
(5) unreacted metal powder in step (4) is removed using hydrochloric acid, refilters, washs, dries to get quiet to resisting
Electric biodegradable polymers composite material.
Preferably, step (1) organic solvent is one of methylene chloride, ethyl acetate, toluene and chloroform or more
Kind.
Preferably, the volume of step (2) the graphene oxide aqueous dispersions is biodegradable polymers dispersion
5~10 times of liquid product.
Preferably, step (2) uses hydrochloric acid solution to adjust the pH value of the graphene oxide aqueous dispersions as 2~5.
Preferably, step (3) mixing speed is 800~1000r/min, and mixing time is 1~3 hour.
Preferably, the mass ratio of step (4) metal powder and graphene oxide is (0.5~2): 1, the metal is
Zinc or aluminium.
Preferably, the graphene oxide that step (4) is obtained step (3) using metal powder under ultrasonic wave dispersion condition
Graphene oxide reduction in the biodegradable polymers lotion of cladding.
Preferably, the preparation method, further comprises the steps of:
(6) the antistatic biodegradable polymers composite material is handled by thermoforming, obtains antistatic give birth to
Object degradation polymer composite material film.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect:
(1) antistatic biodegradable polymers composite material provided by the invention, biodegradable polymer matrix with
Biodegradable polymers microballoon form exists, and redox graphene is coated on biodegradable polymers microsphere surface,
Redox graphene is coated on the stacking that biodegradable polymers microsphere surface can effectively prevent its own, and oxygen reduction
Graphite alkene can significantly improve the mechanical performance and antistatic property of composite material as filler modified biodegradable polymers.
(2) antistatic biodegradable polymers composite material provided by the invention, by first realizing graphene oxide pair
The cladding of degradable polymer microspheres restores graphene oxide, maintains cladding form, forms reduction-oxidation graphite after heat treatment
Alkene mutually overlapped network structure, biodegradable polymers play the role of supporting network structure, by micro-spheres thought,
In-situ reducing graphene oxide constructs redox graphene network structure, enhances mechanical property and antistatic property, is different from existing
It is blended after thering is technology to be chemically modified inorganic nano sheet with polymer, is also influenced caused by environment there is no emulsifier.
(3) preparation method is simple for the antistatic biodegradable polymers composite material of the present invention, and mild condition is fitted
Close industrial mass production.The present invention passes through content to conductive filler in composite material and corresponding composite material and preparation method thereof
Integrated artistic process, the reaction condition of each step etc. improve, can effectively solve the problem that graphene compared with prior art
Hardly possible the dispersion caused by stacking in the polymer, reunion, and improve biodegradable polymers (such as poly (propylene carbonate))
Glass transition temperature, mechanical property and antistatic property.
(4) in composite material preparation process of the present invention, using metal powder under mild acid conditions room temperature reduction-oxidation graphite
Alkene has energy conservation and environmentally protective advantage compared to the methods of hydrazine hydrate and thermal reduction.
(5) high-modulus of redox graphene and high conductivity make reduction-oxidation graphite in composite material of the present invention
Alkene/biodegradable polymers microballoon composite material has good mechanical performance and antistatic property.
(6) redox graphene cladding biodegradable polymers material provided by the invention has good vapor
With the barriering effect of oxygen, be conducive to the storage of material, have in Electronic Packaging and agricultural degradation plastic field wide
Application prospect.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph for the redox graphene cladding poly (propylene carbonate) microballoon that embodiment 1 is prepared；
Fig. 2 is the transmission electron microscope picture for the redox graphene cladding poly (propylene carbonate) microballoon that embodiment 1 is prepared；
Fig. 3 is that poly (propylene carbonate) in embodiment 1/redox graphene conductivity of composite material can scheme.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
The present invention provides a kind of antistatic biodegradable polymers composite material, which includes that biological can drop
Depolymerize object matrix and redox graphene, and the biodegradable polymer matrix is with biodegradable polymers microspheroidal
State exists, and the redox graphene is coated on the biodegradable polymers microsphere surface, described biodegradable
The mass ratio of polymeric matrix and redox graphene is 100:1~100:30.The antistatic biodegradable polymers are multiple
Conductivity of the condensation material at 25 DEG C is 1 × 10-6~35S/m, preferred biodegradable polymers and redox graphene
Between ratio when being 100:10~100:30, the conductivity of composite material is 1~35S/m, meets the property of high-antistatic material
It can require.Biodegradable polymer matrix is poly (propylene carbonate) (being abbreviated as PPC) or polyadipate/terephthalic acid (TPA) fourth two
Ester (is abbreviated as PBAT), and PBAT belongs to thermoplastic biodegradable plastics, is total to by terephthalic acid (TPA), adipic acid and 1,4-butanediol
It is poly- to obtain.Redox graphene is to be obtained by graphene oxide through metal powder reduction, and the metal is zinc or aluminium, oxidation
Graphene surface has oxygen-containing group.
The present invention provides a kind of preparation method of above-mentioned antistatic biodegradable polymers composite material, including it is as follows
Step:
(1) it disperses biodegradable polymers in organic solvent and obtains biodegradable polymers dispersion liquid, it is described
Concentration of the biodegradable polymers in the dispersion liquid is 1g/5mL~1g/50mL；Wherein, biodegradable polymers are
Poly (propylene carbonate) or polyadipate/butylene terephthalate；Organic solvent is methylene chloride, ethyl acetate, toluene and chlorine
One of imitate.
(2) in deionized water by graphene oxide dispersion, graphene oxide aqueous dispersions are obtained, adjusts graphene oxide
The concentration of aqueous dispersions is 0.4mg/ml~6mg/ml, then uses the aqueous solution of hydrochloric acid by the pH value of graphene oxide aqueous dispersions
It is adjusted to 2~5；The purpose for adjusting pH is to improve the lipophilicity of graphene oxide, real when in order to be mixed to form lotion in next step
Cladding of the existing graphene oxide to degradable polymer；The volume of graphene oxide water solution is biodegradable polymers solution
5~10 times.
(3) the biodegradable polymers dispersion liquid that step (1) obtains is added to the oxidation stone of step (2) acquisition
In black alkene aqueous dispersions, stirring, emulsification remove the organic solvent, obtain giving birth to for the graphene oxide cladding of stable dispersion
Object degradation polymer lotion；Mixing speed is 800~1000r/min, and mixing time is 1~3 hour, passes through holding for some strength
Continuous stirring, so that the organic solvent volatilization in degradable polymer dispersion liquid is separated, it is subsequent also to avoid its remaining influence
The stability of former process and clad structure.
(4) metal powder is added in the biodegradable polymers lotion coated to the graphene oxide that step (3) obtains,
The graphite oxide in biodegradable polymers lotion for coating the graphene oxide under the effect of ultrasonic wave aid dispersion
Alkene reduction, obtains the biodegradable polymers microballoon of redox graphene cladding；The biodegradable polymers with also
Former graphene oxide mass ratio is 100:1~100:30；The mass ratio of metal powder and graphene oxide is 0.5~2, described
Metal is one of zinc or aluminium.
(5) it is not anti-that excessive hydrochloric acid removing will be added in the biodegradable polymers composite material dispersion liquid of step (4)
The metal powder answered is refiltered, is washed, drying to get antistatic biodegradable polymers composite material is arrived.
(6) the antistatic biodegradable polymers composite material is handled by thermoforming, obtains antistatic give birth to
Object degradation polymer composite material film.
In order to prepare antistatic biodegradable polymers composite material, while improving its glass transition temperature and mechanicalness
Can, it needs to select a kind of suitable nanofiller.Graphene is a kind of two-dimensional material being made of carbon atom, due to its two dimension knot
The particularity of structure, the advantages that making it have light weight and large specific surface area.In addition to this, since it possesses excellent electrical property
The performances such as energy, thermal property and high mechanical strength are at present very with the nano material of application prospect.But graphene surface lacks
Few functional group thus bad dispersibility, stronger interaction causes its to be easy to stack between lamella, the graphene knot of this stacking
Not only stability is poor for structure, but also reduces the specific surface area of graphene, limits the efficient utilization at its interface, thus affect it
The performance when fields such as energy storage, catalysis, composite material, electronic device are applied.In order to solve graphene in degradable polymer
Bad dispersibility the problem of, the prior art by additionally be added surfactant to improve the dispersion of graphene in the polymer,
But surfactant is difficult to remove in itself once being added, and on the other hand will also result in pollution to environment.
Graphene oxide is the two-dimensional sheet containing carboxyl, hydroxyl and epoxy group obtained by chemical stripping graphite powder
Material.Its end has hydrophily oxygen-containing group and hydrophobic basal plane, thus shows amphipathic.By adjusting the pH of solution
Value, graphene oxide can be adsorbed between interface and reduce interfacial tension, to play the role of surfactant.Utilize this
Graphene oxide is coated on biodegradable polymers surface and restored by feature, can effectively be prevented its stacking, be restored simultaneously
Graphene oxide will significantly improve the mechanical performance and antistatic property of composite material as filler modified biodegradable polymers.
The present invention is first adjusted the hydrophilic and hydrophobic of graphene oxide, then by the dispersion of biodegradable polymers
Drop adds in the aqueous dispersions of graphene oxide the biodegradable polymers microballoon that graphene oxide cladding is prepared, and leads to
Each condition in control preparation process is crossed, including mixing speed and mixing time, the concentration of polymer dispersion liquid, graphite oxide
The concentration of alkene dispersion liquid and subsequent oxidation graphene reducing condition etc., are overlapped to form redox graphene by hot-pressing processing
Network further increases the antistatic property and intensity of composite material.
For in inorganic nano sheet/polymer composites preparation method, inorganic nano sheet is easy to stack the present invention, and poly-
The shortcomings that closing object poor compatibility, being easy to produce mutually separation and fault in material, selecting has amphiphilic graphene oxide, passes through tune
PH value is saved, biodegradable polymers microsphere surface is coated on, prepares high-antistatic after further restoring graphene oxide
Property, high mechanical strength biodegradable polymer.Graphene oxide play the role of surfactant be adsorbed on can biology
Degradation polymer bead surface coats bead using redox graphene is become after metal powder reduction.By constructing microballoon
The structure of cladding is used for so that the reduced graphene for playing electric action is evenly dispersed in the composite without being additionally added
It is living to surface is removed in the pollution and material preparation process of environment to avoid surfactant for the surfactant of dispersed graphite alkene
The complicated processes of property agent.Saturated concentration is high in aqueous solution for the biodegradable polymers microballoon of graphene oxide cladding, and
Even stabilization.Then it is restored under mildly acidic conditions by metal powder, freeze-drying obtains that scale is uniform, the reduction of controlled diameter
The biodegradable polymers microballoon of graphene oxide cladding.There is high-antistatic, high machine by prepared by thermoforming process
Tool intensity biodegradable polymer film, tensile strength improve 60% than biodegradable polymers, vitrifying
Temperature improves 11 DEG C, and thermal decomposition initial temperature improves 5 DEG C, the conductivity of material in redox graphene content 30%
Composite material than direct blending and reducing graphene oxide improves 35 times.With traditional by repairing inorganic nano material surface
Difference is blended after decorations, the present invention only allows for graphene oxide by churned mechanically emulsification and is coated on biodegradable gather
Object microsphere surface is closed, then is restored by metal powder, fixed cladding pattern has significant superiority.
In biodegradable polymers composite material preparation process of the invention, each step coordinated, sequence of steps
It cannot exchange, such as in order to prepare the biodegradable polymers microballoon of graphene oxide cladding, it is necessary to by polymer matrix ground
The dispersion liquid of material is added into graphene oxide aqueous dispersions, and in order to realize good coating function, it is necessary to adjust first
Graphene oxide it is amphipathic；In view of graphene oxide is interacted by hydrogen bond action and biodegradable polymers, it is
This faint active force of maintenance, treatment process of the emulsification package after, it is necessary to select relatively mild operation item as far as possible
Part, such as selection metal powder reduction graphene oxide, can realize the reduction of graphene oxide at room temperature；It is removed using hydrochloric acid
Remove excessive metal powder, rather than other methods, it is to keep the microsphere in order to ensure microballoon embodiment is constantly in acidic environment
System, it is ensured that redox graphene is coated on biodegradable polymers surface, finally by hot pressing, is capable of forming reduction-oxidation
The network structure of graphene, and biodegradable polymers play a part of to support redox graphene network, so obtain
Biodegradable polymers composite material has both excellent antistatic property, mechanical property and heat resistance.
The following are embodiments:
Embodiment 1
A kind of antistatic biodegradable polymers composite material, the polymerized thylene carbonate third including redox graphene cladding
Ester microsphere, after hot-forming, redox graphene is overlapped to form network distribution in poly (propylene carbonate) bead interface.Wherein poly- carbon
The mass ratio of sour Asia propyl ester and redox graphene is about 100:30.Above-mentioned anti-electrostatic polymer composite material, prepared
Journey is as follows:
2h is stirred by ultrasonic to being completely dissolved in 3g poly (propylene carbonate) and 30ml methylene chloride.
Graphene oxide dispersion ultrasonic wave aid dispersion is obtained into the oxidation that 150ml concentration is 6mg/ml in deionized water
Graphene aqueous dispersions.The pH of graphene oxide aqueous dispersions is adjusted to 3, and ultrasound 0.5h with hydrochloric acid.
The dichloromethane solution of poly (propylene carbonate) is added in above-mentioned graphene oxide water solution, and controls stirring speed
Degree is 800r/min, persistently stirs 1h and obtains stable emulsion.1.8g zinc powder is added into above-mentioned emulsion and stirs ultrasound
10min adds excessive hydrochloric acid and removes unreacted zinc powder.Above-mentioned solution is freeze-dried to obtain redox graphene packet
The poly (propylene carbonate) microballoon covered takes the poly (propylene carbonate) microballoon scanning electron microscope of a small amount of above-mentioned redox graphene cladding
(as shown in Figure 1) is observed this it appears that its chondritic, Fig. 2 for the poly (propylene carbonate) microballoon transmission electron microscope picture,
It can be seen that graphene oxide is coated on poly (propylene carbonate) microsphere surface.
Above-mentioned material is obtained into redox graphene/polypropylene carbonate composite material film by hot-forming, on
State membrane material and be cut into standard batten with cut-off knife and carry out extension test, obtain ultimate tensile strength be 31MPa (pure poly (propylene carbonate)
Ultimate tensile strength is 23MPa), it is 36 DEG C of (pure poly- carbonic acid with the glass transition temperature that differential scanning calorimetry (DSC) obtains material
The glass transition temperature of sub- propyl ester is 25 DEG C), it is 276 with the temperature that the thermal decomposition that thermogravimetric analyzer (TGA) measures material reaches 5%
DEG C (5% temperature of thermal decomposition of pure poly (propylene carbonate) be 273 DEG C), the conductivity with four probe test materials is 35S/m, conductance
Rate test result figure is shown in Fig. 3, it can be seen that the composite material that the present invention is prepared has excellent antistatic property.
Embodiment 2
A kind of antistatic biodegradable polymers composite material, the polymerized thylene carbonate third including redox graphene cladding
Ester microsphere, after hot-forming, redox graphene is overlapped to form network distribution in poly (propylene carbonate) bead interface.Wherein poly- carbon
The mass ratio of sour Asia propyl ester and redox graphene is about 100:25.
Above-mentioned anti-electrostatic polymer composite material, preparation process are as follows:
2h is stirred by ultrasonic to being completely dissolved in 1g poly (propylene carbonate) and 50ml ethyl acetate.
Graphene oxide dispersion ultrasonic wave aid dispersion is obtained into the oxidation that 250ml concentration is 1mg/ml in deionized water
Graphene aqueous dispersions.The pH of graphene oxide aqueous dispersions is adjusted to 2, and ultrasound 0.5h with hydrochloric acid.
The dichloromethane solution of poly (propylene carbonate) is added in above-mentioned graphene oxide water solution, and controls stirring speed
Degree is 900r/min, persistently stirs 1h and obtains stable emulsion.0.3g aluminium powder is added into above-mentioned emulsion and stirs ultrasonic 10min,
It adds excessive hydrochloric acid and removes unreacted aluminium powder.Above-mentioned solution is freeze-dried to obtain the poly- of redox graphene cladding
Propylene carbonate microsphere powder.
Above-mentioned material is obtained into redox graphene/polypropylene carbonate composite material film by hot-forming, on
It states membrane material and is cut into standard batten with cut-off knife and carry out extension test to reach ultimate tensile strength being 33MPa, use differential scanning calorimetry
(DSC) obtaining material glass temperature is 32 DEG C, and 5% temperature is reached with the thermal decomposition that thermogravimetric analyzer (TGA) measures material
It is 277 DEG C, the conductivity with four probe test materials is 27S/m, has excellent antistatic property.
Embodiment 3
A kind of antistatic biodegradable polymers composite material, the polymerized thylene carbonate third including redox graphene cladding
Ester microsphere, after hot-forming, redox graphene is overlapped to form network distribution in poly (propylene carbonate) bead interface.Wherein poly- carbon
The mass ratio of sour Asia propyl ester and redox graphene is about 100:10.
Above-mentioned anti-electrostatic polymer composite material, preparation process are as follows:
2h is stirred by ultrasonic to being completely dissolved in 2g poly (propylene carbonate) and 10ml chloroform.
Graphene oxide dispersion ultrasonic wave aid dispersion is obtained into the oxidation that 100ml concentration is 2mg/ml in deionized water
Graphene aqueous dispersions.The pH of graphene oxide aqueous dispersions is adjusted to 3, and ultrasound 0.5h with hydrochloric acid.
The dichloromethane solution of poly (propylene carbonate) is added in above-mentioned graphene oxide water solution, and controls stirring speed
Degree is 1000r/min, persistently stirs 2h and obtains stable emulsion.0.1g zinc powder is added into above-mentioned emulsion and stirs ultrasonic 10min,
It adds excessive hydrochloric acid and removes unreacted zinc powder.Above-mentioned solution is freeze-dried to obtain the poly- of redox graphene cladding
Propylene carbonate microsphere powder.
Above-mentioned material is obtained into redox graphene/polypropylene carbonate composite material film by hot-forming.On
It states membrane material and is cut into standard batten with cut-off knife and carry out extension test to reach ultimate tensile strength being 37MPa, use differential scanning calorimetry
(DSC) obtaining material glass temperature is 29 DEG C, and 5% temperature is reached with the thermal decomposition that thermogravimetric analyzer (TGA) measures material
It is 278 DEG C, the conductivity with four probe test materials is 1.04S/m, has certain antistatic property.
Embodiment 4
A kind of antistatic biodegradable polymers composite material, the polymerized thylene carbonate third including redox graphene cladding
Ester microsphere, after hot-forming, redox graphene is overlapped to form network distribution in poly (propylene carbonate) bead interface.Wherein poly- carbon
The mass ratio of sour Asia propyl ester and redox graphene is about 100:20.
Above-mentioned anti-electrostatic polymer composite material, preparation process are as follows:
2h is stirred by ultrasonic to being completely dissolved in 2g poly (propylene carbonate) and 50ml toluene.
Graphene oxide dispersion ultrasonic wave aid dispersion is obtained into the oxygen that 300ml concentration is 1.3mg/ml in deionized water
Graphite alkene aqueous dispersions.The pH of graphene oxide aqueous dispersions is adjusted to 5, and ultrasound 0.5h with hydrochloric acid.
The toluene solution of poly (propylene carbonate) is added in above-mentioned graphene oxide water solution, and controls mixing speed and is
800r/min persistently stirs 3h and obtains stable emulsion.0.6g aluminium powder is added into above-mentioned emulsion and stirs ultrasonic 10min, then plus
Enter excessive hydrochloric acid and removes unreacted aluminium powder.Above-mentioned solution is freeze-dried to obtain the poly- carbonic acid of redox graphene cladding
Sub- propyl ester microsphere powder.
Above-mentioned material is obtained into redox graphene/polypropylene carbonate composite material film by hot-forming.On
It states membrane material and is cut into standard batten with cut-off knife and carry out extension test to reach ultimate tensile strength being 35MPa, use differential scanning calorimetry
(DSC) obtaining material glass temperature is 31 DEG C, and 5% temperature is reached with the thermal decomposition that thermogravimetric analyzer (TGA) measures material
It is 277 DEG C, the conductivity with four probe test materials is 7.2S/m, has preferable antistatic property.
Embodiment 5
A kind of antistatic biodegradable polymers composite material, the polymerized thylene carbonate third including redox graphene cladding
Ester microsphere, after hot-forming, redox graphene is overlapped to form network distribution in poly (propylene carbonate) bead interface.Wherein poly- carbon
The mass ratio of sour Asia propyl ester and redox graphene is about 100:1.
Above-mentioned anti-electrostatic polymer composite material, preparation process are as follows:
By 5g can poly (propylene carbonate) and 25ml methylene chloride 2h is stirred by ultrasonic to being completely dissolved.
Graphene oxide dispersion ultrasonic wave aid dispersion is obtained into the oxygen that 125ml concentration is 0.4mg/ml in deionized water
Graphite alkene aqueous dispersions.The pH of graphene oxide aqueous dispersions is adjusted to 4, and ultrasound 0.5h with hydrochloric acid.
The dichloromethane solution of poly (propylene carbonate) is added in above-mentioned graphene oxide water solution, and controls stirring speed
Degree is 850r/min, persistently stirs 2h and obtains stable emulsion.0.1g aluminium powder is added into above-mentioned emulsion and stirs ultrasonic 10min,
It adds excessive hydrochloric acid and removes unreacted aluminium powder.Above-mentioned solution is freeze-dried to obtain the poly- of redox graphene cladding
Propylene carbonate microsphere powder.
Above-mentioned material is obtained into redox graphene/polypropylene carbonate composite material film by hot-forming.On
It states membrane material and is cut into standard batten with cut-off knife and carry out extension test to reach ultimate tensile strength being 27MPa, use differential scanning calorimetry
(DSC) obtaining material glass temperature is 27 DEG C, and 5% temperature is reached with the thermal decomposition that thermogravimetric analyzer (TGA) measures material
It is 275 DEG C, is 1.3 × 10 with the conductivity of four probe test materials-3S/m。
Comparative example 1
In order to be compared with above-mentioned antistatic biodegradable polymers composite property, the same method of the present embodiment
Obtained pure poly (propylene carbonate) film, it is specific the preparation method is as follows:
2h is stirred by ultrasonic to being completely dissolved in 5g poly (propylene carbonate) and 25ml ethyl acetate.With hydrochloric acid by 125ml go from
The pH of sub- water is adjusted to 2, and ultrasound 0.5h.The ethyl acetate solution of poly (propylene carbonate) is added in above-mentioned hydrochloric acid solution, and
Control mixing speed is 1000r/min, persistently stirs 3h.By obtained particle filtering, washing, drying, hot-forming.By hot pressing
The poly (propylene carbonate) film of forming is cut into standard batten with cut-off knife and carries out extension test to reach ultimate tensile strength being 23MPa, uses
It is 25 DEG C that differential scanning calorimetry (DSC), which obtains material glass temperature, and the thermal decomposition of material is measured with thermogravimetric analyzer (TGA)
The temperature for reaching 5% is 273 DEG C, is 1 × 10 with the conductivity of four probe test materials-6S/m does not have antistatic property.
Comparative example 2
In order to compare with above-mentioned antistatic biodegradable polymers composite property, the present embodiment includes graphite oxide
The poly (propylene carbonate) microballoon of alkene cladding, hot-forming rear graphene oxide are distributed in poly (propylene carbonate) bead interface, wherein
The mass ratio of poly (propylene carbonate) and graphene oxide be about 100:20 its it is specific the preparation method is as follows:
2h is stirred by ultrasonic to being completely dissolved in 2g poly (propylene carbonate) and 50ml toluene.Graphene oxide is dispersed into ultrasonic wave
Aid dispersion obtains the graphene oxide aqueous dispersions that 300ml concentration is 1.3mg/ml in deionized water.It will be aoxidized with hydrochloric acid
The pH of graphene aqueous dispersions is adjusted to 3, and ultrasound 0.5h.The toluene solution of poly (propylene carbonate) is added to above-mentioned graphite oxide
In aqueous solution, and controlling mixing speed is 850r/min, persistently stirs 3h and obtains stable emulsion.Above-mentioned solution is freeze-dried
Obtain the poly (propylene carbonate) microsphere powder of graphene oxide cladding.Above-mentioned material is obtained into graphite oxide by hot-forming
Alkene/polypropylene carbonate composite material film.Above-mentioned membrane material, which with cut-off knife is cut into standard batten and carries out extension test, reaches maximum drawing
Stretching intensity is 28MPa, and obtaining material glass temperature with differential scanning calorimetry (DSC) is 29 DEG C, with thermogravimetric analyzer (TGA)
It is 270 DEG C that the thermal decomposition for measuring material, which reaches 5% temperature, is 1 × 10 with the conductivity of four probe test materials-6S/m does not have
Standby antistatic property.
Comparative example 3
In order to compare with above-mentioned antistatic biodegradable polymers composite property, the present embodiment includes graphite oxide
The poly (propylene carbonate) microballoon of alkene cladding, hot-forming rear graphene oxide are distributed in poly (propylene carbonate) bead interface, wherein
The mass ratio of poly (propylene carbonate) and graphene oxide be about 100:1 its it is specific the preparation method is as follows:
2h is stirred by ultrasonic to being completely dissolved in 5g poly (propylene carbonate) and 25ml methylene chloride.Graphene oxide dispersion is super
Sound wave aid dispersion obtains the graphene oxide aqueous dispersions that 125ml concentration is 0.4mg/ml in deionized water.It will with hydrochloric acid
The pH of graphene oxide aqueous dispersions is adjusted to 2, and ultrasound 0.5h.The toluene solution of poly (propylene carbonate) is added to above-mentioned oxidation
In graphene aqueous solution, and controlling mixing speed is 900r/min, persistently stirs 3h and obtains stable emulsion.Above-mentioned solution is freezed
It is dried to obtain the poly (propylene carbonate) microsphere powder of graphene oxide cladding.Above-mentioned material is obtained into oxidation stone by hot-forming
Black alkene/polypropylene carbonate composite material film.Above-mentioned membrane material, which with cut-off knife is cut into standard batten and carries out extension test, reaches maximum
Tensile strength is 37MPa, and obtaining material glass temperature with differential scanning calorimetry (DSC) is 33 DEG C, uses thermogravimetric analyzer
(TGA) it is 275 DEG C that the thermal decomposition for measuring material, which reaches 5% temperature, is 1 × 10 with the conductivity of four probe test materials-6S/
M does not have antistatic property.
Comparative example 4:
In order to compare with above-mentioned antistatic biodegradable polymers composite property, the present embodiment includes reduction-oxidation
Graphene and poly (propylene carbonate) blended compound material, hot-forming rear redox graphene are randomly dispersed in polymeric substrates
In, wherein the mass ratio of poly (propylene carbonate) and redox graphene be about 100:30 its it is specific the preparation method is as follows:
2h is stirred by ultrasonic to being completely dissolved in 2g poly (propylene carbonate) and 50ml methylene chloride.By the reduction-oxidation of 600mg
Graphene dispersion is in 100ml deionized water.The pH of redox graphene aqueous dispersions is adjusted to 2, and ultrasound with hydrochloric acid
0.5h.The toluene solution of poly (propylene carbonate) is added in above-mentioned graphene oxide water solution, and controls mixing speed and is
900r/min persistently stirs 3h.By obtained particle filtering, washing, drying, hot-forming, redox graphene/poly- is obtained
Propylene carbonate composite material film.Above-mentioned membrane material, which with cut-off knife is cut into standard batten and carries out extension test, reaches ultimate tensile strength
For 26MPa, obtaining material glass temperature with differential scanning calorimetry (DSC) is 29 DEG C, measures material with thermogravimetric analyzer (TGA)
The thermal decomposition of material reach 5% temperature be 275 DEG C, the conductivity with four probe test materials is 0.98S/m, have centainly resist it is quiet
Electrical property, but compare with embodiment 1, the composite material which prepares does not have due to redox graphene and polymer
Interaction cannot obtain the polymer microballoon of redox graphene cladding, in identical redox graphene additional amount
Under, redox graphene is disorderly distributed in the composite at random, cannot effectively overlap polymer network, correspondingly, real
The conductivity for applying the composite material that example 1 is prepared is 35 times or more of the conductivity of composite material that this comparative example obtains.
Comparative example 5:
In order to compare with above-mentioned antistatic biodegradable polymers composite property, the present embodiment includes reduction-oxidation
Graphene and poly (propylene carbonate) blended compound material, hot-forming rear redox graphene are randomly dispersed in polymeric substrates
In, wherein the mass ratio of poly (propylene carbonate) and redox graphene be about 100:10 its it is specific the preparation method is as follows:
2h is stirred by ultrasonic to being completely dissolved in 2g poly (propylene carbonate) and 50ml methylene chloride.By the reduction-oxidation of 200mg
Graphene dispersion is in 150ml deionized water.The pH of redox graphene aqueous dispersions is adjusted to 3, and ultrasound with hydrochloric acid
0.5h.The toluene solution of poly (propylene carbonate) is added in above-mentioned graphene oxide water solution, and controls mixing speed and is
800r/min persistently stirs 3h, by obtained particle filtering, washing, drying, hot-forming, obtains redox graphene/poly-
Propylene carbonate composite material film.Above-mentioned membrane material, which with cut-off knife is cut into standard batten and carries out extension test, reaches ultimate tensile strength
For 28MPa, obtaining material glass temperature with differential scanning calorimetry (DSC) is 27 DEG C, measures material with thermogravimetric analyzer (TGA)
The thermal decomposition of material reach 5% temperature be 276 DEG C, the conductivity with four probe test materials is 0.25S/m, have centainly resist it is quiet
Electrical property.
Mechanical performance, thermal property and the electric conductivity of the material of the present invention of table 1
Biodegradable polymer matrix material poly (propylene carbonate) in above-described embodiment (can gather oneself two with PBAT
Acid/butylene terephthalate) replacement completely, obtained PBAT based composites；Correspondingly, in preparation method, it can except dissolution
The type of the organic solvent of biological degradation polyalcohol matrix may need outside appropriate adjustment, other reaction conditions, such as reactant
Type and proportion, mixing time etc. can remain unchanged；Wherein, the organic solvent suitable for polytrimethylene carbonate body is preferred
For methylene chloride, ethyl acetate, toluene, one of chloroform；Organic solvent suitable for PBAT matrix be preferably methylene chloride,
Chloroform, benzene, any one in toluene.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of antistatic biodegradable polymers composite material, which is characterized in that the composite material includes biodegradable
Polymeric matrix and redox graphene, the biodegradable polymer matrix is in the form of biodegradable polymers microballoon
In the presence of, and the redox graphene is coated on the biodegradable polymers microsphere surface, it is described biodegradable poly-
The mass ratio for closing object matrix and redox graphene is 100:1~100:30.
2. composite material as described in claim 1, which is characterized in that the antistatic biodegradable polymers composite material
Conductivity at 25 DEG C is 1 × 10-6~35S/m.
3. composite material as described in claim 1, which is characterized in that the biodegradable polymer matrix is polymerized thylene carbonate
Propyl ester or polyadipate/butylene terephthalate.
4. composite material as described in claim 1, which is characterized in that the redox graphene is passed through by graphene oxide
Metal powder reduction obtains, and the metal is zinc or aluminium.
5. a kind of preparation method of antistatic biodegradable polymers composite material, which comprises the steps of:
(1) it disperses biodegradable polymers in organic solvent and obtains biodegradable polymers dispersion liquid, it is described to give birth to
Concentration of the object degradation polymer in the dispersion liquid is 1g/5mL~1g/50mL；Wherein, the biodegradable polymers are
Poly (propylene carbonate) or polyadipate/butylene terephthalate；
(2) in deionized water by graphene oxide dispersion, graphene oxide aqueous dispersions are obtained, wherein the graphene oxide
Concentration be 0.4mg/ml~6mg/ml, the pH value of the graphene oxide aqueous dispersions is 2~5；
(3) the biodegradable polymers dispersion liquid that step (1) obtains is added to the graphene oxide of step (2) acquisition
In aqueous dispersions, stirring, emulsification remove the organic solvent, obtain biological can dropping for the graphene oxide cladding of stable dispersion
Depolymerize object lotion；
(4) oxygen in the biodegradable polymers lotion for the graphene oxide cladding for being obtained step (3) using metal powder
The reduction of graphite alkene, obtains the biodegradable polymers microballoon of redox graphene cladding；The biodegradable polymeric
Object and the redox graphene mass ratio are 100:1~100:30；
(5) unreacted metal powder in step (4) is removed using hydrochloric acid, refilters, washs, dries, obtains antistatic give birth to
Object degradation polymer composite material.
6. preparation method as claimed in claim 5, which is characterized in that step (1) organic solvent is methylene chloride, acetic acid
One of ethyl ester, toluene and chloroform are a variety of.
7. preparation method as claimed in claim 5, which is characterized in that the body of step (2) the graphene oxide aqueous dispersions
Product is 5~10 times of the biodegradable polymers dispersion liquid volume.
8. preparation method as claimed in claim 5, which is characterized in that step (3) mixing speed is 800~1000r/
Min, mixing time are 1~3 hour.
9. preparation method as claimed in claim 5, which is characterized in that step (4) metal powder and graphene oxide
Mass ratio is (0.5~2): 1, the metal is zinc or aluminium.
10. preparation method as claimed in claim 5, which is characterized in that further comprise the steps of:
(6) by the antistatic biodegradable polymers composite material by thermoforming handle, obtain it is antistatic can biology drop
Depolymerize object composite material film.
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| CN112876710A (en) * | 2021-01-18 | 2021-06-01 | 山东阜坤新材料有限公司 | Biodegradable antibacterial graphene in-situ polymerization copolyester packaging film and preparation process thereof |
| CN114479385A (en) * | 2022-03-08 | 2022-05-13 | 贵阳学院 | Conductive flame-retardant biodegradable PBAT composite material and preparation method and application thereof |
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| US20100036023A1 (en) * | 2008-08-08 | 2010-02-11 | Weiqing Weng | Graphite Nanocomposites |
| CN105623136A (en) * | 2016-03-17 | 2016-06-01 | 中国科学院深圳先进技术研究院 | Polymer conductive composite and preparation method thereof |
| CN106745463A (en) * | 2017-01-20 | 2017-05-31 | 华中科技大学 | A kind of sewage water treatment method of utilization reducing agent in-situ reducing graphene oxide |
| CN106995601A (en) * | 2017-04-06 | 2017-08-01 | 华中科技大学 | A kind of biodegradable polymers composite and preparation method thereof |
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| US20100036023A1 (en) * | 2008-08-08 | 2010-02-11 | Weiqing Weng | Graphite Nanocomposites |
| CN105623136A (en) * | 2016-03-17 | 2016-06-01 | 中国科学院深圳先进技术研究院 | Polymer conductive composite and preparation method thereof |
| CN106745463A (en) * | 2017-01-20 | 2017-05-31 | 华中科技大学 | A kind of sewage water treatment method of utilization reducing agent in-situ reducing graphene oxide |
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| CN112876710A (en) * | 2021-01-18 | 2021-06-01 | 山东阜坤新材料有限公司 | Biodegradable antibacterial graphene in-situ polymerization copolyester packaging film and preparation process thereof |
| CN112876710B (en) * | 2021-01-18 | 2022-03-11 | 山东阜坤新材料有限公司 | Biodegradable antibacterial graphene in-situ polymerization copolyester packaging film and preparation process thereof |
| CN114479385A (en) * | 2022-03-08 | 2022-05-13 | 贵阳学院 | Conductive flame-retardant biodegradable PBAT composite material and preparation method and application thereof |
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