KR20130049444A - Preparing method for polymer composite coated carbon nano material - Google Patents

Preparing method for polymer composite coated carbon nano material Download PDF

Info

Publication number
KR20130049444A
KR20130049444A KR1020110114473A KR20110114473A KR20130049444A KR 20130049444 A KR20130049444 A KR 20130049444A KR 1020110114473 A KR1020110114473 A KR 1020110114473A KR 20110114473 A KR20110114473 A KR 20110114473A KR 20130049444 A KR20130049444 A KR 20130049444A
Authority
KR
South Korea
Prior art keywords
polymer
carbon
coating
carbon nanomaterial
dispersion solution
Prior art date
Application number
KR1020110114473A
Other languages
Korean (ko)
Inventor
최병삼
송경화
이한샘
곽진우
Original Assignee
현대자동차주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 현대자동차주식회사 filed Critical 현대자동차주식회사
Priority to KR1020110114473A priority Critical patent/KR20130049444A/en
Publication of KR20130049444A publication Critical patent/KR20130049444A/en

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/70—Nanostructure
    • Y10S977/734—Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
    • Y10S977/742—Carbon nanotubes, CNTs

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Preparation of a carbon nanomaterial coating polymer comprising administering a carbon nanomaterial to a dispersion solution added with a dispersant, dispersing by ultrasonication, and adding the polymer to the dispersion solution to coat the carbon nanomaterial on a polymer surface. It is about a method.
When manufacturing through the present invention, it is possible to suppress the agglomeration phenomenon due to the interworking force between the nanomaterials and to improve the dispersibility of various materials when manufacturing the functional composite material using the nanomaterials. In addition, the mechanical strength and durability of the interior and exterior materials of the vehicle can be improved by inducing uniform dispersion in the polymer.

Description

Preparation Method for Polymer Composite Coated Carbon Nano Material

The present invention relates to a method for producing a polymer composite to improve the mechanical properties using carbon nanomaterials.

Polypropylene, the most commonly used polymer for automobiles, is used as a material for vehicle bumpers and interior and exterior products due to its high thermal durability and strength.However, due to the future technology and light weight of automobiles, the single polymer currently used cannot satisfy the demand. . Therefore, in order to improve mechanical strength and electrical properties, which are weak points of polymers, efforts to manufacture composites by mixing with nanomaterials are being conducted in many material companies, academia, and research institutes. However, there is a limit to existing melt mixing methods to improve the dispersibility of nanomaterials, which is one of the most important matters in heterogeneous mixing of nanomaterials and polymers. In order to produce composites using carbon nanomaterials and polymers, simple mixed melt dispersion is adopted to perform extrusion and injection molding processes, which do not loosen the carbon nanomaterials and thus reduce the dispersibility of carbon nanomaterials. In particular, in the case of carbon nanomaterials, agglomeration of nanomaterials is intensified due to Vander waals interaction. Therefore, despite the carbon nanomaterial content of more than 20 wt% in the composite prepared by melt dispersion had a problem that the mechanical durability is lowered.

In the present invention, in order to overcome the problem of poor mechanical dispersion due to poor melt dispersion, the surface of the polymer, for example, the surface of the polypropylene is coated with a carbon nanomaterial of 0.001 ~ 0.1 wt% or less by agglomeration due to the interworking force between the nanomaterials It is an object of the present invention to develop a manufacturing method of suppressing the phenomenon and inducing uniform dispersion in a polymer to improve mechanical strength and durability of interior and exterior materials of a vehicle.

The present invention comprises the steps of: (i) administering a carbon nanomaterial to a dispersion solution to which a dispersant is added, dispersing by ultrasonic treatment; And

(ii) adding a polymer to the dispersion solution to coat the carbon nanomaterial on the polymer surface;

It provides a method for producing a carbon nanomaterial coating polymer comprising a.

Through the above-mentioned means for solving the problems, the present invention provides the following effects.

(i) Through the manufacturing method of the present invention it is possible to suppress the agglomeration phenomenon due to the mutual attraction between nanomaterials. Therefore, it is possible to contribute to the improvement of the dispersibility of various materials when manufacturing a functional composite material using nano materials.

(ii) It is possible to improve the mechanical strength and durability of the interior and exterior materials of the vehicle by inducing uniform dispersion in the polymer through the manufacturing method of the present invention.

1 is a schematic diagram showing a structure in which carbon nanoparticles are coated on polypropylene through a manufacturing method of the present invention, and the rightmost figure is a cross-sectional view thereof.
Figure 2 shows the process before and after the preparation of the dispersion solution of carbon nanomaterial, the left side is the pre-preparation solution, the right is the post-preparation solution photograph.
Figure 3 is a photograph before and after the carbon nanomaterial is coated on the polymer surface, the left side is before the coating, the right side is the polymer after coating.
Figure 4 is a SEM photograph of the carbon nano material of the surface of the polymer of the present invention.
5 is a SEM photograph of a composite cross section after injection of the coated polymer surface of the present invention.

According to one aspect of the invention, the present invention comprises the steps of (i) administering a carbon nanomaterial to a dispersion solution to which a dispersant is added, dispersing by ultrasonic treatment; And

(ii) adding a polymer to the dispersion solution to coat the carbon nanomaterial on the polymer surface;

It provides a method for producing a carbon nanomaterial coating polymer comprising a.

According to a preferred embodiment of the present invention, the carbon nanomaterial added to the dispersion solution has a content of 0.001-20 wt%. More preferably, it is 0.001-10 wt%.

According to a preferred embodiment of the present invention, the carbon nanomaterial is one or a mixture of two or more selected from the group consisting of single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, carbon fibers, graphite and graphene to be.

According to a preferred embodiment of the present invention, the polymer of (ii) is one or a mixture of two or more selected from the group consisting of polyester, polyethylene, polypropylene, polystyrene, polycarbonate and polyamide. More preferably, the polymer uses polypropylene.

According to a preferred embodiment of the present invention, the coating step (ii) is a wet coating.

According to a preferred embodiment of the present invention, the wet coating is a spray, dip, self-assembly, bar or flow coating. More preferably, the coating treatment is carried out using a spray wet coating method.

According to a preferred embodiment of the present invention, the solvent of (i) is characterized in that the organic solvent or purified water. More specifically, the organic solvent is methanol, ethanol, 2-propanol, butanol, butanol, dimethylformamide (N, N-Dimethylformamide), and the like.

According to a preferred embodiment of the present invention, the dispersant is characterized in that the sodium dodecyl sulfate (SDS), sodium dodecylbenzenesulfonate (SDBS) or Cetrimonium bromide (CTAB).

According to another aspect of the present invention, the present invention provides a polymer composite coated with a carbon nanomaterial prepared by the manufacturing method.

Hereinafter, the present invention will be described in detail through specific examples, and the scope of the present invention is not limited to these examples.

Example

Step 1: Carbon nano materials  Dispersion Solution Preparation

300 mg of unrefined multi-walled carbon nanotubes (NC7000) as a filler to improve the mechanical and electrical properties of polymer composites , SDBS, CTAB) 300 mg and 500 mL of deionized secondary purified water were placed in an easy-to-sonic toll beaker and then ultrasonically probed at 60 kHz and 700 W for 10 minutes using a probe-type ultrasonic generator. Dispersed. A cooling jacket was used to suppress the temperature rise of the solution during sonication.

After preparing the carbon nanotube dispersion solution, 5 g of water-dispersed polyurethane (PUD) was added to improve adhesion to polypropylene as a coating material, and 30 mL of methanol was added to promote rapid volatilization after coating. Figure 2 compares the color before and after the preparation of the carbon nanotube dispersion solution, the carbon nanotube dispersion solution is dark black.

Step 2: Carbon Nanotube Coating

3 kg of polypropylene pellet (EP200R), which was dried at 80 ° C. in a drying oven for 24 hours, was placed in a constant temperature chamber at 70 ° C., and an aqueous carbon nanotube solution was put in an experimental spray gun, and then 100 μm coated on the surface of polypropylene. For coating evenly on the surface of the polypropylene, the container containing the polypropylene pellets was shaken during coating.

In order to remove the moisture of the coated polypropylene pellets it was dried for 24 hours at 80 ℃ drying oven. The carbon nanotubes of the coated polypropylene surface were observed using FE-SEM (JEOL) (FIG. 3). The white polymer is immersed in an aqueous carbon nanotube solution and coated with a black carbon solution. When the carbon nanotubes deposited on the surface of the polymer are confirmed by SEM, nanorods are attached to the surface (FIG. 4).

Step 3: polypropylene injection coated with carbon nanotubes;

Carbon nanotube coated polypropylene was injected using a 150 ton injection machine, and the cross section of the injection specimen was observed. Judging by the SEM photograph of FIG. 5, it was confirmed that the carbon nanotubes were evenly dispersed in the polypropylene.

Comparative example  1 and 2:

Polypropylene and carbon nanotubes in a weight ratio of 95: 5 (Comparative Example 1) and 80: 20 (Comparative Example 2) were evaluated by cross-section of the injection specimen obtained by extrusion and injection. The phenomenon occurred. Even when the carbon nanotubes were mixed at 20 wt%, the agglomeration occurred in the injection specimen.

Experimental Results: Dispersibility Measurement

The results of measuring the dispersibility of the polypropylene polymer prepared in Example 1 and the dispersibility experiment of the polypropylene polymer prepared by the method of Comparative Examples 1 and 2 are shown in Table 1 below.

Experimental results The polypropylene polymer prepared by the coating method by the method according to Example 1 was excellent in dispersibility, but the composite produced through the manufacturing method of Comparative Examples 1 and 2 did not appear dispersibility, aggregation phenomenon, etc. This happened.

division Poly
Propylene
Content (wt%) CNT
content
( wt %) CNT
Dispersion Method Dispersibility Example 1 95 5 coating O Comparative Example 1 95 5 mix X Comparative Example 2 80 20 mix X

Claims (9)

(i) administering the carbon nanomaterial to a dispersion solution to which a dispersant is added and dispersing by ultrasonic treatment; And
(ii) adding a polymer to the dispersion solution to coat the carbon nanomaterial on the polymer surface;
Method for producing a carbon nano material coating polymer comprising a.
The method of claim 1, wherein the carbon nanomaterial added to the dispersion solution is characterized in that the content of 0.001-20 wt%.
The method of claim 1, wherein the carbon nano material is a single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, carbon fibers, graphite and graphene, characterized in that one or two or more selected from the group consisting of How to.
The method of claim 1, wherein the polymer of (ii) is one, or a mixture of two or more selected from the group consisting of polyester, polyethylene, polypropylene, polystyrene, polycarbonate and polyamide.
The method of claim 1, wherein the coating of (ii) is a wet coating.
The method of claim 5, wherein the wet coating is a spray, dip, self-assembly, mayor bar or flow coating.

The method of claim 1, wherein the solvent of (i) is an organic solvent or purified water.
The method of claim 1 wherein the dispersing agent is SDS, SDBS or CTAB.
A polymer composite coated with a carbon nanomaterial prepared by the method of any one of claims 1 to 8.
KR1020110114473A 2011-11-04 2011-11-04 Preparing method for polymer composite coated carbon nano material KR20130049444A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020110114473A KR20130049444A (en) 2011-11-04 2011-11-04 Preparing method for polymer composite coated carbon nano material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020110114473A KR20130049444A (en) 2011-11-04 2011-11-04 Preparing method for polymer composite coated carbon nano material

Publications (1)

Publication Number Publication Date
KR20130049444A true KR20130049444A (en) 2013-05-14

Family

ID=48660191

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020110114473A KR20130049444A (en) 2011-11-04 2011-11-04 Preparing method for polymer composite coated carbon nano material

Country Status (1)

Country Link
KR (1) KR20130049444A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104262953A (en) * 2014-08-21 2015-01-07 巨石集团有限公司 Graphene-coated glass fiber reinforced resin-based composite material and preparation method thereof
WO2015030498A1 (en) * 2013-09-02 2015-03-05 (주) 엘지화학 Thermoplastic polymer to which carbon nanomaterial is bound and method for preparing same
KR20150026157A (en) * 2013-09-02 2015-03-11 주식회사 엘지화학 Treatment method of carbon-nanomaterial and carbon-nanomaterial obtained from the method
WO2020111849A1 (en) * 2018-11-30 2020-06-04 롯데케미칼 주식회사 Method for manufacturing semi-conductive polypropylene resin foamed particles and foamed molded article

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015030498A1 (en) * 2013-09-02 2015-03-05 (주) 엘지화학 Thermoplastic polymer to which carbon nanomaterial is bound and method for preparing same
KR20150026157A (en) * 2013-09-02 2015-03-11 주식회사 엘지화학 Treatment method of carbon-nanomaterial and carbon-nanomaterial obtained from the method
CN104603191A (en) * 2013-09-02 2015-05-06 Lg化学株式会社 Thermoplastic polymer to which carbon nanomaterial is bound and method for preparing same
US10266675B2 (en) 2013-09-02 2019-04-23 Lg Chem, Ltd. Thermoplastic polymer combined with carbon nanomaterial and method of preparing the same
CN104603191B (en) * 2013-09-02 2020-05-08 Lg化学株式会社 Thermoplastic polymer combined with carbon nano material and preparation method thereof
US10676595B2 (en) 2013-09-02 2020-06-09 Lg Chem, Ltd. Methods for combining thermoplastic polymer with carbon nanomaterial
CN104262953A (en) * 2014-08-21 2015-01-07 巨石集团有限公司 Graphene-coated glass fiber reinforced resin-based composite material and preparation method thereof
WO2020111849A1 (en) * 2018-11-30 2020-06-04 롯데케미칼 주식회사 Method for manufacturing semi-conductive polypropylene resin foamed particles and foamed molded article
KR20200065559A (en) * 2018-11-30 2020-06-09 롯데케미칼 주식회사 Method for preparing semi-conductive polypropylene resin expanded beads and molded body thereof

Similar Documents

Publication Publication Date Title
CN106957454B (en) A kind of nano material coated fire retardant and preparation method thereof
Breuer et al. Big returns from small fibers: a review of polymer/carbon nanotube composites
Qiu et al. Exchangeable interfacial crosslinks towards mechanically robust elastomer/carbon nanotubes vitrimers
KR101135672B1 (en) Conductive thermosets by extrusion
Lee et al. Highly improved interfacial affinity in carbon fiber-reinforced polymer composites via oxygen and nitrogen plasma-assisted mechanochemistry
Choudhary et al. Polymer/carbon nanotube nanocomposites
Sahoo et al. Improvement of mechanical and thermal properties of carbon nanotube composites through nanotube functionalization and processing methods
US10000653B2 (en) Printing ink dispersions comprising discrete carbon nanotubes
KR101090729B1 (en) Highly conductive resin composition having carbon composite
EP1956062A1 (en) Conductive coating material
US7976731B2 (en) Metal complexes for enhanced dispersion of nanomaterials, compositions and methods therefor
CN107513162A (en) A kind of preparation method of graphene/nylon 6 nano-composite
JP2008540818A (en) Thermoplastic long fiber composite, method for producing the same, and product obtained therefrom
KR101627016B1 (en) Highly dispersible carbon nano structures and method for preparation thereof, and polymer composite comprising the carbon nano structures
Dai et al. Mechanical properties of carbon nanotubes-polymer composites
Beyou et al. Polymer nanocomposites containing functionalised multiwalled carbon nanoTubes: a particular attention to polyolefin based materials
Akram et al. Review on polymer/carbon nanotube composite focusing polystyrene microsphere and polystyrene microsphere/modified CNT composite: preparation, properties, and significance
WO2007050408A2 (en) Metal complexes for enhanced dispersion of nanomaterials, compositions and methods therefor
KR20130049444A (en) Preparing method for polymer composite coated carbon nano material
Poochai et al. Enhancing dispersion of carbon nanotube in polyacrylonitrile matrix using admicellar polymerization
KR20130134446A (en) Functionalized graphene and polymer-functionalized graphene hybrid complex and the fabrication methods thereof
KR101984207B1 (en) Polyketone-carbon based filler composites and preparation methods thereof
Espinosa-González et al. Polystyrene composites with very high carbon nanotubes loadings by in situ grafting polymerization
Panda et al. Unsaturated polyester nanocomposites
Pantano Carbon nanotube based composites: processing, properties, modelling and application

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
E601 Decision to refuse application