WO2010134682A1 - Composition composite électroconductrice de polyamide, et tubes de transport de combustible l'utilisant - Google Patents

Composition composite électroconductrice de polyamide, et tubes de transport de combustible l'utilisant Download PDF

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WO2010134682A1
WO2010134682A1 PCT/KR2009/007981 KR2009007981W WO2010134682A1 WO 2010134682 A1 WO2010134682 A1 WO 2010134682A1 KR 2009007981 W KR2009007981 W KR 2009007981W WO 2010134682 A1 WO2010134682 A1 WO 2010134682A1
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polyamide
resin
copolymer
poly
ethylene
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Korean (ko)
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허진영
홍정숙
하두한
이영실
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제일모직 주식회사
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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
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • 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
    • 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
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    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • 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
    • C08L23/12—Polypropene
    • 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
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present disclosure relates to conductive polyamide composite compositions and fuel transport tubes using the same.
  • the non-conductive polyamide resin composition mainly used in the conventional automotive fuel system is inferior in safety due to the friction between the tube and the fuel as the fuel circulates. Recently, a conductive material has been used for the tube to prevent such static electricity. In general, in order to impart conductivity to the polyamide resin, the conductive filler is added in a high content. In this case, the appearance is poor and expensive.
  • polyamide resin has been used for various applications in automotive interior and exterior parts because of excellent mechanical strength, wear resistance, heat resistance, chemical resistance, electrical insulation, arc resistance and the like.
  • a co-extrusion process such as a fuel tube or a hose
  • it is necessary to melt the rubber in the molding so that mixing of the rubber phase is required, and the compatibility, flexibility, viscosity, workability, etc. of the polyamide and rubber phase are required.
  • the application content of the carbon black for implementing the conductivity is usually 20% by weight or more, there was a technical limitation in the process to uniform dispersion of the rubber phase and the conductive filler of the tube.
  • One aspect of the present invention is to provide a conductive polyamide composite composition excellent in conductivity and compatibility.
  • Another aspect of the present invention is to provide a fuel transport tube made using the conductive polyamide composite composition.
  • One aspect of the invention is (A) 30 to 99% by weight of the first polymer comprising the polyamide resin (A-1) and (A-2) polyolefin resin, polyester resin, polyolefin thermoplastic elastomer resin, olefin air 100 parts by weight of a base resin comprising 1 to 70% by weight of a second polymer selected from the group consisting of coalescing and combinations thereof; (B) 1 to 15 parts by weight of carbon black; And (C) provides a conductive polyamide composite composition comprising 0.01 to 5 parts by weight of carbon nanotubes.
  • the olefin copolymer may be included in an amount of 65 to 100 parts by weight based on 100 parts by weight of the resin selected from the group consisting of the polyolefin resin, the polyester resin, the polyolefin thermoplastic elastomer resin, and a combination thereof.
  • the polyamide resin may be poly4-aminobutyl acid (poly (4-aminobutyric acid), polyamide 4); Polycaprolactam (polyamide 6); Poly (7-aminoheptanoic acid), polyamide 7); Poly (8-aminoocatanoic acid); polyamide 8); Poly (9-aminononanoic acid), polyamide 9); Poly (10-aminodecanoic acid), polyamide 10); Poly (11-aminoundecanoic acid), polyamide 11); Polylaurylactam (polyamide 12); Polytetramethylene adipamide (poly (tetramethylene adipamide), polyamide 4,6); Polyhexamethylene adipamide (poly (hexamethylene adipamide), polyamide 6,6); Polyhexamethylene azelamide (poly (hexamethylene azelamide), polyamide 6,9); Polyhexamethylene sebacamide (poly (hexamethylene sebacamide), polyamide 6,10); Polyhexamethylene do
  • the polyolefin resin is 0.94 kg / m 3 To 0.965 kg / m 3 High density polyethylene (HDPE) with a density of 0.91 kg / m 3 To 0.94 kg / m 3 Linear low density polyethylene (LLDPE), polypropylene, ethylene-vinyl alcohol copolymer, ethylene-propylene copolymer, and combinations thereof.
  • HDPE High density polyethylene
  • LLDPE Linear low density polyethylene
  • the polyester resin may be prepared by mixing polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin, polyhexamethylene terephthalate resin, polycyclohexane dimethylene terephthalate resin, and some other monomers in these resins. Qualitatively modified resins and combinations thereof.
  • the polyolefin-based thermoplastic elastomer resin may be selected from the group consisting of ethylene-propylene diene copolymer resin (EPDM), ethylene-propylene rubber (EPR), and combinations thereof.
  • EPDM ethylene-propylene diene copolymer resin
  • EPR ethylene-propylene rubber
  • the olefin copolymer may be selected from the group consisting of an olefin-acrylate copolymer, an olefin-maleic anhydride modified copolymer, and a combination thereof, and the olefin-acrylate copolymer may be an ethylene methyl-acrylate copolymer or ethylene. Ethyl-acrylate copolymers, ethylene butyl-acrylate copolymers, ethylene vinyl-acrylate copolymers, and combinations thereof.
  • the olefin-maleic anhydride-modified copolymer may be selected from ethylene butene-maleic anhydride copolymer. Copolymer, ethylene octene-maleic anhydride copolymer, ethylene propylene-maleic anhydride copolymer, and combinations thereof.
  • the carbon black may be selected from the group consisting of ketjen black, acetylene black, furnace black, channel black, and combinations thereof.
  • the carbon nanotubes include single wall carbon nanotubes, double wall carbon nanotubes, multiwall carbon nanotubes, and combinations thereof. It may be selected from the group consisting of.
  • Another aspect of the present invention provides a fuel transport tube made using the conductive polyamide composite composition.
  • Conductive polyamide composite composition according to an aspect of the present invention by using a mixture of carbon black and carbon nanotubes, the amount of the conductive filler is significantly reduced when manufacturing a fuel transport tube, the appearance is improved, economical, and excellent electrical conductivity Appears to prevent static electricity, and is excellent in various physical properties such as resistance to oil, tensile strength, impact strength and formability.
  • FIG. 1 is an electron micrograph showing a form in which carbon nanotubes are mixed with carbon black in a specimen using the conductive polyamide composite composition according to Example 4.
  • FIG. 1 is an electron micrograph showing a form in which carbon nanotubes are mixed with carbon black in a specimen using the conductive polyamide composite composition according to Example 4.
  • FIG. 2 is an electron micrograph showing a form in which carbon black is concentrated on a polyamide in a specimen using the conductive polyamide composite composition according to Comparative Example 3.
  • FIG. 2 is an electron micrograph showing a form in which carbon black is concentrated on a polyamide in a specimen using the conductive polyamide composite composition according to Comparative Example 3.
  • (A) 30 to 99% by weight of the first polymer comprising (A-1) polyamide resin and (A-2) polyolefin resin, polyester resin, polyolefin-based thermoplastic elastomer resin, 100 parts by weight of a base resin comprising 1 to 70% by weight of a second polymer selected from the group consisting of olefin copolymers and combinations thereof; (B) 1 to 15 parts by weight of carbon black; And (C) provides a conductive polyamide composite composition comprising 0.01 to 5 parts by weight of carbon nanotubes.
  • the base resin comprises a first polymer comprising (A-1) a polyamide resin, (A-2) a polyolefin resin, a polyester resin, a polyolefin thermoplastic elastomer resin, an olefin copolymer, It comprises a second polymer selected from the group consisting of a combination of these.
  • the first polymer according to an embodiment of the present invention comprises a polyamide resin, wherein the polyamide resin contains an amide group in the polymer main chain, and polymerizes with amino acids, lactams or diamines and dicarboxylic acids as main constituents.
  • Polyamide resin contains an amide group in the polymer main chain, and polymerizes with amino acids, lactams or diamines and dicarboxylic acids as main constituents.
  • amino acid examples include 6-aminocapronic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid, and the like.
  • lactam examples include ⁇ -caprolactam, ⁇ -laurolactam, and the like
  • diamine examples include tetramethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, and undecamethylene.
  • dicarboxylic acid examples include adipic acid, sericinic acid, azelaic acid, sebacic acid, dodecane diacid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, Aliphatic, alicyclic, or aromatic dicarboxylic acids, such as 5-sodium sulfoisophthalic acid, 2, 6- naphthalenedicarboxylic acid, hexahydro terephthalic acid, and hexahydroisophthalic acid, are mentioned.
  • Polyamide homopolymers or copolymers derived from these raw materials can be used alone or in the form of mixtures, respectively.
  • polyamide resin examples include poly4-aminobutyric acid (poly (4-aminobutyric acid), polyamide 4); Polycaprolactam (polyamide 6); Poly (7-aminoheptanoic acid), polyamide 7); Poly (8-aminoocatanoic acid); polyamide 8); Poly (9-aminononanoic acid), polyamide 9); Poly (10-aminodecanoic acid), polyamide 10); Poly (11-aminoundecanoic acid), polyamide 11); Polylaurylactam (polyamide 12); Polytetramethylene adipamide (poly (tetramethylene adipamide), polyamide 4,6); Polyhexamethylene adipamide (poly (hexamethylene adipamide), polyamide 6,6); Polyhexamethylene azelamide (poly (hexamethylene azelamide), polyamide 6,9); Polyhexamethylene sebacamide (poly (hexamethylene sebacamide), polyamide 6,10); Polyhexamethylene
  • polyamide 4 examples include those selected from the group consisting of polyamide 4,6, polyamide 11 and combinations thereof, and more specifically, polyamide 11 may be used.
  • polyamide 11 it is highly resistant to gasoline and has low hygroscopicity.
  • the polyamide resin preferably has a melting point of 185 ° C. or higher and a relative viscosity (measured at 25 ° C. by adding 1% by weight of polyamide resin to m-cresol), and has a melting point and relative viscosity in the above range.
  • the mechanical properties and heat resistance of the polyamide composite composition are excellent.
  • polyamide resin may be used without limitation one or more types of polyamide having a glass transition temperature of 50 °C or more.
  • the first polymer including the polyamide resin may be included in an amount of 30 to 99 wt% based on the total amount of the base resin, and specifically, 55 to 99 wt%.
  • the first polymer containing the polyamide resin is included in the above range, it is excellent in conductivity, excellent physical properties such as tensile strength, impact strength, and can maintain the gasoline resistance at an appropriate level.
  • the base resin in addition to the first polymer including the polyamide resin, in the group consisting of polyolefin resin, polyester resin, polyolefin-based thermoplastic elastomer resin, olefin-based copolymer, and combinations thereof to be described below
  • the second polymer selected is included together.
  • the second polymer selected from the group consisting of the polyolefin resin, the polyester resin, the polyolefin thermoplastic elastomer resin, the olefin copolymer, and a combination thereof selectively disperses the conductive filler onto the polyamide resin in the conductive polyamide composite composition. Give the effect to be. This may serve to reduce the content of the conductive filler required to impart conductivity. Due to the use of the second polymer, by reducing the content of the conductive filler used in the conductive polyamide composite composition, it is possible to reduce the cost and economical, it is possible to implement a wide range of physical properties such as impact strength.
  • the hygroscopicity of the polyamide resin It improves the cost and reduces the cost of polyamide resin.
  • the conductive polyamide composite composition may be stabilized in the presence of the olefin copolymer according to a conventional production method.
  • the olefin copolymer may be included in an amount of 65 to 100 parts by weight based on 100 parts by weight of the resin selected from the group consisting of the polyolefin resin, the polyester resin, the polyolefin thermoplastic elastomer resin, and a combination thereof.
  • the polyolefin resin is a high density polyethylene (HDPE) having a density of 0.94 kg / m 3 to 0.965 kg / m 3 , linear low density polyethylene having a density of 0.91 kg / m 3 to 0.94 kg / m 3 density polyethylene, LLDPE), polypropylene, ethylene-vinyl alcohol copolymer, ethylene-propylene copolymer and combinations thereof may be used.
  • HDPE high density polyethylene
  • LLDPE linear low density polyethylene having a density of 0.91 kg / m 3 to 0.94 kg / m 3 density polyethylene
  • polyester resin as the aromatic polyester resin, a resin polycondensed by melt polymerization from a terephthalic acid or a terephthalic acid alkyl ester and a glycol component having 2 to 10 carbon atoms can be used.
  • the alkyl means alkyl having 1 to 10 carbon atoms.
  • aromatic polyester resins include polyethylene terephthalate resins, polytrimethylene terephthalate resins, polybutylene terephthalate resins, polyhexamethylene terephthalate resins, polycyclohexane dimethylene terephthalate resins, and some others to these resins. It is possible to use a second polymer selected from the group consisting of a mixture of monomers and a resin modified to be amorphous, and more specifically, among these, polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene tere Phthalate resin, amorphous polyethylene terephthalate resin, etc. can be used.
  • the polyester resin may have a range of intrinsic viscosity [ ⁇ ] of 0.85 kPa to 1.52 kPa / g, and specifically, may have a range of 1.03 kPa to 1.22 kPa / gk.
  • the polyester resin may have a specific gravity of 1.15 kPa to 1.4 g / cm 3, and may have a melting point of 210 kPa to 280 ° C.
  • the polyolefin-based thermoplastic elastomer resin may be selected from the group consisting of ethylene-propylene diene copolymer resin (EPDM), ethylene-propylene rubber (EPR), and combinations thereof.
  • EPDM ethylene-propylene diene copolymer resin
  • EPR ethylene-propylene rubber
  • the olefin copolymer may be selected from the group consisting of an olefin-acrylate copolymer, an olefin-maleic anhydride modified copolymer, and a combination thereof, and specifically, an olefin-maleic anhydride modified copolymer may be used.
  • an olefin-maleic anhydride modified copolymer may be used.
  • compatibility with the second polymer selected from the group consisting of polyamide resin, polyolefin resin, polyester resin, polyolefin thermoplastic elastomer resin, and combinations thereof can be effectively imparted. .
  • the olefin-acrylate copolymer is selected from the group consisting of ethylene methyl-acrylate copolymer, ethylene ethyl-acrylate copolymer, ethylene butyl-acrylate copolymer, ethylene vinyl-acrylate copolymer and combinations thereof. Can be used.
  • the olefin-maleic anhydride modified copolymer may be selected from the group consisting of ethylene butene-maleic anhydride copolymer, ethylene octene-maleic anhydride copolymer, ethylene propylene-maleic anhydride copolymer, and combinations thereof.
  • the olefin-maleic anhydride-modified copolymer may include 0.1 to 10 parts by weight of maleic anhydride with respect to 100 parts by weight of a main chain, specifically, 0.5 to 5 parts by weight.
  • maleic anhydride branch is contained in the said range, it is advantageous for physical properties, such as the compatibility improvement of polyamide resin and polyolefin resin which are basic resins.
  • the second polymer selected from the group consisting of the polyolefin resin, the polyester resin, the polyolefin thermoplastic elastomer resin, the olefin copolymer, and a combination thereof may be included in an amount of 1 to 70 wt% based on 100 parts by weight of the base resin. It may be included in 15 to 60% by weight.
  • the second polymer is included in the above range, not only excellent mechanical strength and impact strength can be secured, but also excellent conductivity and resistance to gasoline.
  • the compatibility of the polyamide resin with a second polymer selected from the group consisting of polyolefin resin, polyester resin, polyolefin thermoplastic elastomer resin and combinations thereof It is excellent in this, and does not form its own phase which consists only of an olefin type copolymer, and can obtain uniform dispersion as a whole, and its external appearance is good.
  • Carbon black according to an embodiment of the present invention may be selected from the group consisting of ketjen black, acetylene black, furnace black, channel black and combinations thereof Among them, specifically, ketjen black may be used, which is more conductive.
  • the carbon black particles 10 to 30 nm in diameter are agglomerated with each other in a size of 10 ⁇ m to implement conductivity.
  • the carbon black may be included in an amount of 1 to 15 parts by weight, and specifically 5 to 10 parts by weight based on 100 parts by weight of the base resin.
  • the conductivity is excellent, thereby lowering the content of the filler for the conductivity can be economical, it is easy to implement excellent physical properties.
  • Carbon nanotubes according to an embodiment of the present invention is a single wall carbon nanotube (single wall carbon nanotube), double wall carbon nanotube (double wall carbon nanotube), multi-wall carbon nanotube (multi wall carbon nanotube) tube) and combinations thereof.
  • the carbon nanotubes may be included in an amount of 0.01 to 5 parts by weight, specifically 0.1 to 1 part by weight, based on 100 parts by weight of the base resin.
  • the physical properties of the base resin for example, mechanical strength such as tensile strength, thermal stability, and the like can be maintained.
  • the conductive polyamide composite composition according to the embodiment of the present invention significantly reduced the amount of the conductive filler by using a mixture of carbon black and carbon nanotubes. This improved the dispersion efficiency of additives such as compatibilizers.
  • Carbon nanotubes have a disadvantage in that they are difficult to disperse during the process due to their large aspect ratio (aspect ratio> 100). Therefore, a high dispersion melt mixer should be used in the melt mixing step to increase dispersion efficiency.
  • the conductive polyamide composite composition according to the embodiment of the present invention may include a resin stabilizer, a plasticizer, or the like as an additive.
  • the resin stabilizer may include, for example, a first polymer comprising a polyamide resin included in the conductive polyamide composite composition, a polyolefin resin, and a polyester in the process of manufacturing a molded article from the conductive polyamide composite composition by extrusion or injection. It stabilizes a second polymer selected from the group consisting of resins, polyolefin-based thermoplastic elastomer resins, olefin-based copolymers, and combinations thereof to serve to inhibit decomposition (eg, pyrolysis) or reaction of these resins with each other.
  • a first polymer comprising a polyamide resin included in the conductive polyamide composite composition, a polyolefin resin, and a polyester in the process of manufacturing a molded article from the conductive polyamide composite composition by extrusion or injection.
  • a second polymer selected from the group consisting of resins, polyolefin-based thermoplastic elastomer resins, olefin-based copolymers,
  • a second polymer selected from the group consisting of polyamide resins, polyolefin resins, polyester resins, polyolefin-based thermoplastic elastomer resins, olefin copolymers, and combinations thereof in the conductive polyamide composite composition may be Its properties can be better expressed, and the thermal stability, moldability, etc. of the conductive polyamide composite composition can be further improved.
  • the resin stabilizer any conventionally known resin stabilizer can be used without limitation.
  • the resin stabilizer may be phosphoric acid, triphenylphosphite, trimethylphosphite, triisodecylphosphite, tri- (2,4-di-t-butylphenyl) phosphite, 3,5-di-t -Butyl-4-hydroxybenzylphosphonic acid, tetrakis propionate methane, and combinations thereof.
  • the plasticizer not only improves the flowability and moldability of the conductive polyamide composite composition, but also improves the dispersion of carbon nanotubes and carbon black.
  • the plasticizer may be ethylene bis-stearamide, pentaerythritol, polycarprolactone, high density polyethylene (HDPE), caster oil, o-toluene Ortho-toluene sulfonamide, p-toluene sulfonamide And combinations thereof may be selected from the group consisting of.
  • the molded article may be manufactured through a conventional method of mixing the above-described components to prepare a conductive polyamide composite composition and melt extruding the prepared conductive polyamide composite composition in a mixer.
  • the conductive polyamide composite composition is 60 At ⁇ ⁇ , the surface resistance was maintained at 10 7 dl / cm 2 under immersion of 20% ethanol and fuel, showing an excellent antistatic effect.
  • the conductive polyamide composite composition is excellent in various physical properties such as moldability, chemical resistance, impact properties. That is, the conductive polyamide composite composition is excellent in overall physical properties such as not only conductivity but also moldability, so that the conductive polyamide composite can be used in high volatility fuel transport tubes and can be applied to various fields of automotive fuel systems. Can be provided.
  • a fuel transport tube made using the conductive polyamide composite composition described above.
  • the fuel transport tube comprises a first polymer comprising a polyamide resin and a base resin comprising a second polymer selected from the group consisting of polyolefin resins, polyester resins, polyolefin thermoplastic elastomer resins, olefin copolymers, and combinations thereof. And an olefin copolymer, carbon black, carbon nanotube, and optionally a resin stabilizer and a plasticizer dispersed in the base resin.
  • the fuel transport tube by using a conductive polyamide composite composition according to an embodiment of the present invention by producing a molded article comprising carbon black and carbon nanotubes, the carbon of several microns size is uniformly dispersed in the molded article By effectively connecting the carbon nanotubes between the black can realize electrical conductivity.
  • these plastic molded articles have excellent physical properties such as moldability, thermal stability and chemical resistance.
  • A-2-1 polyolefin resin which is a 1st polymer containing (A-1) polyamide resin and (A-2) 2nd polymer as (A) base resin used by the Example and comparative example which are mentioned later,
  • A-2-2 polyester resin,
  • A-2-4 olefin copolymer
  • B carbon black
  • C carbon nanotube
  • Polyamide 11 (BESNO P40TL, manufactured by Arkema) having a viscosity measured at 220 ° C. of 10,000 [Pa ⁇ s] (0.1 [1 / s] condition) or more was used.
  • Linear low-density polyethylene (4222F from Samsung Total) having a weight average molecular weight (Mw) of 1,000 ⁇ g / mol or more was used.
  • Shinite K001 manufactured by SHINONG CORPORATION having a specific gravity of 1.31 g / cm 3, a melting point of 228 ° C., and an intrinsic viscosity of 0.83 was used.
  • Ethylene-propylene diene copolymer resin (EPDM KEP020P from Kumho Petrochemical) was used.
  • Ethylene butene-maleic anhydride copolymer (Fusabond MN493D from DuPont) was used.
  • Multi-walled carbon nanotubes with tube diameters from 1 mm to 30 nm are used.
  • Nanocyl NC7000 was used as the multi-walled carbon nanotube.
  • the conductive polyamide composite compositions according to Examples 1 to 4 and Comparative Examples 1 to 4 were melt kneaded in a twin screw melt extruder heated to 250 ° C. to prepare pellets.
  • the pellet was dried at 100 ° C. for 4 hours, and then ASTM specimens for mechanical properties and conductivity evaluation, such as flexural strength, tensile strength and impact strength, were prepared using a screw-type injection machine heated to 250 ° C.
  • the dispersion of carbon black and carbon nanotubes was observed in the specimen of Example 4 using a transmission electron microscope (TEM), and the results are shown in FIG. 1.
  • TEM transmission electron microscope
  • the dispersibility of carbon black was observed in the specimen of Comparative Example 2 and shown in FIG. 2.
  • the carbon black in the first polymer comprising a polyamide resin and the second polymer selected from the group consisting of a polyolefin resin, a polyester resin, a polyolefin thermoplastic elastomer resin, an olefin copolymer and a combination thereof
  • melt mixing the carbon nanotubes in an amount in the range according to an embodiment of the present invention it was confirmed that the conductivity and mechanical properties are excellent.
  • the compatibility of the conductive polyamide composite is increased, and thus the impact reinforcing effect was exhibited.
  • Carbon nanotubes can act as an electrical bridge (electrical bridge) between the carbon black particles to reduce the content of the conductive filler contained for the conductive implementation.
  • Dispersion of carbon black is shown by expanding the comparative example 2 to a high magnification (see FIG. 2), and most of the carbon black is located in the polyamide resin, particularly concentrated at the interface between the resins, and polyolefin resin, polyester resin, polyolefin-based It is hardly observed on the thermoplastic elastomer resin or the olefin copolymer.
  • the conductivity of the molded article to which the conductive polyamide composite composition according to one embodiment of the present invention is applied is a mixture of carbon black and carbon nanotubes, whereby carbon black and carbon nanotubes are polyolefin resins, polyester resins, and polyolefins. It has a higher affinity for a polyamide resin than a thermoplastic elastomer resin or an olefin copolymer and is concentrated in the periphery of the polyamide resin.
  • the carbon nanotubes electrically connect the carbon black particles, so that the content of a low conductive filler The conductivity could be secured.
  • the specimens of Examples 1 to 4 exhibit tensile strength through effective dispersion of carbon black and carbon nanotubes and commercialization of polyamide resins, polyolefin resins, polyester resins, polyolefin thermoplastic elastomer resins or olefin copolymers. Mechanical properties such as impact strength and impact were excellent overall.

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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)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
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Abstract

L'invention porte sur une composition composite électroconductrice de polyamide comprenant: (A) une résine de base comprenant (A-1) un premier polymère comprenant une résine de polyamide et (A-2) un deuxième polymère choisi parmi: des résines de polyoléfines, des résines élastomères thermoplastiques à base de polyoléfines, des résines de copolymères à base d'oléfines, et leurs combinaisons; (B) du noir de charbon; et (C) des nanotubes de carbone. L'invention porte également sur lesdits tubes de transport de combustible.
PCT/KR2009/007981 2009-05-22 2009-12-30 Composition composite électroconductrice de polyamide, et tubes de transport de combustible l'utilisant WO2010134682A1 (fr)

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WO2020138735A1 (fr) * 2018-12-27 2020-07-02 에스케이케미칼 주식회사 Tube de transport de carburant ayant d'excellentes propriétés mécaniques et thermiques et une excellente résistance à la perméation de carburant

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KR102162652B1 (ko) * 2016-02-01 2020-10-08 캐보트 코포레이션 카본 블랙을 함유하는 열 전도성 중합체 조성물

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