KR20130036114A - A method for preparing carbon nano tube reinforced polypropylene - Google Patents
A method for preparing carbon nano tube reinforced polypropylene Download PDFInfo
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- KR20130036114A KR20130036114A KR1020130030445A KR20130030445A KR20130036114A KR 20130036114 A KR20130036114 A KR 20130036114A KR 1020130030445 A KR1020130030445 A KR 1020130030445A KR 20130030445 A KR20130030445 A KR 20130030445A KR 20130036114 A KR20130036114 A KR 20130036114A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
- C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/26—Mechanical properties
Abstract
Description
The present invention relates to a method for producing a nanocomposite material in which carbon nanomaterials are dispersed in a polypropylene material which is a thermoplastic.
Background Art In recent years, olefin resins such as polyethylene, polypropylene, and polybutene have one of the most widespread uses in fields such as automobiles and home appliances because they have excellent basic physical properties such as light weight and high rigidity. Olefin-based resins are used as an aspect in which various additives are added depending on the required physical properties of the olefin-based resin. Since the additive is usually a powder, in particular, the dispersibility in blending with the olefin resin is insufficient, and it is not easy to meet the required properties.
Carbon nanomaterial reinforced polymer composites have the advantage of having excellent stiffness, strength and electrical conductivity even at relatively low carbon nanomaterial content. Carbon nanopolymer composites having excellent mechanical properties and electrical conductivity can be applied not only for aerospace materials but also for electromagnetic shielding materials.
Recently, carbon nano materials such as carbon nano tubes (CNT) and carbon nano fibers (CNF) to satisfy the simultaneous demanded properties of weight reduction and mechanical properties reinforcement There is an increasing interest in measuring the dispersion of carbon nanomaterials in the polymer composite material reinforced by using.
WO 2011/096596 provides a general purpose dispersant for additives for olefinic resins, the construction of which comprises:
It is a dispersing agent of the polyolefin additive containing the alkyl methacrylate (a1) unit which has a C2 or more alkyl group as a main component, and contains the alkyl methacrylate type polymer of 15,000-145,000 mass mean molecular weights.
KR10-2013-0002140 is a lightweight polypropylene resin composition for automobile interiors, and provides a thermoplastic resin composition reinforced with fibrous magnesium oxides and a molded article for automobile interiors using the same.
KR10-2012-0134382 is a method for producing a carbon nanotube / polyolefin composite material having excellent mechanical properties and physical properties.
(1) a purification step of removing impurities contained in carbon nanotubes;
(2) chemical surface treatment of the carbon nanotubes; And
(3) melt-mixing the chemical surface-treated carbon nanotubes with a polyolefin resin.
Recently, the research flow in the field of materials has a lot of interest in the development of reinforcement materials using thermoplastics, and in particular, thermoplastic composites using reinforcements such as carbon nanotubes (CNT), which are known as reinforcement materials, and especially five general purpose materials such as polypropylene. Although a great deal of research is being conducted on plastics, a special dispersing method is necessary because the melting of thermoplastics is easy but the nanoparticles are difficult to disperse in the polymer matrix due to a very high viscosity. In other words, in order to manufacture thermoplastic nanocomposites, high dispersion of nanoparticles is required. However, in the prior art, nanoparticles are dispersed in a small unit of μm and nm to check the surface and internal fracture state of the material. Evaluate the dispersion of the particles. However, these conditions mean only a very small range of results, and due to the simple result selection of photographs, there are difficulties in verifying nanoparticle dispersion to determine the dispersion state of nanoparticles. Therefore, carbon nanotube dispersed polypropylene according to the above technique is difficult to use as a polypropylene material having a degree of commercially available strength.
Accordingly, an object of the present invention is to pursue the nanocompositing of PP using CNTs in accordance with the development trend of the automobile industry, simplify the manufacturing process and meet the result of the increase of mechanical properties due to the addition of a small amount of expensive CNTs. To provide a CNT polypropylene resin composition in consideration of weight reduction of the product.
SUMMARY OF THE INVENTION
a) preparing a PP powder / Xylene mixture by selecting a polypropylene having a diameter of 500 μm to 1000 μm at a weight ratio of 0.5 wt% to 10 wt% of the nanoparticles leading to xylene,
b) stirring the mixture at 100-150 ° C. and 1-3 hours,
c) preparing a CNT / Xylene dispersion solution by mixing carbon nanotubes (CNT) and xylene in a weight ratio within 0.5 wt% to 10 wt%;
d) injecting the CNT / Xylene dispersion solution prepared by performing step c) to the swelling PP powder / Xylene mixture obtained by performing step b),
e) dispersing the ultrasonic wave under ultrasonic dispersing condition (Cycle time 0.5 s,
d) after the ultrasonic dispersion, removing the solvent present in the powder in a vacuum oven for 2 to 3 hours, 130 ~ 150 ℃ conditions, solvent degassing step and additionally in the vacuum oven for 20 to 24 hours at 100 ~ 150 ℃ conditions It provides a method for producing a CNT / PP composite material comprising the step of preparing a final CNT / PP powder by drying.
After the step d), the present invention may further comprise a molding step of e) molding the final CNT / PP powder with an injection machine.
The polymer composite material produced by the composite material manufacturing method of carbon nanopolypropylene (PP) of the present invention has the advantage that the carbon nano material impregnated therein maintains a high dispersion state, thereby producing a quantitative CNT / PP material. There is this.
In addition, since the carbon nano polypropylene (PP) composite material manufacturing method of the present invention is manufactured in the form of CNT / PP powder, it is possible to efficiently manufacture pellets using an extruder, an extruder, etc. As a result of confirming the dispersion degree state, it shows the excellent dispersion degree, and also has an advantage in the commercialization of a material.
Figure 1 shows the type of CNT / PP powder and FE-SEM results.
2 is a diagram evaluating dispersion by measuring volume resistance according to electrical resistance measurement.
3 is a thermal stability evaluation results using TGA.
The present invention relates to a method for producing a polypropylene nanocomposite material using carbon nanotubes and a molded article using the same. Conventionally, in order to contain nanoparticles in thermoplastics, a method of preparing a specimen through a simple mixing process in an injection molding machine or mixing of nanoparticles through a mechanical dispersion process such as a three-roll mill was performed.
However, the present invention improves the method of dispersing carbon nanotubes using ultrasonic dispersion by using a phenomenon in which polypropylene is swelled by calculating solubility as a method for mixing minimal nanoparticles into polypropylene. CNTs of the CNT / Xylene nanoparticle dispersion solution are dispersed on the surface of the swelled polypropylene particle, and carbon nanotubes are impregnated on the PP surface during the dispersion process to prepare CNT / PP powder. Using the powder thus prepared, it is possible to prepare an injection material that is easy to mold the CNT polypropylene nanocomposite material using a molding equipment such as an injection machine, an extruder, or a hot press. Ultimately, the application of CNT polypropylene nano composites to be used as exterior materials for vehicles increases mechanical properties as well as various applications of automotive materials by securing conductivity and reducing weight.
It is an object of the present invention to provide a method aimed at producing nanocomposites that maintain a high dispersion of carbon nanomaterials in polypropylene materials, which are representative thermoplastics.
In addition, the purpose of the present invention is to overcome the disadvantage that the polypropylene is a material having a very high chemical resistance, so that the melting using the solvent method is difficult, CNT dispersed using the swelling effect generated on the material surface using xylene The solution provides a method for producing polypropylene particles impregnated with CNT particles on the swelling polypropylene surface.
More specifically, the present invention,
a) mixing a polypropylene having a diameter of 500㎛ ~ 1000㎛ by selecting the weight ratio of the nanoparticles leading to xylene (0.5 wt% ~ 10wt%). The small size of the PP particles increases the surface area that can react with the solvent xylene. For this reason, it is effective to make the size of the PP particles small so that the swelling effect on the PP surface is large. In addition, the weight ratio is from 0.5 wt% to 10 wt%, and in this range, it is possible to produce CNT / PP composites with easy dispersion of particles.
b) The step of stirring the mixture for 100 ~ 150 ℃ and 1-3 hours is a step to obtain a swelling PP powder / Xylene mixture.
c) In the step of preparing a CNT / Xylene dispersion solution by mixing carbon nanotubes (CNT) and xylene in a weight ratio within 0.5 wt% ~ 10wt%, there is an effect on the dispersion according to the CNT content. Aggregation may occur due to van der Waals attraction between the CNT particles, and the optimum dispersion state may be changed by using a dispersion solvent to disperse the particles. Experiments were conducted to determine the minimum and maximum amounts of CNT particles in dispersion. Based on this, the internal dispersion of CNT / PP composites was 0.5% by weight based on the electrical resistance evaluation method. Could have results within 10%. In addition, in the dispersed state of 10 wt% or more, the coagulation phenomenon between the CNT particles and the CNT particles is generated, so that it is confirmed that the maximum weight ratio is used up to 10 wt% to ensure uniform dispersion state of the CNT particles.
d) injecting the CNT / Xylene dispersion solution prepared by performing step c) to the swelling PP powder / Xylene mixture obtained by performing step b), and e) ultrasonic dispersion conditions after the addition step (Hielscher ultrasound Ultrasonic dispersion at the technology company, UP200S model, dispersion time with Cycle time 0.5 s,
d) a process for securing CNT / PP powder after the ultrasonic dispersion has a scavenging process of xylene solvent. 2 to 3 hours in a vacuum oven, 130 ~ 150 ℃ conditions to remove the solvent present in the powder has a process. As an additional process, the CNT / PP powder was first identified through the solvent degassing process and further dried in a vacuum oven at 100-150 ° C. for 20-24 hours to obtain a final material, CNT / PP powder.
e) thereafter provides a CNT / PP composite material manufacturing method comprising the step of molding using an injection machine. The use of a solution to produce CNT / PP powders is a deterrent to moldability in thermoplastic composites. Therefore, when using the injection molding machine for high-speed molding, whether or not the solvent causes bubbles in the injection molding machine, there is a possibility of generating a lot of bubbles inside the specimen. To optimize this point, solvent degassing conditions must be passed as a final process.
Description of the composite material manufacturing method of carbon nanopolypropylene (PP) of the present invention is as follows. First, the polypropylene in the pallet state is prepared as a powder having a micro size diameter with a fine mill. The prepared PP powder is administered to a solvent called xylene and stirred for 2 hours at about 130 ° C. In this process, PP powder is swelled. Insert separately prepared CNT / Xylene nanoparticle dispersion into swelled PP powder / Xylene solvent. After that, CNT particles are adsorbed on the surface of the swelled PP by ultrasonic dispersing process, spending 2 hours 30 minutes, 130 ° C, and evaporating the remaining solvent using a vacuum oven to produce CNT / PP. It is characterized by producing a powder.
The present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the examples.
[Examples and Comparative Examples]
The polypropylene resin compositions of Examples and Comparative Examples were prepared using the compositions and contents shown in Table 1 below.
[Table 1]
* HP908: Homo polypropylene with a melt index of 8.8 g / 10 min
* M1400: Impact polypropylene with melt index 8 g / 10 min
* MWNT (CM-95): 10 ~ 15 nm in diameter and 30 nm in length prepared by chemical vapor deposition
Experimental Example Measurement of physical properties and physical property values of compositions of Examples and Comparative Examples
1) FE-SEM photographing: The surface of the powder confirmed in the process of manufacturing the powder of the CNT / PP through the FE-SEM photographing to confirm the particles of the CNT. Dispersion evaluation of the CNT particles was carried out, and it was confirmed that there is a possibility of using CNT / PP powder.
2) Electrical Resistance Dispersion Evaluation: In order to check the conductivity effect generated when the specimen was manufactured using CNT / PP, the dispersion degree of CNT in the specimen was evaluated by using the electrical resistance measurement method. Was evaluated by application. The results according to the dispersion evaluation results were confirmed, and the specimens were measured in a size of 40 x 40 x 1 mm, and the impregnation positions of the wires were confirmed in 16 groups and the wires were impregnated at intervals of 10 mm.
3) Tensile strength of the film: measured at room temperature 25 ℃ by ASTM D-882 method, the specimen size was 25 × 130 × 0.1mm. In order to satisfy the mechanical strength, the nanocomposite was manufactured using carbon nanotubes and tested. In the present invention, to improve the film properties of the material identified as a small amount in order to utilize as a vehicle exterior material, the overall concentration was used to utilize the nanoparticles of 1 wt%. The film was prepared using hot press.
4) Tensile strength of the plastic: measured at room temperature by the ASTM D-638 method, the specimen size was tested using a 5.66 × 3 × 45 mm necked specimen, the method of preparing the specimen was prepared through the present invention One CNT / PP powder was molded using an injection molding machine to prepare a specimen, and then experimented to check physical properties.
5) Thermal analysis: The thermal decomposition (atmosphere: nitrogen) phenomenon of specimens by thermal analysis equipment (Q50) and TGA equipment by TA is compared and analyzed by the weight loss of the sample. The degree of thermal stability enhancement of the PP material was measured by the influence of the CNT particles.
Table 2 Tensile Strength of Comparative Examples and Examples (Film Type)
The change of the mechanical properties when the film form was manufactured using the hot press and tested. In both types of polypropylene, the mechanical properties increased due to the dispersion of nanoparticles. In the case of homo PP, the increase in mechanical properties was clearly observed. In the case of impact PP, a small amount of mechanical properties was increased in the content ratio of 1 wt%. Through these results, it was confirmed that the mechanical properties are increased. In addition, one important point is that the smaller the particle size of the polypropylene, the greater the effect of increasing the physical properties. For the HP908 model, the particle size is a powder with a small diameter of about μm. In the case of M1400, the result has a diameter of mm, and it is confirmed that the result of utilizing the effect of CNT adsorption on the surface of the PP, the smaller the size of the particles can be confirmed that the results of stronger physical properties increase.
Table 3 Tensile Strength of Comparative Examples and Examples (Tensile Specimen Type)
In the case of using the tensile specimens, higher results were obtained than the tensile results of the film type, and it was confirmed that the reinforcing effect by the CNTs generally existed. Since it is a result of molding using an injection molding machine, it can be said that there is an effect of increasing physical properties by mixing between more CNTs and PP.
[Table 4] Evaluation of heat resistance according to DSC photographing results
Table 4 and Figure 3 are the results of the experiment to determine the heat resistance and thermal stability. Experimental results showed that DSC was improved in heat resistance with increasing CNT content and improved melting point and thermally stable material. In addition, Figure 3 shows the TGA results, the thermal stability is improved with the increase in the content of CNT when used in the field of heat resistance confirmed that the heat resistance is enhanced compared to the conventional PP.
Detailed description of the method for producing a composite material of carbon nanopolypropylene (PP) of the present invention begins with the production of micro-sized particles using a PP pallet using a fine grinding machine. This is because PP is a material having excellent chemical resistance, and thus exhibits insoluble properties in most solvents. However, the surface of the PP has a swelling state, and in this process, the attraction of the particles is increased through experiments.
The second preparation is to prepare a CNT dispersion solvent, in order to keep the CNT particles in a highly dispersed state in the solvent, and to evenly impregnate the CNT particles on the swelled PP surface.
CNT / swelling PP particles with a solvent were prepared through ultrasonic dispersion while putting the PP powder into a solution in which CNTs were dispersed. The solvent must be removed to obtain only the prepared particles. In the process of removing the solvent, the swelled PP is obtained to obtain the state of the existing rigid PP again on the soft surface, and the CNT particles attached to the PP surface in the swelled state are strongly CNT on the PP surface as the swelling state of the PP progresses. It proceeds to make the impregnation.
Figure 2 is an evaluation of the results of the measurement of the volume resistance produced through the above example, although the high electrical resistance is measured, the resistance value of mega ohms is confirmed, but the overall resistance of the uniform state was confirmed. This is a result indicating that the dispersion state of the CNT is evenly spread as a whole, and it can be predicted that stable electrical resistance results can be obtained by increasing the electrical resistance content of the specimen.
The utilization of the material using the CNT / PP powder thus obtained is confirmed in various ways. In addition, it is possible to mold the material using an autoclave or an injection molding machine, so the moldability is excellent.
It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (5)
b) stirring the mixture at 100-150 ° C. and 1-3 hours,
c) preparing a CNT / Xylene dispersion solution by mixing carbon nanotubes (CNT) and xylene in a weight ratio within 0.5 wt% to 10 wt%;
d) injecting the CNT / Xylene dispersion solution prepared by performing step c) to the swelling PP powder / Xylene mixture obtained by performing step b),
e) dispersing the ultrasonic wave under ultrasonic dispersing condition (Cycle time 0.5 s, Amplitude 60% condition) after the dosing step,
d) after the ultrasonic dispersion, removing the solvent present in the powder in a vacuum oven for 2 to 3 hours, 130 ~ 150 ℃ conditions, solvent degassing step and additionally in the vacuum oven for 20 to 24 hours at 100 ~ 150 ℃ conditions CNT / PP composite material manufacturing method comprising the step of preparing a final CNT / PP powder by drying.
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| KR1020130030445A KR20130036114A (en) | 2013-03-21 | 2013-03-21 | A method for preparing carbon nano tube reinforced polypropylene |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015099367A1 (en) * | 2013-12-27 | 2015-07-02 | 주식회사 동진쎄미켐 | Method for preparing carbon-metal composite |
| KR20160088010A (en) * | 2015-01-15 | 2016-07-25 | 경상대학교산학협력단 | Method of evaluation for dispersion of conductive particles in composite material |
| KR20210083055A (en) | 2019-12-26 | 2021-07-06 | 다이텍연구원 | Manufacturing method of carbon nanotube reinforced polypropylene |
| KR20240022305A (en) | 2022-08-11 | 2024-02-20 | 주식회사 제이푸드테크 | Eco-friendly nanocomposites and manufacturing method thereof |
-
2013
- 2013-03-21 KR KR1020130030445A patent/KR20130036114A/en not_active Application Discontinuation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015099367A1 (en) * | 2013-12-27 | 2015-07-02 | 주식회사 동진쎄미켐 | Method for preparing carbon-metal composite |
| KR20160088010A (en) * | 2015-01-15 | 2016-07-25 | 경상대학교산학협력단 | Method of evaluation for dispersion of conductive particles in composite material |
| KR20210083055A (en) | 2019-12-26 | 2021-07-06 | 다이텍연구원 | Manufacturing method of carbon nanotube reinforced polypropylene |
| KR20240022305A (en) | 2022-08-11 | 2024-02-20 | 주식회사 제이푸드테크 | Eco-friendly nanocomposites and manufacturing method thereof |
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