CN107892796B - Epoxy group ionic liquid/multi-walled carbon nanotube/polymer composite material and preparation method thereof - Google Patents

Epoxy group ionic liquid/multi-walled carbon nanotube/polymer composite material and preparation method thereof Download PDF

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CN107892796B
CN107892796B CN201711132862.XA CN201711132862A CN107892796B CN 107892796 B CN107892796 B CN 107892796B CN 201711132862 A CN201711132862 A CN 201711132862A CN 107892796 B CN107892796 B CN 107892796B
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ionic liquid
composite material
polymer
carbon nanotube
epoxy
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CN107892796A (en
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吕雪
刘闯
孙树林
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Changchun University of Technology
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    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

The invention provides an epoxy ionic liquid/multi-walled carbon nanotube/polymer composite material and a preparation method thereof, belonging to the field of high polymer materials. The composite material is obtained by blending epoxy group ionic liquid, multi-walled carbon nano-tubes and polymers; the polymer is a polyester polymer. The invention also provides a preparation method of the epoxy ionic liquid/multi-walled carbon nanotube/polymer composite material. According to the invention, the epoxy group ionic liquid and the multi-walled carbon nanotube are adopted to compound and modify the polymer, so that the ionic liquid conductive composite material has high electrochemical activity and stability and strong conductivity of the carbon nanotube conductive composite material, the ionic liquid in the composite material can effectively prevent the carbon nanotube from agglomerating, and the ionic liquid and the carbon nanotube have synergistic effect, so that the carbon nanotube filler amount is effectively and greatly reduced, the ideal conductivity is achieved, the cost is reduced, and the material processing performance is improved.

Description

Epoxy group ionic liquid/multi-walled carbon nanotube/polymer composite material and preparation method thereof
Technical Field
The invention relates to the field of high polymer materials, in particular to an epoxy group ionic liquid/multi-walled carbon nanotube/polymer composite material and a preparation method thereof.
Background
Because the polymer material has excellent performance and receives more and more attention, the polymer material is rapidly developed and widely applied. The conductive polymer materials are mainly classified into a composite type and a structural type, wherein the composite type conductive polymer materials are widely applied to the fields of electronics, chemical engineering, energy, space navigation and the like, and are known to be one of the most promising conductive polymer materials. For the composite conductive polymer material, in order to enable the conductive filler to form a perfect conductive network structure in a matrix, the conductive filler needs to reach a certain addition concentration to play a role, and when the addition amount of the conductive filler exceeds a percolation threshold, the material can show excellent electrical properties.
Polybutylene terephthalate (PBT) is a crystalline linear saturated polyester resin. PBT has irreplaceable superiority in industry, has become the fifth most common engineering plastic following Polyamide (PA), Polycarbonate (PC), Polyoxymethylene (POM) and modified polyphenylene ether (MPPO), and has found wide application in many fields, such as in the fields of electronics and electrical, in the automotive industry, in industrial accessories, and the like. In recent years, the global market demand of PBT reaches 35-40 million tons/year, and the annual average growth rate is as high as 6-8%. PBT is widely concerned by higher mechanical strength, heat resistance and processability, but the PBT is easy to generate electrostatic effect in the using process and has potential safety hazard. In order to improve the antistatic performance, a certain conductive agent such as graphite, carbon black, carbon nano tubes and the like is added into the PBT to improve the conductive performance, so that the application range of the PBT can be further expanded.
Since the first discovery of Carbon Nanotubes (CNTs) in 1991, their unique nanostructures and excellent mechanical, electrical, and thermal properties have attracted much attention. Research on the introduction of CNTs into polymers to improve various properties of composite materials has also become an important research direction. In general, carbon nanotubes have a large specific surface area and a high surface free energy, which leads to poor dispersibility and high agglomeration tendency during the process of compounding with polymers. The inert surface of the carbon nanotube has poor bonding capability with the polymer matrix interface, so that the excellent performance of the carbon nanotube cannot be exerted. At present, experts at home and abroad carry out a great deal of research on the problem, and the interfacial bonding capability between the carbon nano tube and the polymer matrix is improved mainly by methods of functionalized covalent bonds, polymer wrapping and the like. In general, the mechanical properties and processability of the material vary with the amount of conductive agent added. As the addition amount of the carbon nanotube as a conductive agent increases, the mechanical properties and the processability of the material are greatly reduced, the use value is lost, and the practical significance is lost, so that the use amount of the carbon nanotube is effectively controlled.
Generally, the percolation threshold of the filled carbon nanotube conductive composite material is about 1.5 to 3.0 percent, but when the epoxy group ionic liquid is added into the system, the filling amount of the carbon nanotubes can be effectively reduced (about 40 percent reduction). Since the filling of the carbon nanotubes can affect the related properties of the material, such as increasing the melt viscosity of the composite system and deteriorating the processability, how to reduce the filling amount of the conductive component is a problem of improving the composite conductive polymer material. Therefore, the modification method for reducing the content of the conductive component has wide application fields and research values.
Disclosure of Invention
The invention aims to provide an epoxy ionic liquid/multi-wall carbon nanotube/polymer composite material and a preparation method thereof, wherein the addition amount of a conductive component in the composite material is small, which is reduced by about 40% compared with the simple compounding of a polymer and a carbon nanotube, and the composite material has excellent conductive performance.
The invention firstly provides an epoxy ionic liquid/multi-walled carbon nanotube/polymer composite material, which is obtained by blending the epoxy ionic liquid, the multi-walled carbon nanotube and a polymer;
the polymer is a polyester polymer.
Preferably, the preparation method of the epoxy group ionic liquid comprises the following steps:
mixing epoxy chloropropane and N-methylimidazole, reacting for 3-5h at 30-45 ℃, then heating to 5 ℃ to 65 ℃ every half hour, keeping the temperature of 65 ℃ for reacting for 3h, and stopping the reaction to obtain the epoxy group ionic liquid.
Preferably, the molar ratio of the epichlorohydrin to the N-methylimidazole is (1.2-2): 1.
Preferably, the polyimide polymer is polyethylene terephthalate, polybutylene terephthalate or polyarylate.
Preferably, the mass percentages of the epoxy-based ionic liquid, the multi-wall carbon nanotube and the polymer are (1-10): (0.1-5): (85-98.5).
The invention also provides a preparation method of the epoxy ionic liquid/multi-walled carbon nanotube/polymer composite material, which comprises the following steps:
mixing the epoxy group ionic liquid, the multi-walled carbon nano-tube and the polymer, then blending the blend in a ThermoHaake internal mixer, and drying to obtain the epoxy group ionic liquid/multi-walled carbon nano-tube/polymer composite material.
Preferably, the temperature for blending in the Thermo Haake internal mixer is 220-240 ℃, the blending time is 5-6min, and the rotating speed is 55-60 r/min.
The invention has the advantages of
The invention firstly provides an epoxy ionic liquid/multi-walled carbon nanotube/polymer composite material, which is obtained by blending the epoxy ionic liquid, the multi-walled carbon nanotube and a polymer; the polymer is a polyimide polymer. Compared with the prior art, the self-made novel epoxy group ionic liquid is adopted, and the ionic liquid contains an epoxy group, pi-pi interaction exists between the epoxy group ionic liquid and the carbon nano tube, and simultaneously, the epoxy group and the end group reaction interaction between the polyester polymer ensure that the ionic liquid has good compatibility in the polyester polymer, so that the ionic liquid and the carbon nano tube generate synergistic action, and effectively assist the dispersion of the carbon nano tube in a matrix, so that the carbon nano tube can be uniformly distributed, a good conductive network is formed, and the electrical property of the material is effectively improved; in addition, compared with single-component multi-walled carbon nanotubes, the epoxy group ionic liquid and the multi-walled carbon nanotubes are adopted to compound and modify the polymer, so that the ionic liquid composite material has the electrochemical activity and stability of the ionic liquid conductive composite material and the strong conductivity of the carbon nanotube conductive composite material, the ionic liquid in the composite material can effectively prevent the carbon nanotubes from agglomerating, and the synergistic effect of the ionic liquid and the carbon nanotubes is also considered, the filling amount of the carbon nanotubes is effectively and greatly reduced, the ideal conductivity is achieved, the cost is reduced, and the processing performance of the material is improved.
The invention also provides a preparation method of the epoxy ionic liquid/multi-walled carbon nanotube/polymer composite material, the method has simple process and easily obtained raw materials, and the prepared composite material can effectively reduce the filler of the conductive component, effectively reduce the cost, simultaneously reduce the influence on the processing performance of the material and expand the application field range of the material.
Drawings
FIG. 1 is an infrared spectrum of an epoxy-based ionic liquid prepared in example 1 of the present invention.
FIG. 2 is a graph comparing the conductivity of PBT/IL/MWCNTs-1 prepared in comparative example 1 with that of PBT/IL/MWCNTs-4 prepared in example 4.
FIG. 3 is a graph comparing the conductivity of PBT/IL/MWCNTs-2 prepared in comparative example 2 with that of PBT/IL/MWCNTs-5 prepared in example 5.
FIG. 4 is a graph comparing the conductivity of PBT/IL/MWCNTs-3 prepared in comparative example 3 with that of PBT/IL/MWCNTs-6 prepared in example 6.
FIG. 5 is a graph comparing the conductivity of PET/IL/MWCNTs-1 prepared in comparative example 4 with the conductivity of PET/IL/MWCNTs-2 prepared in example 8.
FIG. 6 is a graph of the conductivity relationship for PBT/IL/MWCNTs-7 prepared in example 7 of the present invention.
Fig. 7 is a dc conductivity relationship for example 9 of the present invention.
FIG. 8 is a schematic diagram illustrating the principle of the preparation method of the epoxy-based ionic liquid/multi-walled carbon nanotube/polymer composite material according to the present invention.
Detailed Description
The invention firstly provides an epoxy ionic liquid/multi-walled carbon nanotube/polymer composite material, which is obtained by blending the epoxy ionic liquid, the multi-walled carbon nanotube and a polymer; the polymer is a polyimide polymer.
The epoxy group ionic liquid/multi-walled carbon nanotube/polymer conductive composite material is prepared by adopting a melt blending method, the electrical property of the composite material is improved by utilizing the synergistic effect of the epoxy group ionic liquid and the carbon nanotube, the conductive composite material can effectively reduce the filler of a conductive component, can effectively reduce the cost, and simultaneously reduces the influence on the processing property of the material and expands the application field range of the conductive composite material.
According to the present invention, the preparation method of the epoxy-based ionic liquid preferably comprises:
mixing epoxy chloropropane and N-methylimidazole, reacting for 3-5h at 30-45 ℃, wherein the color of the solution is changed into orange yellow until the solution is changed into reddish brown in the reaction process, when reactants are changed into reddish brown, the reaction rate can be accelerated by raising the temperature, as the epoxy group is active, a ring-opening reaction can release a large amount of heat, and in order to avoid the ring-opening reaction, the temperature of the system can not be raised rapidly, so that the reaction is carried out by adopting a sectional heating mode to control the reaction degree, and the preference is that: after reacting for 3-5h, heating to 5 ℃ to 65 ℃ every half an hour, keeping the temperature of 65 ℃ and reacting for 3h, stopping the reaction, and gradually increasing the viscosity of the system along with the extension of the reaction time to obtain the epoxy group ionic liquid. The mol ratio of the epichlorohydrin to the N-methylimidazole is preferably (1.2-2): 1.
According to the invention, the self-made novel epoxy group ionic liquid is adopted, and the ionic liquid contains an epoxy group, so that pi-pi interaction exists between the epoxy group ionic liquid and the carbon nano tube, and simultaneously, the epoxy group and the end group reaction interaction between the polyester polymer ensure that the epoxy group ionic liquid has good compatibility in the polyester polymer, and further generate synergistic action with the carbon nano tube, so that the carbon nano tube can be uniformly distributed, a good conductive network is formed, and the electrical property of the material is effectively improved. The schematic diagram of the reaction process is shown in fig. 8.
According to the invention, the polyester-based polymer is preferably polybutylene terephthalate (PBT) or polyethylene terephthalate (PET).
According to the invention, the mass percentages of the epoxy-based ionic liquid, the multi-wall carbon nanotube and the polymer are preferably (1-10): (0.1-5): (85-98.9). More preferably (3-7): (0.5-3.5): (89.5-96.5).
The content of the epoxy group ionic liquid is 1.0-10.0%, and the optimal processing performance and electrical performance of the material can be maintained within the content range.
The content of the multi-wall carbon nano tube is 0.1-5.0%, when the content is less than 0.1%, the conductivity of the material is poor, and when the content exceeds 5.0%, the mechanical property of the material is greatly reduced and the cost is increased.
The invention also provides a preparation method of the epoxy ionic liquid/multi-walled carbon nanotube/polymer composite material, which comprises the following steps:
and (3) carrying out melt blending on the epoxy group ionic liquid, the multi-walled carbon nano tube and the polymer, then carrying out blending on the blend in a ThermoHaake internal mixer, and drying to obtain the epoxy group ionic liquid/multi-walled carbon nano tube/polymer composite material. The blending temperature in the Thermo Haake internal mixer is preferably 225 ℃ and 240 ℃, the blending time is 5-6min, and the rotating speed is 55-60 r/min. The drying temperature is preferably 80-90 ℃, and the drying time is preferably 24-36 h.
In order to illustrate the present invention more clearly, the following examples are given without any limitation to the scope of the present invention.
Example 1 preparation of epoxy-based Ionic liquids
Weighing epichlorohydrin and N-methylimidazole according to the molar ratio of 1.2:1, adding into a three-neck flask at room temperature, and adding N2Protecting, mechanically stirring, reacting at 45 deg.C for 5h, and changing the color of the solution to orange yellow until red brown. After the reaction is carried out for 5 hours, the temperature is increased by 5 ℃ to 65 ℃ every half an hour, the reaction is stopped after the reaction is carried out for 3 hours under the condition of keeping the temperature at 65 ℃, and the viscosity of the system is gradually increased along with the extension of the reaction time. After the reaction was stopped, the product was washed repeatedly with diethyl ether. And then, recrystallizing and purifying the product by using acetone, drying in vacuum and weighing to obtain the epoxy group ionic liquid product, wherein the monomer conversion rate is 83.11%.
FIG. 1 is an infrared spectrum of an epoxy-based ionic liquid prepared in example 1 of the present invention. FIG. 1 illustrates that epoxy-based ionic liquids were successfully prepared in the present invention.
Example 2 preparation of epoxy-based Ionic liquids
Weighing epichlorohydrin and N-methylimidazole according to a molar ratio of 2:1, adding into a three-neck flask at room temperature, and adding N2Protecting, mechanically stirring, reacting at 45 deg.C for 5h, and changing the color of the solution to orange yellow until red brown. After the reaction is carried out for 5 hours, the temperature is increased by 5 ℃ to 65 ℃ every half an hour, the reaction is stopped after the reaction is carried out for 3 hours under the condition of keeping the temperature at 65 ℃, and the viscosity of the system is gradually increased along with the extension of the reaction time. After the reaction was stopped, the product was washed repeatedly with diethyl ether. Then acetone is used for recrystallization and purification of the product, the product is weighed after vacuum drying,the product epoxy group ionic liquid is obtained, and the monomer conversion rate is 54.28%.
Example 3 preparation of epoxy-based Ionic liquids
Weighing epichlorohydrin and N-methylimidazole according to the molar ratio of 1.5:1, adding into a three-neck flask at room temperature, and adding N2Protecting, mechanically stirring, reacting at 45 deg.C for 5h, and changing the color of the solution to orange yellow until red brown. After the reaction is carried out for 5 hours, the temperature is increased by 5 ℃ to 65 ℃ every half an hour, the reaction is stopped after the reaction is carried out for 3 hours under the condition of keeping the temperature at 65 ℃, and the viscosity of the system is gradually increased along with the extension of the reaction time. After the reaction was stopped, the product was washed repeatedly with diethyl ether. And then, recrystallizing with acetone to purify the product, drying in vacuum, and weighing to obtain the epoxy group ionic liquid product, wherein the monomer conversion rate is 59.37%.
Comparative example 1
Polybutylene terephthalate (PBT) was mixed with the epoxy-based Ionic Liquid (IL) prepared in example 1 and multi-walled carbon nanotubes (MWCNTs) in a mass ratio of 98.5: 0: 1.5 Experimental setting scheme, mixing and proportioning, blending the prepared blend in a Thermo Haake internal mixer at the rotating speed of 60r/min and the temperature of 240 ℃ for 5min, and then putting the blend into a vacuum oven at 80 ℃ for drying for 24h to obtain the epoxy group ionic liquid/multi-wall carbon nanotube/polymer composite material PBT/IL/MWCNTs-1.
Comparative example 2
Polybutylene terephthalate (PBT) was mixed with the epoxy-based Ionic Liquid (IL) prepared in example 1 and multi-walled carbon nanotubes (MWCNTs) in a mass ratio of 98.0: 0.0: 2.0 experiment, setting a scheme to carry out mixing proportioning, blending the prepared blend in a Thermo Haake internal mixer at the rotating speed of 60r/min and the temperature of 240 ℃ for 5min, and then putting the blend into a vacuum oven at the temperature of 80 ℃ for drying for 24h to obtain the epoxy group ionic liquid/multi-wall carbon nanotube/polymer composite material PBT/IL/MWCNTs-2.
Comparative example 3
Polybutylene terephthalate (PBT) was mixed with the epoxy-based Ionic Liquid (IL) prepared in example 1 and multi-walled carbon nanotubes (MWCNTs) in a mass ratio of 97.5: 0.0: 2.5 Experimental setting scheme, mixing and proportioning, blending the prepared blend in a Thermo Haake internal mixer at the rotating speed of 60r/min and the temperature of 240 ℃ for 5min, and then putting the blend into a vacuum oven at 80 ℃ for drying for 24h to obtain the epoxy group ionic liquid/multi-wall carbon nanotube/polymer composite material PBT/IL/MWCNTs-3.
Comparative example 4
Polyethylene terephthalate (PET) was mixed with the epoxy-based Ionic Liquid (IL) prepared in example 1 and multi-walled carbon nanotubes (MWCNTs) in a mass ratio of 98.0: 0.0: 2.0 experiment, setting a scheme to carry out mixing proportioning, blending the prepared blend in a Thermo Haake internal mixer at the rotating speed of 60r/min and the temperature of 240 ℃ for 5min, and then putting the blend into a vacuum oven at the temperature of 80 ℃ for drying for 24h to obtain the epoxy group ionic liquid/multi-wall carbon nano tube/polymer composite material PET/IL/MWCNTs-1.
Example 4
Polybutylene terephthalate (PBT) was mixed with the epoxy-based Ionic Liquid (IL) prepared in example 1 and multi-walled carbon nanotubes (MWCNTs) in a mass ratio of 93.5: 5.0: 1.5 Experimental setting scheme, mixing and proportioning, blending the prepared blend in a Thermo Haake internal mixer at the rotating speed of 60r/min and the temperature of 240 ℃ for 5min, and then putting the blend into a vacuum oven at 80 ℃ for drying for 24h to obtain the epoxy group ionic liquid/multi-wall carbon nanotube/polymer composite material PBT/IL/MWCNTs-4.
FIG. 2 is a graph comparing the conductivity of PBT/IL/MWCNTs-1 prepared in comparative example 1 with that of PBT/IL/MWCNTs-4 prepared in example 4. As can be seen from FIG. 2, comparative example 1 and example 4The MWCNTs content in the composite material is the same, but the conductive effect of the comparative example 1 is poor, and in contrast, the conductivity of the invention in the example 4 is from 10-9Increased to 10-5The electrical properties are excellent.
Example 5
Polybutylene terephthalate (PBT) was mixed with the epoxy-based Ionic Liquid (IL) prepared in example 1 and multi-walled carbon nanotubes (MWCNTs) in a mass ratio of 93.0: 5.0: 2.0 the experimental setting scheme is used for mixing and proportioning, namely the composition proportion of the blend. And blending the prepared blend in a Thermo Haake internal mixer at the rotating speed of 60r/min and the temperature of 240 ℃ for 5min, and then putting the blend into a vacuum oven at the temperature of 80 ℃ for drying for 24h to obtain the epoxy group ionic liquid/multi-wall carbon nanotube/polymer composite material PBT/IL/MWCNTs-5.
FIG. 3 is a graph comparing the conductivity of PBT/IL/MWCNTs-2 prepared in comparative example 2 with that of PBT/IL/MWCNTs-5 prepared in example 5. As can be seen from FIG. 3, the MWCNTs content in comparative example 2 and example 5 is the same, but the conductivity of comparative example 2 is inferior, in contrast to the conductivity of inventive example 5 of from 10-6Increased to 10-4The electrical properties are excellent.
Example 6
Polybutylene terephthalate (PBT) was mixed with the epoxy-based Ionic Liquid (IL) prepared in example 2 and multi-walled carbon nanotubes (MWCNTs) in a mass ratio of 92.5: 5.0: 2.5 the experimental setting scheme is used for mixing and proportioning, namely the composition proportion of the blend. And blending the prepared blend in a Thermo Haake internal mixer at the rotating speed of 60r/min and the temperature of 240 ℃ for 5min, and then putting the blend into a vacuum oven at the temperature of 80 ℃ for drying for 24h to obtain the epoxy group ionic liquid/multi-wall carbon nanotube/polymer composite material PBT/IL/MWCNTs-6.
FIG. 4 is a graph comparing the conductivity of PBT/IL/MWCNTs-3 prepared in comparative example 3 with that of PBT/IL/MWCNTs-6 prepared in example 6. As can be seen from FIG. 4, the MWCNTs content is the same in comparative example 3 and example 6, but the conductive effect of comparative example 3 is poor, and in contrast, the conductivity of example 6 of the present invention is increased from 10-5 to 10-3, and the electrical properties are excellent.
Example 7
Polybutylene terephthalate (PBT) was mixed with the epoxy-based Ionic Liquid (IL) prepared in example 3 and multi-walled carbon nanotubes (MWCNTs) in a mass ratio of 92.0: 5.0: 3.0 the experimental setting scheme is mixed and proportioned, namely the composition ratio of the blend. And blending the prepared blend in a Thermo Haake internal mixer at the rotating speed of 60r/min and the temperature of 240 ℃ for 5min, and then putting the blend into a vacuum oven at the temperature of 80 ℃ for drying for 24h to obtain the epoxy group ionic liquid/multi-wall carbon nanotube/polymer composite material PBT/IL/MWCNTs-7.
FIG. 6 is a graph of the conductivity relationship of PBT/IL/MWCNTs-7 obtained in example 7 of the present invention, when the conductivity is increased from 10 with increasing frequency-5Increased to 10-3The electrical properties are excellent.
Example 8
Polyethylene terephthalate (PET) was mixed with the epoxy-based Ionic Liquid (IL) prepared in example 1 and multi-walled carbon nanotubes (MWCNTs) in a mass ratio of 93.0: 5.0: 2.0 experiment, setting a scheme to carry out mixing proportioning, blending the prepared blend in a Thermo Haake internal mixer at the rotating speed of 60r/min and the temperature of 240 ℃ for 5min, and then putting the blend into a vacuum oven at the temperature of 80 ℃ for drying for 24h to obtain the epoxy group ionic liquid/multi-wall carbon nano tube/polymer composite material PET/IL/MWCNTs-2.
FIG. 5 is a graph comparing the conductivity of PET/IL/MWCNTs-1 prepared in comparative example 4 with the conductivity of PET/IL/MWCNTs-2 prepared in example 8. As can be seen from FIG. 5, the MWCNTs content is the same in comparative example 4 and example 8, but the conductivity of comparative example 4 is inferior, in contrast to the conductivity of example 8 of the present inventionRate from 10-6Increased to 10-4The electrical properties are excellent.
Example 9
Polybutylene terephthalate (PBT) was mixed with the epoxy-based Ionic Liquid (IL) prepared in example 1 and multi-walled carbon nanotubes (MWCNTs) in a mass ratio of (92.5-94.5): 5.0: (0.5-2.5) and (97.5-99.5): 0.0: (0.5-2.5) carrying out mixing proportioning according to an experimental setting scheme, blending the prepared blend in a Thermo Haake internal mixer at the rotating speed of 60r/min and the temperature of 240 ℃ for 5min, and then putting the blend in a vacuum oven at the temperature of 80 ℃ for drying for 24h to obtain the epoxy group ionic liquid/multi-walled carbon nanotube/polymer composite material.
FIG. 7 is a graph of the DC conductivity of PET/IL/MWCNTs obtained in example 9 of the present invention as a function of MWCNTSM. From the trend of the curve, the system added with the epoxy group ionic liquid has a good conductive effect when the content of MWCNTs is low, and the modification method provided by the invention effectively reduces the addition amount of the MWCNTs.

Claims (6)

1. The composite material is characterized in that the composite material is obtained by blending epoxy ionic liquid, multi-walled carbon nanotubes and a polymer;
the polymer is a polyester polymer;
the preparation method of the epoxy group ionic liquid comprises the following steps:
mixing epoxy chloropropane and N-methylimidazole, reacting for 3-5h at 30-45 ℃, then heating to 5 ℃ to 65 ℃ every half hour, keeping the temperature of 65 ℃ for reacting for 3h, and stopping the reaction to obtain the epoxy group ionic liquid.
2. The epoxy-based ionic liquid/multi-walled carbon nanotube/polymer composite material as claimed in claim 1, wherein the molar ratio of epichlorohydrin to N-methylimidazole is (1.2-2): 1.
3. The epoxy-based ionic liquid/multi-walled carbon nanotube/polymer composite material of claim 1, wherein the polyester-based polymer is polyethylene terephthalate, polybutylene terephthalate, or polyarylate.
4. The epoxy-based ionic liquid/multi-walled carbon nanotube/polymer composite material as claimed in claim 1, wherein the mass percentages of the epoxy-based ionic liquid, the multi-walled carbon nanotube and the polymer are (1-10): (0.1-5): (85-98.5).
5. The method for preparing the epoxy-based ionic liquid/multi-walled carbon nanotube/polymer composite material as claimed in claim 1, wherein the method comprises:
mixing the epoxy group ionic liquid, the multi-walled carbon nano-tube and the polymer, then blending the blend in a Thermo Haake internal mixer, and drying to obtain the epoxy group ionic liquid/multi-walled carbon nano-tube/polymer composite material.
6. The method for preparing the epoxy ionic liquid/multi-walled carbon nanotube/polymer composite material as claimed in claim 5, wherein the temperature for blending in the Thermo Haake internal mixer is 220-240 ℃, the blending time is 5-6min, and the rotation speed is 55-60 r/min.
CN201711132862.XA 2017-11-15 2017-11-15 Epoxy group ionic liquid/multi-walled carbon nanotube/polymer composite material and preparation method thereof Expired - Fee Related CN107892796B (en)

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