KR20140099997A - Polyketone resin composition with improved electric conductivity - Google Patents
Polyketone resin composition with improved electric conductivity Download PDFInfo
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- KR20140099997A KR20140099997A KR1020130012510A KR20130012510A KR20140099997A KR 20140099997 A KR20140099997 A KR 20140099997A KR 1020130012510 A KR1020130012510 A KR 1020130012510A KR 20130012510 A KR20130012510 A KR 20130012510A KR 20140099997 A KR20140099997 A KR 20140099997A
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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
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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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
- C08L73/00—Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a polyketone resin composition having improved electrical conductivity, and more particularly, to a polyketone resin composition having improved electrical conductivity, and more particularly, to a polyketone resin composition containing a predetermined amount of a specific conductive material, To a resin composition.
Description
The present invention relates to a polyketone resin composition having improved electrical conductivity, and more particularly, to a polyketone resin composition having improved electrical conductivity, and more particularly, to a polyketone resin composition containing a predetermined amount of a specific conductive material, To a resin composition.
The present invention is derived from the research carried out as part of the WPM project of the Ministry of Knowledge Economy.
National R & D project supporting the present invention
Assignment number: 10037857
Department name: Ministry of Knowledge Economy
Research Project: WPM Business
Research title: Development of polyketone material
Organizer: Hyosung Corporation
Research period: Sep. 1, 2010 ~ Mar. 2017
Conventional automobile fuel filler door parts are mostly made of nylon with 10 ~ 40% of inorganic filler.
Particularly, there is a problem in that a conductive primer is applied after component injection to use parts coated with in-line painting in the assembly line of a finished car, which causes an excessive process cost. In addition, due to dimensional changes and deterioration of physical properties due to moisture absorption of nylon material, there were limitations in designing various products, such as appearance abnormality and inability to detach from the Fill Filler Door during use after assembling the automobile.
On the other hand, most of conductive gear parts among electronic products such as ATM devices and printer parts of the related art have been provided with electric conductivity by containing a conductive material such as carbon nanotubes (POM) as a material of polyacetal or polyoxymethylene.
However, when the POM material is used, the substantial content of the conductive material is largely limited due to thermal decomposition or the like, so that it is difficult to exhibit the required level of electric conductivity.
Accordingly, it is required to develop new materials which can be effectively applied to a wide range of fields including automobile fuel injection ports and conductive gear parts, while satisfying basic mechanical properties and dimensional stability as well as excellent electrical conductivity.
Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made in view of the above problems, and it is an object of the present invention to provide a polyketone resin composition capable of exhibiting excellent electrical conductivity as well as mechanical properties and dimensional stability basically required for industrial materials .
In order to accomplish the above object, the present invention provides a polyketone resin composition comprising: a polyketone resin; And at least one of carbon nanotubes and conductive carbon black.
Also provided is a polyketone resin composition comprising 25 to 99.5% by weight of a polyketone resin, 0 to 10% by weight of carbon nanotubes, 0 to 30% by weight of conductive carbon black, and 0 to 40% by weight of an inorganic filler do.
Specifically, the polyketone resin composition is characterized by comprising 30 to 99.5% by weight of a polyketone resin, 0.5 to 10% by weight of carbon nanotubes, 0 to 30% by weight of conductive carbon black, and 0 to 40% to provide.
The present invention also provides a polyketone resin composition characterized in that the electrical conductivity is 10 0.5 to 10 7 Ω / square.
Further, there is provided a polyketone resin composition characterized by being used as a material of a fuel filler door or a conductive gear part.
The polyketone resin composition of the present invention can remarkably improve the electrical conductivity while maintaining advantageous characteristics inherent in polyketone resin such as excellent mechanical stiffness and dimensional stability, and can reduce the manufacturing cost in the case of using nylon material have.
As a result, it can be widely applied to various industrial fields such as a fuel filler door and a conductive gear part of an electronic part, an automobile part, an electric / electronic part, a household goods, and contributes to the durability and cost competitiveness of parts.
Hereinafter, the present invention will be described in detail.
The polyketone resin composition of the present invention includes polyketone (PK) resin; And at least one of a carbon nanotube (CNT) and a conductive carbon black (Carbon Black).
The polyketone resin, which is the subject of the composition of the present invention, is a new resin developed in recent years and is excellent in mechanical properties such as impact strength and molding characteristics and is a thermoplastic synthetic resin which is usefully applied to various molded articles and parts. The mechanical properties of polyketone resins belong to the category of high performance plastics, and they are attracting much attention as eco-friendly materials as well as being a polymer material synthesizing carbon monoxide as a raw material.
In particular, polyketone resin has lower moisture absorption than nylon (0.45%, 50% RH, 23 ℃), which makes it possible to design various products with less change in dimensions and physical properties due to moisture absorption.
However, a pure polyketone resin is a non-conductor having an electric conductivity of 10 12 to 10 14 Ω / square, and can not be practically used as an industrial material requiring electrical conductivity.
Accordingly, in the present invention, by supplying a predetermined amount of carbon nanotubes and / or conductive carbon black, which are conductive materials, to the polyketone resin, it is possible to secure the inherent characteristics of the polyketone resin excellent in resistance to water absorption, durability, dimensional stability, A polyketone resin composition having improved conductivity is proposed. In particular, unlike conventional POM materials, the present invention is advantageous in that an electrically conductive polyketone resin composition can be prepared by injecting an electrically conductive material without thermal decomposition by adjusting the melt index (MI).
The polyketone resin is generally synthesized from carbon monoxide and olefin. For example, U.S. Patent No. 4,843,144 discloses line alternating polymers synthesized from olefins such as ethylene and propylene and carbon monoxide. The polyketone resin produced in this patent has been shown to have excellent impact resistance, high rebound resilience at room temperature and low temperature, and excellent creep properties.
In recent years, among polyketones, there is a growing interest in a series of alternating polyketones in which ketone groups and at least one ethylenically unsaturated hydrocarbon are alternately polymerized and improved in mechanical properties and molding characteristics. For example, U.S. Patent No. 4,880,903 discloses a polyketone terpolymer in which ketone groups, ethylene, and other olefinically unsaturated hydrocarbons (such as propylene) are alternately polymerized and formed.
The contents of the aforementioned U.S. Patent Nos. 4,843,144 and 4,880,903 are incorporated herein by reference.
Specifically, the polyketone resin as a main component of the polyketone resin composition of the present invention is a linear alternating structure composed of a ketone group and at least one ethylenically unsaturated hydrocarbon, and contains substantially one carbon monoxide (or a ketone group) per one ethylenically unsaturated hydrocarbon, And has excellent physical properties, appearance characteristics and molding properties.
In one embodiment, the polyketone resin may include a repeating unit represented by the following formula (1).
[Chemical Formula 1]
- {- CO - (- CH 2 -CH 2 -) -} x - {CO- (G) -} y -
Wherein G is derived from monomers of at least three ethylenically unsaturated hydrocarbons polymerized through ethylenic unsaturation and x: y is at least 2: 1.
Ethylenically unsaturated hydrocarbons suitable for use as the precursor of the polyketone resin include ethyne having up to 20 carbon atoms, preferably up to 10 carbon atoms, alpha -olefins (e.g., propene, 1-butene aliphatic hydrocarbons such as isobutene, 1-hexene and 1-octene, or aryl aliphatic hydrocarbons in which aryl substituents are formed on aliphatic molecules, in particular ethylenically unsaturated carbon Is an aryl aliphatic hydrocarbon having an aryl substituent on the atom. Examples of the aryl aliphatic hydrocarbon in the ethylenic unsaturated hydrocarbon include styrene, p-methylstyrene, p-ethylstyrene, and m-isopropyl styrene.
Such ethylenically unsaturated hydrocarbons and ketone compounds are copolymerized to form a linear alternating polyketone. Among them, a linear alternating polyketone formed by copolymerization of ethene and a ketone compound, or a mixture of at least three Linear alternating polyketone formed by copolymerization of an ethylenically unsaturated hydrocarbon having a carbon atom is preferable in view of the fact that the copolymerization reaction is easy and the molecular weight of the copolymerized linear alternating polyketone is relatively uniform. In short, the preferred polyketone resin is a copolymer of carbon monoxide and ethene, more preferably a second ethylenically unsaturated hydrocarbon having carbon monoxide, ethene and at least three carbon atoms (especially propene) is a linear terpolymer with an a-olefin.
The polyketone resin preferably has an intrinsic viscosity (LVN) of 0.5 to 10 dl / g, more preferably 0.8 to 4 dl / g, and most preferably 1 to 1.5 dl / g. If the intrinsic viscosity of the polyketone resin is less than 0.5 dl / g, the mechanical properties may be deteriorated. If the intrinsic viscosity exceeds 10 dl / g, the workability may be deteriorated.
The polyketone resin has a number-average molecular weight, as measured by gel permeation chromatography, of preferably 100 to 200,000, more preferably 20,000 to 90,000. The physical properties of the polymer depend on the molecular weight, whether the polymer is a copolymer or a terpolymer, and in the case of a terpolymer, the physical properties of the second hydrocarbon moiety are determined.
The melting point of the polyketone resin is usually in the range of 175 ° C to 300 ° C, specifically 210 ° C to 270 ° C.
Specifically, the polyketone resin composition containing the conductive material of the present invention comprises a combination of a polyketone resin, a carbon nanotube, a conductive carbon black, and an inorganic filler. The electrically conductive polyketone resin composition of the present invention can be provided by mixing and uniformly dispersing one or both of the carbon nanotubes and the conductive carbon black in the (alternating) polyketone resin.
The carbon nanotubes are components for imparting electrical conductivity to the composition of the present invention and can impart a very improved electrical conductivity to a polyketone resin as a base material in a small amount. Carbon nanotubes are a new material in which six hexagons of carbon are connected to each other to form a tubular shape. The electric conductivity is similar to that of copper. The thermal conductivity is the same as that of diamond which is the best in nature, and its strength is 100 times better than steel. In addition, carbon fibers are broken even when only 1% is deformed, while carbon nanotubes are durable enough to withstand 15% deformation. The types of carbon nanotubes usable in the present invention are not particularly limited. For example, single wall carbon nanotubes (SWCNTs) and multiwall carbon nanotubes (MWCNTs) may be used singly or in combination.
The conductive carbon black is also a component for imparting electrical conductivity to the composition of the present invention. The kind of the conductive carbon black that can be used in the present invention is not particularly limited, and ordinary carbon black materials having excellent electric conductivity can be used. For example, typical carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, and summer black may be used singly or in combination of two or more.
The inorganic filler is a component for improving the mechanical strength of the composition of the present invention and the molded article thereof, and performs a function of lowering the moisture absorption amount. The inorganic fillers usable in the present invention are not particularly limited and include, for example, kaolin, silica (such as natural silica, synthetic silica, fused silica, etc.), silica nitride, alumina, aluminum nitride, boronite And the like may be used alone or in combination of two or more. The form of the inorganic filler is not particularly limited, either, and any inorganic filler in the form of each phase and globular form may be used.
The polyketone resin composition of the present invention includes at least one of carbon nanotubes and conductive carbon black as an electrically conductive material. Preferably, all of the carbon nanotubes, the conductive carbon black and the inorganic filler are added to the polyketone resin in a harmonious manner to realize various physical properties such as mechanical properties, dimensional stability and electrical conductivity.
In one preferred embodiment, the polyketone resin composition of the present invention comprises 25 to 99.5 wt% (specifically, 30 to 99.5 wt%) of a polyketone resin, 0 to 10 wt% (specifically, 0.5 to 10 wt% 0 to 30% by weight (specifically, 2 to 30% by weight) of conductive carbon black and 0 to 40% by weight (more specifically, 10 to 40% by weight) of inorganic filler.
If the content of the polyketone resin is less than 25% by weight, the inherent mechanical strength, dimensional stability, molding characteristics, etc. of the polyketone resin deteriorate and practicality may be lacked. If the content exceeds 99.5% by weight, the carbon nano tube and the conductive carbon black The reduction in relative content can make it difficult to impart the desired level of electrical conductivity.
When the content of the carbon nanotubes or the conductive carbon black is 0.5 wt% or less and less than 2 wt%, respectively, it may be difficult to improve the electrical conductivity of the polyketone resin composition. When the content is more than 10 wt% Excellent mechanical properties (e.g., impact strength) inherent to the ketone resin, dimensional stability, and molding properties (e.g., extrudability) may not be exhibited.
If the content of the inorganic filler is less than 10% by weight, the mechanical strength (e.g., impact strength) may be lowered. If the content is more than 40% by weight, the viscosity may increase and the flowability may be deteriorated.
The polyketone resin composition of the present invention may additionally contain additives commonly used in the art within the scope not deviating from the object.
For example, at least one kind of various additives such as a flame retardant, a pigment, an antioxidant, a heat stabilizer, a lubricant, a processing aid, and a light stabilizer is appropriately mixed and uniformly dispersed to constitute an electroconductive polyketone composition can do.
The method for producing the polyketone resin composition of the present invention is not particularly limited and can be produced by a conventional method in the art.
For example, the polyketone resin composition and the molded article of the present invention can be produced by melt-blending the respective components at a temperature of 230 ° C using a co-axial twin screw extruder, pelletizing the components, and injection-molding the components at 230 ° C .
More specifically, there is provided a method for preparing a catalyst composition, comprising: preparing a catalyst composition comprising a palladium compound, an acid having a pKa value of 6 or less, and a bidentate compound of phosphorus; Preparing a mixed solvent (polymerization solvent) containing an alcohol (for example, methanol) and water; Conducting the polymerization in the presence of the catalyst composition and the mixed solvent to prepare a linear terpolymer of carbon monoxide, ethylene and propylene; Removing the remaining catalyst composition from the linear terpolymer with a solvent (e.g., alcohol and acetone) to obtain a polyketone resin; And mixing and kneading the polyketone resin with a carbon nanotube, a conductive carbon black, and an inorganic filler, and extruding the polyketone resin composition. The polyketone resin composition of the present invention can be prepared by injection molding, .
The reaction temperature in the polymerization is suitably in the range of 50 to 100 ° C and the reaction pressure in the range of 40 to 60 bar. The resulting polymer is recovered through filtration and purification processes after polymerization, and the remaining catalyst composition is removed with a solvent such as alcohol or acetone. The extrusion temperature is preferably 230 to 260 占 폚, and the screw rotation speed is preferably in the range of 100 to 300 rpm. If the extrusion temperature is less than 230 캜, kneading may not occur properly, and if the extrusion temperature exceeds 260 캜, problems related to the heat resistance of the resin may occur. On the other hand, if the screw rotating speed is less than 100 rpm, the kneading may not be smoothly performed, and when the rotational speed is higher than 300 rpm, the conductive material and the inorganic filler may be broken and the electrical conductivity and the mechanical strength may be lowered.
As described above, the polyketone resin composition of the present invention can be molded into a variety of products by extrusion, injection molding, or the like. Specifically, the polyketone resin composition of the present invention is injection-molded or extruded to produce polyketone sheets, films, plates, OA appliances, electric / electronic parts, housing parts, automobile parts, Various industrial materials can be manufactured.
Particularly, the polyketone resin composition of the present invention is excellent in mechanical properties and dimensional stability, and has a significantly improved electrical conductivity (for example, 10 0.5 to 10 7 Ω / square) compared to the Neat polyketone resin. Fuel Filler Door) or as a material for conductive gear parts.
Hereinafter, the present invention will be described more specifically by way of examples. However, these examples are provided only for the understanding of the present invention, and the scope of the present invention is not limited to these examples in any sense.
Example 1 to 10
An injection specimen of a polyketone resin composition was prepared according to the ingredients and the content (unit: wt%) shown in Table 1 below.
Specifically, a polyketone terpolymer (PK) polymerized from ethylene, carbon monoxide and propylene was directly fed into a 40 mm biaxial screw operated at 200 rpm, CNT, conductive carbon black and inorganic filler were fed side by side and the extruder barrel was heated to 240 ° C Temperature was set to a pellet shape. The injection specimens were manufactured in accordance with the ISO standard, and electrical properties and mechanical properties were evaluated. The results are shown in Table 1 below.
Comparative Example
CNT, conductive carbon black, and polyketone terpolymer (PK) polymerized from ethylene, carbon monoxide and propylene without inorganic filler.
[Table 1]
As shown in Table 1, in the comparative example using only polyketone resin (Neat Resin), no electrical conductivity was observed. On the other hand, in the case of an example in which a polyketone resin and a conductive material were properly blended, the electrical conductivity was improved by at least 10 7 times up to 10 13.5 times as much as that of the comparative example, showing excellent mechanical properties.
Claims (5)
Wherein the polyketone resin composition contains 25 to 99.5% by weight of a polyketone resin, 0 to 10% by weight of carbon nanotubes, 0 to 30% by weight of conductive carbon black, and 0 to 40% by weight of an inorganic filler.
Wherein the polyketone resin composition comprises 30 to 99.5% by weight of a polyketone resin, 0.5 to 10% by weight of carbon nanotubes, 0 to 30% by weight of conductive carbon black, and 0 to 40% by weight of an inorganic filler.
Wherein the polyketone resin composition has an electrical conductivity of 10 0.5 to 10 7 Ω / square.
Characterized in that the polyketone resin composition is used as a material of a fuel filler door or a conductive gear part.
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| KR1020130012510A KR20140099997A (en) | 2013-02-04 | 2013-02-04 | Polyketone resin composition with improved electric conductivity |
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| KR1020130012510A KR20140099997A (en) | 2013-02-04 | 2013-02-04 | Polyketone resin composition with improved electric conductivity |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20160059886A (en) * | 2014-11-19 | 2016-05-27 | 주식회사 효성 | Composition of polyketone comprising conductive carbon black and elastic polyurethane |
| KR20160080664A (en) * | 2014-12-30 | 2016-07-08 | 주식회사 효성 | Composite material with high thermal conductive and housing for outdoor use comprising the same |
| KR101675288B1 (en) * | 2015-05-27 | 2016-11-11 | 주식회사 효성 | Polyketone wire for tennis racket inculding polyketone fiber |
| KR101675289B1 (en) * | 2015-05-27 | 2016-11-11 | 주식회사 효성 | Polyketone skiboard inculding polyketone fiber |
| WO2016060511A3 (en) * | 2014-10-17 | 2017-05-04 | (주) 효성 | Polyketone resin composition having excellent conductivity |
| WO2021107722A1 (en) * | 2019-11-29 | 2021-06-03 | 롯데케미칼 주식회사 | Polyolefin-based resin foam, and molded product produced therefrom |
| CN113337072A (en) * | 2021-05-28 | 2021-09-03 | 南京跃贝新材料科技有限公司 | Antistatic highlight polyketone material and preparation method thereof |
-
2013
- 2013-02-04 KR KR1020130012510A patent/KR20140099997A/en not_active Application Discontinuation
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016060511A3 (en) * | 2014-10-17 | 2017-05-04 | (주) 효성 | Polyketone resin composition having excellent conductivity |
| KR20160059886A (en) * | 2014-11-19 | 2016-05-27 | 주식회사 효성 | Composition of polyketone comprising conductive carbon black and elastic polyurethane |
| KR20160080664A (en) * | 2014-12-30 | 2016-07-08 | 주식회사 효성 | Composite material with high thermal conductive and housing for outdoor use comprising the same |
| KR101675288B1 (en) * | 2015-05-27 | 2016-11-11 | 주식회사 효성 | Polyketone wire for tennis racket inculding polyketone fiber |
| KR101675289B1 (en) * | 2015-05-27 | 2016-11-11 | 주식회사 효성 | Polyketone skiboard inculding polyketone fiber |
| WO2021107722A1 (en) * | 2019-11-29 | 2021-06-03 | 롯데케미칼 주식회사 | Polyolefin-based resin foam, and molded product produced therefrom |
| CN113337072A (en) * | 2021-05-28 | 2021-09-03 | 南京跃贝新材料科技有限公司 | Antistatic highlight polyketone material and preparation method thereof |
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