KR20220030766A - Filler for polymer composites and the process for producing the same - Google Patents

Abstract

The present invention relates to a polymer composite film and a manufacturing method thereof, and more specifically, to a manufacturing method of a polymer composite which mixes and exfoliates graphene and a carbon nanotube by low physical shear force (by high dispersion) to provide excellent electrical properties without damaging physical properties and electrical properties.

Description

Polymer composite filler and its manufacturing method {Filler for polymer composites and the process for producing the same}

The present invention relates to a polymer composite filler and a method for manufacturing the same, and more particularly, to a polymer composite filler in which graphene and carbon nanotubes are highly dispersed, and excellent in electrical properties, and to a method for manufacturing a polymer composite filler.

Polymer nanocomposite has improved mechanical properties by peeling and dispersing inorganic/metal particles on a nano-scale in polymer materials such as thermoplastic resins and thermosetting resins, that is, without damage to impact resistance, toughness and transparency ① strength and rigidity, ② Gas and liquid permeation inhibitory performance, ③ Flame retardant and flame retardant, ④ Abrasion resistance, ⑤ High temperature stability is greatly improved.

As a prior art related to such a polymer nanocomposite, in Korean Patent Publication No. 10-2013-0139003 (published on December 20, 2013), a linear low-density polyethylene composite prepared by melt-mixing graphene and carbon nanotubes in a linear low-density polyethylene polymer In addition, in Patent Publication No. 10-2017-0098083 (published on August 29, 2017), the steps of preparing a master batch by extruding carbon nanotubes and a first olefin-based polymer resin and the prepared master batch A technology for preparing a conductive resin composition by mixing a second olefinic polymer resin with the second olefinic polymer resin is described.

On the other hand, carbon nanotubes, which are frequently used as a two-dimensional material added to improve polymer properties, have excellent properties and are one of the materials that are spotlighted as a new nano material in various fields. Specifically, carbon nanotubes are fibrous materials with a diameter of nanometers, a length/diameter ratio of several thousand, a large surface area of several hundred m ² /g, and excellent mechanical properties as well as excellent thermal and electrical conductivity. has

On the other hand, graphene as another additive in the polymer composite is a honeycomb-shaped two-dimensional planar carbon allotrope composed of sp2 bonds of carbon atoms. Of the four outermost electrons in the carbon atom, three electrons form an s-bond to form a hexagonal structure, and graphene due to the long-range p-conjugation formed by the remaining one electrons has excellent physical and electrical properties.

In addition, graphene has 100 times higher electron mobility than silicon, which is a main raw material for semiconductor materials, and 100 times higher electrical conductivity than copper. The tensile strength is more than 200 times that of steel, and the electrical conductivity does not decrease even if the area is increased or bent by more than 10% due to good elasticity. In addition, it has more than twice the thermal conductivity of diamond, which has the highest thermal conductivity among existing materials.

The graphene synthesis process is made by methods such as physical and chemical exfoliation, chemical vapor deposition, and epitaxial growth.

However, when manufacturing a polymer composite material containing carbon nanotubes or graphene, there is a problem such as a rapid increase in the viscosity of the polymer resin during the mixing process, so that it is difficult to achieve uniform dispersion in the polymer resin. Therefore, there is a difficulty in actual expression of the excellent physical properties expected of the composite material.

Specifically, if carbon nanotubes and graphene do not form a uniform dispersed phase in the polymer resin and do not form a bond with the resin at the interface, the graphene aggregates, and as a result, cracks, pores, or pinholes in the composite material. (pin hole), etc. are generated, and the overall physical properties of the composite material are rather greatly reduced.

As described above, in the case of conventionally complexing fine fillers in micrometers or nanometers, for example, metal fillers, ceramic fillers, or carbon fillers, in particular, nano-carbons such as carbon nanotubes or graphene with a polymer resin through a compounding process, There was a limit to dispersing while containing the filler in a high content.

At the laboratory level, the dispersion properties of carbon nanotubes that try to stick together by van der Waals attraction are well controlled by chemical and physical methods. However, in the case of mass-production, the process cost is very high, the dispersion of carbon nanotubes is not well controlled due to various constraints such as time, and as a result, incomplete contact between the carbon nanotubes occurs.

As such, when a polymer resin composite material containing carbon nanotubes and/or graphene is mass-produced, the dispersion characteristics of the carbon nanotubes are not well controlled, and accordingly, the physical properties of the carbon nanotubes are not fully expressed. It is difficult to guarantee improvement of various properties such as mechanical, electrical, and thermal performance of composite materials.

Therefore, research is needed to improve the physical properties of the nanomaterial added as a polymer composite filler in order to improve these problems and improve the low electrical conductivity pointed out as a disadvantage of the conventional polymer composite.

Laid-open Patent Publication No. 10-2013-0139003 (published date: 2013.12.20) Laid-Open Patent Publication No. 10-2017-0098083 (published date: 2017.08.29.)

The present invention has been devised to solve the above problems, and an object of the present invention is to provide a polymer composite filler having excellent physical and electrical properties, including highly dispersed graphene and carbon nanotubes.

In addition, the present invention not only maintains the intrinsic physical properties of graphene and carbon nanotubes by using relatively low energy in peeling graphene and carbon nanotubes, but also is highly dispersed to provide a polymer composite filler exhibiting high electrical conductivity. An object of the present invention is to provide a manufacturing method.

In the present invention to solve the above problems, the polymer composite filler includes graphene and carbon nanotubes, and the mass ratio of the graphene and carbon nanotubes is in the range of 8:2 to 2:8, and the polymer composite The specific surface area of the filler provides a polymer composite filler, characterized in that in the range of 10 ~ 500 m2 / g.

The average particle diameter of the graphene may be 0.2 to 20 μm, and the specific surface area of the graphene may be 50 to 600 m ² /g.

The average particle diameter of the carbon nanotubes may be 5 to 25 nm, and the specific surface area of the carbon nanotubes may be 120 to 600 m ² /g.

The polymer may be thermosetting, thermoplastic or elastomer.

In addition, the present invention comprises the steps of: a) preparing graphene and carbon nanotubes in a mass ratio of 2:8 to 8:2; and b) putting the graphene and carbon nanotubes into a material peeling device and milling them at a speed in the range of 200 to 500 rpm to obtain a polymer composite filler; provides a method for producing a polymer composite filler comprising: a.

The speed of the material peeling device may be in the range of 350 to 400 rpm.

The average particle diameter of the carbon nanotubes may be 5 to 25 nm, and the specific surface area of the carbon nanotubes may be 120 to 600 m ² /g.

The average particle diameter of the graphene may be 0.2 to 20 μm, and the specific surface area of the graphene may be 50 to 600 m ² /g.

The polymer may be thermosetting, thermoplastic or elastomer.

In addition, the present invention provides a polymer composite filler prepared by the above manufacturing method.

As described above, in the polymer composite filler according to the present invention, graphene and carbon nanotubes are highly dispersed, the specific surface area is very high, and the physical properties and electrical conductivity properties are very excellent.

In addition, the polymer composite filler prepared according to the present invention is highly dispersed without damaging the appearance of graphene and carbon nanotubes due to low physical shearing force, and thus has excellent physical and electrical properties to be usefully used in manufacturing a polymer composite can

In addition, in the polymer composite according to the present invention, even if the filler is contained in a low content, the fillers maintain their intrinsic physical properties and are highly dispersed, so that mechanical properties and electrical properties can be greatly improved.

1 is a schematic diagram showing a form in which carbon nanotubes and graphene are peeled off during the preparation of a polymer composite filler according to the present invention.
2 is a result of measuring the flexural strength and flexural modulus of the polymer composite filler prepared by using the polymer composite filler according to Examples 4 to 11, Comparative Example 10, Comparative Example 11 and Comparative Example 13;
3 is a result of measuring the tensile strength and tensile modulus of a polymer composite filler prepared by using the polymer composite filler according to Examples 4 to 11, Comparative Example 10, Comparative Example 11, and Comparative Example 13;
4 is a result of measuring the surface electrical resistance of the polymer composite filler prepared by using the polymer composite filler according to Examples 14 to 17 and Comparative Examples 14 to 17.

Hereinafter, preferred embodiments according to the present invention will be described in detail with reference to the accompanying drawings. In addition, the present embodiment does not limit the scope of the present invention, but is presented only as an example, and various changes are possible within the scope without departing from the technical gist of the present invention.

"Polymer composite" applied to the present invention refers to a material prepared by compounding a polymer composite filler including carbon nanotubes and graphene with a polymer.

In the polymer composite filler according to the present invention, the polymer composite filler includes graphene and carbon nanotubes, and the mass ratio of the graphene and carbon nanotubes is in the range of 2:8 to 8:2, and the ratio of the polymer composite filler is in the range of 2:8 to 8:2. It is characterized in that the surface area is in the range from 10 to 500 m ² /g.

At this time, the polymer composite filler according to the present invention preferably includes graphene and carbon nanotubes in a mass range of 2:8 to 8:2, and when the content of graphene is included in less than 20%, the amount of carbon nanotubes is Dispersibility may be deteriorated, and if the content of graphene exceeds 80%, it is necessary to contain an additional filler to improve the electrical and thermal properties of the polymer composite.

In addition, the polymer composite filler according to the present invention not only contains graphene and carbon nanotubes in a certain mass ratio, but also contains a large number of carbon nanotube bundles and individually exfoliated graphene, so that the specific surface area is very high and highly dispersed. It is considered to have excellent physical and electrical properties when manufacturing a polymer composite by retaining it.

The graphene (graphene) refers to a carbon structure of a single-layered two-dimensional nanosheet in the form of sp2 carbon atoms forming a hexagonal honeycomb lattice, and graphene in the polymer composite filler according to the present invention The average particle diameter of the pin may be 0.2 to 20 μm, and the specific surface area of the graphene may be 50 to 600 m ² /g. At this time, when the specific surface area of graphene is contained less than 50 m ² /g, it is not sufficiently located between the separated carbon nanotube bundles or single carbon nanotubes, so it is not very helpful in improving the dispersibility of carbon nanotubes. , and also may cause a problem in that carbon nanotubes are re-agglomerated after the dispersion process.

In addition, in the present invention, the average particle diameter of the carbon nanotubes is 5 to 25 nm, and the specific surface area of the carbon nanotubes is 120 to 600 m ² /g.

In addition, the polymer composite filler according to the present invention can improve the mechanical properties and electrical properties of the polymer composite by high dispersion in a nano-scale in a thermosetting polymer, a thermoplastic polymer, or an elastomer.

As an example, the polymer base material that can be used in the present invention may be used without limitation as long as it is known to be generally used in the art. For example, as the thermoplastic polymer, ethylene-based resin, propylene-based resin, polystyrene-based resin, polycarbonate, styrene-based copolymer such as acrylonitrile-butadiene-styrene, polyvinyl-based resin, polyethylene derephthalate, polyacrylic resin , polyamide-based resins, thermoplastic polyurethane-based resins, and various general-purpose resins, polyphenylene sulfide, polyketone, polyacetal, polyphenylene oxide, ionomer, polybutylene terephthalate, polyimide-based resin, polysulfone-based resin Engineering plastics such as paper and fluororesin and special resins can be used, and thermosetting polymers include phenol resin, epoxy resin, silicone resin, urea resin, melamine resin, urea resin, polyester resin, polyurethane resin, etc. .

In addition, the polymer composite filler having such excellent physical properties is basically required to be processed in a highly dispersed form while minimizing physical damage to the material in the process of manufacturing the filler in order to have a certain level of mechanical properties and excellent electrical properties. .

Therefore, the method for producing a polymer composite filler according to the present invention comprises: a) preparing graphene and carbon nanotubes in a mass ratio of 2:8 to 8:2; and b) adding the graphene and carbon nanotubes to a material peeling device and milling them at a speed in the range of 200 to 500 rpm to obtain a polymer composite filler.

In this regard, in step a), graphene and carbon nanotubes having excellent mechanical and electrical properties are prepared in a mass range of 3:7 to 4:6, and in this case, the effect according to the content ratio of graphene and carbon nanotubes is as described above.

In addition, the average particle diameter of the graphene used in step a) is 0.2 to 20 μm, the specific surface area of the graphene may be 50 to 600 m ² /g, and the average particle diameter of the carbon nanotubes is 5 to 25 nm, and the specific surface area of the carbon nanotubes may be 120 to 600 m ² /g.

The material peeling device used in step b) may use a device that separates the material inside the device by using a shear force generated by eccentric motion and angular motion, in which case the material peeling device The speed is preferably in the range of 200 to 500 rpm.

As shown in FIG. 1 below, the low shear force generated by the low speed in the range of 200 to 500 rpm according to the present invention minimizes physical damage to the graphene or carbon nanotube surface, while the thick carbon nanotube bundle (thick) CNT bundle) into thin CNT bundles, short carbon nanotube bundles or single carbon nanobutes (individual CNT), short single carbon nanotubes (shortened individual CNT), or It is possible to effectively separate agglomerated graphene into a single graphene (individual graphene).

The thin carbon nanotube bundle (thin CNT bundle), the short carbon nanotube bundle (shortened CNT bundle), the single carbon nanobuty (individual CNT), the short carbon nanotube (shortened individual CNT) contained in the polymer composite filler according to the present invention ), single graphene (individual graphene) can be highly dispersed in the polymer composite to effectively improve the physical properties of the polymer composite.

In addition, as an example, the speed of the material peeling device according to the present invention is preferably in the range of 200 to 500 rpm, and more preferably in the range of 350 to 400 rpm. At this time, when the speed of the material peeling device is less than 200 rpm, the thick CNT bundle or agglomerated graphene is not sufficiently separated and the specific surface area is lowered, and the filler prepared at a low speed is a polymer composite It is difficult to disperse in the interior and the target property improvement cannot be reached. In addition, when the speed of the material peeling device exceeds 600 rpm, a significant amount of carbon nanotubes or graphene may be broken or broken, thereby deteriorating the intrinsic physical properties of carbon nanotubes or graphene.

In addition, when the graphene and carbon nanotubes are dispersed in the material peeling device at a speed in the range of 200 to 500 rpm, the operating time of the material peeling device is preferably 5 to 60 minutes, more preferably for 10 to 40 minutes Milling graphene and carbon nanotubes to prepare a polymer composite filler is suitable for improving the dispersibility of carbon nanotubes.

In addition, the polymer that is the target object to be strengthened using the polymer composite filler according to the present invention may be a thermosetting polymer, a thermoplastic polymer or an elastomer, and the polymer composite prepared by mixing the polymer composite filler according to the present invention to the polymer is It has very good physical and electrical properties.

Accordingly, in the case of manufacturing the filler and the polymer composite, the polymer composite filler content according to the present invention may be contained in an amount of 0.05 to 20% by weight of the polymer composite material. Even if it contains such a low content, it is possible to obtain a polymer composite material with significantly improved mechanical properties and electrical properties because the fillers are highly dispersed while maintaining the intrinsic properties of the filler.

In addition, the method for manufacturing a polymer composite material according to the present invention is as follows.

First, a polymer material and the filler are supplied to a twin-screw extruder to prepare a polymer/filler masterbatch (a kind of pellet) through melt extrusion.

The extrusion molding is a single process in which unit operations such as mixing, grinding, heating, molding and drying occur in a short time. The material introduced through the barrel moves into the barrel and is dispersed, distributed, mixed and sheared by a screw, and the temperature and pressure inside the barrel can be controlled, and the material moved by the screw is finally transferred to a die. ) means to be discharged to the outside through the process, but is not limited thereto.

Injection molding, compression molding, transfer molding, blow molding) and calendering method of polymer/filler masterbatch and polymer resin manufactured through melt blending by twin screw extruder (calender molding) is additionally performed to mold a product of a desired shape.

Therefore, in the polymer composite containing the polymer composite filler according to the present invention, the filler can be uniformly dispersed as described above, and the problem of poor contact between the fillers can be solved, and thus the overall physical properties, especially the electrical conductivity properties, are excellent. can be

Hereinafter, the present invention will be described in more detail through examples. These examples are only for illustrating the present invention, and it will be apparent to those of ordinary skill in the art that the scope of the present invention is not to be construed as being limited by these examples.

Examples 1-3 and Comparative Examples 1-3: TPU (Thermoplastic polyurethane)

Examples 1-3

MBT3146 (specific surface area: 250-270 m2/g), MBT3137 (specific surface area: 220-250 m2/g) prepared through a kneading exfoliation process at 390 rpm for 20 minutes at a mixing ratio of graphene and carbon nanotubes of 4:6 or 3:7 g) was extruded to manufacture thermoplastic polyurethane (98A TPU: Dong-A Chemicals ACE Thane EP-98A) pellets having a Shoei hardness of 95, with 4 wt.% and 7 wt.% content, and injection molding of the filler Specimens having a content of 4 wt.%, 7 wt.%, were prepared.

Comparative Examples 1 to 3

MBT3146 (specific surface area: 330-360m2/g), MBT3137 (specific surface area: 290-310 m2/g) was extruded to form 95A TPU having a content of 4 wt.% and 7 wt.%, and a specimen having a filler content of 4 wt.% and 7 wt.% was prepared through injection molding.

Examples 4 to 11 and Comparative Examples 4 to 7: PP

Examples 4-7

Polyethylene with a content of 10 wt.% through extrusion molding using MBT2137 (specific surface area: 200-220 m2/g) prepared through a kneading exfoliation process at 390 rpm for 20 minutes at a mixing ratio of graphene and carbon nanotubes of 3:7 A masterbatch was prepared. 10wt.% polypropylene masterbatch is mixed with base polypropylene 5%, 10%, 50%, 100%, and the filler content is 0.5wt.%, 1wt.%, 5wt.%, 10wt.% through injection molding. Table 1 below shows the results of manufacturing injection specimens and measuring electrical conductivity and mechanical properties.

Examples 8-11

Using MBT2146 (specific surface area: 200-220 m2/g) prepared through a kneading exfoliation process at 390 rpm for 20 minutes at a mixing ratio of graphene and carbon nanotubes of 4:6 A polyethylene masterbatch having a content of 10 wt.% was prepared through extrusion molding. 10wt.% polypropylene mastbatch is mixed with base polypropylene 5%, 10%, 50%, 100%, and the filler content is 0.5wt.%, 1wt.%, 5wt.%, 10wt.% through injection molding. Table 1 below shows the results of manufacturing injection specimens and measuring electrical conductivity and mechanical properties.

Comparative Examples 4 to 5

Polyethylene with a content of 10 wt.% through extrusion molding using MBT2137 (specific surface area: 290-320 m2/g) prepared through a kneading exfoliation process at 850 rpm for 20 minutes at a mixing ratio of graphene and carbon nanotubes of 3:7 A masterbatch was prepared. A 10 wt.% polypropylene mastbatch is mixed with a base polypropylene 50% and 100% to prepare an injection specimen having a filler content of 5 wt.% and 10 wt.% through injection molding, and the results of electrical conductivity and mechanical properties are measured below. Table 1 shows.

Comparative Examples 6 to 7

Polyethylene master having a content of 10 wt.% through extrusion molding using MBT2146 (specific surface area: 290-320 m2g) prepared through a kneading exfoliation process at 850 rpm for 20 minutes at a mixing ratio of graphene and carbon nanotubes of 4:6 A batch was prepared. By mixing 10 wt.% polypropylene masterbatch with base polypropylene 50% and 100%, injection molding with filler content of 5 wt.% and 10 wt.% was prepared, and electrical conductivity and mechanical properties were measured. Table 1 shows.

comparative example 8 to 9: Graphene

A polypropylene masterbatch having a content of 10 wt.% was prepared by extrusion molding graphene having a specific surface area of 300 to 450 m2/g and a particle size of 0.5 to 3 um using a twin-screw extruder. A 10wt.% polypropylene mastbatch was mixed with a base polypropylene 50wt.%, 100%, and an injection specimen having a filler content of 5wt.%, 10wt.% was prepared through injection molding, and the results of electrical conductivity and mechanical properties were measured. It is shown in Table 1 below.

comparative example 10 ~ 13: CNT

A polypropylene masterbatch having a content of 10 wt.% was prepared through extrusion molding of multi-wall carbon nanotubes having a particle diameter of 6-12 nm, a length of 100-200 μm, and a specific surface area of 250-350 m2/g. 10wt.% polypropylene mastbatch is mixed with base polypropylene 1%, 10%, 50%, 100%, and the filler content is 0.1wt.%, 1wt.%, 5wt.%, 10wt.% through injection molding. The results of manufacturing injection specimens and measuring electrical conductivity and mechanical properties are shown in Table 1 and FIGS. 2 and 3 below.

polymer Filler loading matter Kneading Peeling Speed
(rpm) Surface electrical resistance (ohm/sq) Example 1 95A TPU 4% MBT3146 390 10 ⁴ Example 2 95A TPU 4% MBT3137 390 10 ³ to 10 ⁴ Example 3 95A TPU 7% MBT3137 390 10 ² to 10 ³ Example 4 pp 0.5% MBT2137 390 > 10 ¹² Example 5 pp One% MBT2137 390 > 10 ¹² Example 6 pp 5% MBT2137 390 10 ⁶ to 10 ⁷ O/sq Example 7 pp 10% MBT2137 390 10 ² to 10 ³ O/sq Example 8 pp 0.5% MBT2146 390 > 10 ¹² Example 9 pp One% MBT2146 390 > 10 ¹² Example 10 pp 5% MBT2146 390 10 ⁵ ~ 10 ⁶ Example 11 pp 10% MBT2146 390 10 ² to 10 ³ Comparative Example 1 95A TPU 4% MBT3146 850 > 10 ¹² Comparative Example 2 95A TPU 4% MBT3137 850 > 10 ¹² Comparative Example 3 95A TPU 7% MBT3137 850 10 ¹¹ ~ 10 ¹² Comparative Example 4 pp 5% MBT2137 850 > 10 ¹² Comparative Example 5 pp 10% MBT2137 850 10 ¹⁰ ~ 10 ¹¹ Comparative Example 6 pp 5% MBT2146 850 > 10 ¹² Comparative Example 7 pp 10% MBT2146 850 10 ¹⁰ ~ 10 ¹¹ Comparative Example 8 pp 5% Graphene > 10 ¹² O/sq Comparative Example 9 pp 10% Graphene 10 ¹⁰ ~ 10 ¹¹ /sq Comparative Example 12 pp 5% CNT 10 ⁶ to 10 ⁷ Comparative Example 13 pp 10% CNT 10 ² to 10 ³

As shown in Table 1, the polymer composite filler prepared according to the present invention was highly dispersed without significantly damaging the appearance of graphene and carbon nanotubes due to low physical shearing force, and thus, as shown in Examples 1 to 3, When the composite filler of the present invention was formed into a composite with a thermoplastic polyurethane, compared to Comparative Examples 1 to 3 using a filler prepared at a high rate, much lower electrical resistance was exhibited at the same filler content, and in Examples 4 to 11, When the composite filler of the present invention forms a polypropylene composite, Comparative Examples 4 to 7 using a filler prepared at a high speed and a graphene-only filler having a particle size of 0.2 to 4um and a specific surface area of 50 to 600 m2/g are used. It showed a lower surface electrical resistance than Examples 8 and 9. In addition, Examples 4 to 11 have a similar or lower surface to Comparative Examples 12 and 13 using a carbon nanotube sole filler having a purity of 98%, a length of 100 to 200 μm, a particle size of 6 to 9 nm, and a specific surface area of 400-600 m2/g. Shows electrical resistance.

Example 14 to 17

390rpm with the graphene and carbon nanotube mixing ratio 3:7 Acrylonitrile-butadiene-styrene (ABS) masterbatch with a content of 10 wt.% through extrusion molding using MBT3237 (specific surface area: 270-300 m2/g) prepared through kneading and peeling process for 20 minutes in prepared. A 10wt.% ABS mastbatch is mixed with polycarbonate (PC) with 30, 45%, 65%, and 90%, and the filler content is 3wt.%, 4.5wt.%, 6.5wt.%, 9wt.% through injection molding. The results of measuring the surface resistance by preparing the injection specimen are shown in Table 2 and Figure 4 below.

Comparative Examples 14 to 17

An ABS masterbatch having a content of 10 wt.% was prepared by extrusion molding EC300J (carbon black) of Ketjen of Japan. A 10wt.% ABS mastbatch is mixed with polycarbonate (PC) with 30, 45%, 65%, and 90%, and the filler content is 3wt.%, 4.5wt.%, 6.5wt.%, 9wt.% through injection molding. Table 2 and Figure 4 show the results of surface electrical resistance measurement by preparing PC/ABS injection specimens.

base polymer master
batch polymer Filler loading matter Kneading Peeling Speed
(rpm) Example 14 PC ABS 3% MBT3237 390 Example 15 PC ABS 4.5% MBT3237 390 Example 16 PC ABS 6.5% MBT3237 390 Example 17 PC ABS 9% MBT3237 390 Comparative Example 14 PC ABS 3% EC300J Comparative Example 15 PC ABS 4.5% EC300J Comparative Example 16 PC ABS 6.5% EC300J Comparative Example 17 PC ABS 9% EC300J

As shown in Figure 4 below, Examples 14 to 17 corresponding to the polymer composite filler prepared according to the present invention exhibited lower electrical resistance than Comparative Examples 14 and 17 using carbon black as a composite filler. Confirmed.

Experimental Example 1: Tensile test and flexural test

Using a mechanical universal testing machine (Salt, ST-1002-50kN, universal testing machine, UTM), the tensile properties were measured with a dog-bone type ASTM D638 injection specimen at a cross head speed of 5 mm/min.

The bending test is shown in FIG. 2 by measuring an injection specimen conforming to ASTM D790 standard with a three-point bending test method at a cross head speed of 2 mm/min.

As shown in Figures 2 and 3 below, the polymer composites (Examples 4 to 11) prepared according to the present invention are polymer composites (Comparative Example 10, Comparative Example 11, and Comparative Example 10) including only carbon nanobute as a filler. Compared to Example 13), it was confirmed that the flexural strength, elastic modulus, tensile strength, and tensile modulus of elasticity were significantly improved.

Although the present invention has been shown and described with reference to specific embodiments, it will be appreciated by those skilled in the art that various modifications and changes can be made without departing from the spirit and scope of the invention as set forth in the appended claims. If so, anyone can easily figure it out.

Claims (10)

In the polymer composite filler,
The polymer composite filler includes graphene and carbon nanotubes,
The mass ratio of the graphene and carbon nanotubes is in the range of 8:2 to 2:8,
Polymer composite filler, characterized in that the specific surface area of the polymer composite filler is in the range of 10 ~ 500 m2 / g.
According to claim 1,
The average particle diameter of the graphene is 0.2 to 20 μm, and the specific surface area of the graphene is 50 to 600 m ² /g Polymer composite filler.
According to claim 1,
The average particle diameter of the carbon nanotubes is 5 to 25 nm, and the specific surface area of the carbon nanotubes is 120 to 600 m ² /g Polymer composite filler, characterized in that.
The method of claim 1,
The polymer is a polymer composite filler, characterized in that the thermosetting, thermoplastic or elastomer.
In the method for producing a polymer composite filler,
a) preparing graphene and carbon nanotubes in a mass ratio range of 2:8 to 8:2; and
b) adding the graphene and carbon nanotubes to a material peeling device and milling at a speed in the range of 200 to 500 rpm to obtain a polymer composite filler; Method for producing a polymer composite filler comprising a.
6. The method of claim 5,
The speed of the material peeling device is a method of manufacturing a polymer composite filler, characterized in that in the range of 350 to 400rpm.
6. The method of claim 5,
The carbon nanotube has an average particle diameter of 5 to 25 nm, and the specific surface area of the carbon nanotube is 150 to 600 m ² /g.
6. The method of claim 5,
The average particle diameter of the graphene is 0.2 to 20 μm, and the specific surface area of the graphene is 50 to 600 m ² /g.
6. The method of claim 5,
The polymer is a method for producing a polymer composite filler, characterized in that the thermosetting, thermoplastic or elastomer.
A polymer composite filler prepared by any one of the manufacturing methods according to any one of claims 5 to 9.

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