KR100792783B1 - Thermoplastic polyphenylene ethers / polyamides resin composition and process for preparing the same - Google Patents

Abstract

A conductive thermoplastic resin composition based on polyphenylene ether/polyamide is provided to improve electrical and physical properties and surface properties including heat resistance, moisture resistance, dimensional stability, workability and conductivity. A conductive thermoplastic resin composition based on polyphenylene ether/polyamide comprises: 100 parts by weight of a resin blend comprising 5-95 wt% of a polyphenylene ether resin grafted with an unsaturated carboxylic acid or anhydride thereof and obtained by grafting 0.01-3 parts by weight of reactive monomers comprising an unsaturated carboxylic acid or anhydride thereof to 100 parts by weight of a polyphenylene ether resin in the presence of an organic peroxide, and 5-95 wt% of a polyamide resin; and 0.1-10 parts by weight of acid-treated carbon nanotubes.

Description

Polyphenylene ether / polyamide-based thermoplastic resin composition and preparation method thereof {Thermoplastic polyphenylene ethers / polyamides resin composition and process for preparing the same}

1 is a scanning electron micrograph of a nanocomposite containing multi-walled carbon nanotubes in a polyphenylene ether / polyamide-based thermoplastic resin.

The present invention relates to a polyphenylene ether / polyamide-based thermoplastic resin composition and a method for producing the same, polyphenylene ether / polyamide-based thermoplastic resin composition and improved physical and surface properties such as moisture resistance, dimensional stability and conductivity, and It relates to a manufacturing method thereof.

Conductive polyphenylene ether and polyamide alloys were developed by GE Advanced Materials in 1998 for automotive fenders. Conductive polyphenylene ether and polyamide alloy resins with design flexibility are plastic resins that can be electrostatically coated and withstand high temperatures of 203 ° C. Advantages of using conductive polyphenylene ether and polyamide alloy materials over coating systems based on organic solvents include: 1) better color appearance and variety, 2) elimination of conductive primer treatment, and manufacturing processes. Cost reduction and cost reduction due to reduction of inventory burden on resins by color due to various surface treatments, 3) improved scratch resistance, 4) excellent chemical resistance, 5) over 200 ℃ to withstand the coating of metal parts and silver High heat resistance, 6) Significant reductions in VOC usage.

Polyphenylene ether and polyamide-based alloy resins having such advantages have been widely used in automobile parts, electrical and electronic parts, and mechanical parts. However, polyphenylene ether resins have disadvantages such as poor solvent resistance and impact resistance and poor workability. In addition, polyamide resin is widely used as a general-purpose engineering plastic, but its use is limited as an engineering plastic because of its excellent chemical resistance and excellent processability, but poor heat resistance and impact resistance. Therefore, a lot of researches have been conducted to complement the drawbacks of these two resins.

For example, U.S. Patent No. 3,379,792 discloses resin compositions containing 0.01 to 25% by weight of polyamide resins in polyphenylene ether resins. However, in this case, when the content of the polyamide resin is 20% by weight or more, phase compatibility occurs because of poor compatibility between the polyphenylene ether and the polyamide, and as a result, the physical properties of the molded article are significantly reduced. U.S. Patent No. 4,315,086 discloses 100 parts by weight of a resin composition consisting of 5 to 95% by weight of polyphenylene ether and 95 to 5% by weight of polyamide (A) liquid diene polymer, (B) epoxy compound and (C) ( A resin composition containing 0.01 to 30 parts by weight of a compound selected from the group consisting of a) an ethylene carbon-carbon double bond or a triple bond, and (b) a compound having a carboxylic acid, an acid anhydride, an acid amide, or a hydroxyl group. Is starting. EP 046,040 discloses a copolymer or vinyl aromatic comprising (a) a polyphenylene ether resin, (b) a vinyl aromatic compound and an α, β-unsaturated dicarboxylic anhydride unit in order to improve heat resistance, oil resistance and impact resistance. A resin composition comprising a copolymer composed of an imide compound unit of a compound with an α, β-unsaturated dicarboxylic acid, (c) a polyamide, and optionally (d) an impact modifier. PCT patent application PCT / US86 / 01511 does not have a free group initiator, at least one carbon-carbon double or triple bond and at least one carboxylic acid, acid anhydride, acid imide, imide, A process for the modification of polyphenylene ethers is disclosed by mixing at least one functional compound having ester, amino or hydroxyl groups in a liquid polyphenylene ether.

Conventional conductive plastics are commercially available for products containing carbon fibers, products containing carbon black, products containing metal fibers, and products containing inherent conductive polymers such as polyaniline. There is a problem that the market is limited because of the low formability.

On the other hand, nanotechnology is recognized as the technology of the future in various fields that will lead the 21st century. Especially, in the case of polymer nanocomposite technology using carbon nanotubes, the anisotropy of structure and physical properties of carbon nanotubes, single wall, double wall, Structural diversity with various structures such as multi-walls and wound forms, which have the properties of conductors and semiconductors, have high electrical conductivity, electrical characteristics that strongly amplify the electric field at the end of the tube when an electric field is applied, and strong covalent coupling in the longitudinal direction Due to the high Young's modulus and mechanical strength, the application fields of the secondary battery, fuel cell, display, semiconductor technology, etc. are very diverse. If mass production technology and polymer compounding technology of high-purity multi-walled carbon nanotubes are established, it will have economical, mechanical properties, and conductivity, and will be able to replace most of the materials used in the existing technology. In addition, the carbon nanotube polymer composite material is made of carbon and thus has an environmentally friendly advantage. Since carbon nanotubes and carbon black contain less amount than conductive materials, they have excellent physical properties and excellent surface properties.

SUMMARY OF THE INVENTION The present invention has been made in an effort to provide a conductive polyphenylene ether / polyamide-based thermoplastic resin composition having improved moisture resistance and dimensional stability, and improved electrical conductivity and surface properties.

Another object of the present invention is to provide a method for preparing the conductive polyphenylene ether / polyamide-based thermoplastic resin composition.

The present invention to achieve the above technical problem,

5 to 95% by weight of an unsaturated carboxylic acid or anhydride group-grafted polyphenylene ether resin obtained by grafting a reactive monomer containing an unsaturated carboxylic acid or an anhydride group thereof to a polyphenylene ether resin in the presence of an organic peroxide; And 100 parts by weight of a resin mixture comprising 5 to 95% by weight of a polyamide resin; And

Provided is a conductive polyphenylene ether / polyamide-based thermoplastic resin composition containing 0.1 to 10 parts by weight of acid treated carbon nanotubes.

According to one embodiment of the present invention, a mixture of a vinyl aromatic polymer and a polyphenylene ether resin may be used as the polyphenylene ether resin.

According to one embodiment of the present invention, the graft polyphenylene ether resin is polyphenylene ether resin, or 100 parts by weight of a mixture of vinylaromatic polymer and polyphenylene ether resin, 0.01 to 2 parts by weight of organic peroxide and unsaturated It is preferable to melt-knead 0.01-3 weight part of reactive monomers containing a carboxylic acid or its anhydride group, and to graft an unsaturated carboxylic acid or its anhydride group.

According to one embodiment of the present invention, the impact modifier may further include 0.1 to 20 parts by weight based on 100 parts by weight of the resin mixture.

According to one embodiment of the present invention, the dispersant may further comprise 0.1 to 2 parts by weight based on 100 parts by weight of the resin mixture.

The present invention to achieve the above other technical problem,

Step of grafting a reactive monomer having an unsaturated carboxylic acid or an anhydride group to a polyphenylene ether resin by reaction extrusion in the presence of an organic peroxide to obtain an unsaturated carboxylic acid or anhydride group graft polyphenylene ether resin ; And

Provided is a method for producing a conductive polyphenylene ether / polyamide-based thermoplastic resin comprising melting and kneading a polyamide and an acid treated carbon nanotube to an obtained unsaturated carboxylic acid or anhydride group graft polyphenylene ether resin. .

As another example of the other technical problem, the present invention,

Polyamide and acid treated carbon nanotubes were introduced in the middle region of the twin screw extruder while grafting a reactive monomer having an unsaturated carboxylic acid or its anhydride group to the polyphenylene ether resin by reaction extrusion in the presence of an organic peroxide. It provides a method for producing a conductive polyphenylene ether / polyamide-based thermoplastic resin comprising the step.

According to one embodiment of the production method, a mixture of a vinyl aromatic polymer and a polyphenylene ether resin may be used as the polyphenylene ether resin.

Hereinafter, the present invention will be described in more detail.

The present invention provides a conductive polyphenyl having improved electrical conductivity and surface properties while maintaining the physical properties of the resin by adding a small amount of carbon nanotubes having excellent electrical conductivity to impart conductivity to a resin mixture including polyphenylene ether and polyamide. It is to provide a ene ether / polyamide-based resin composition.

To this end, the conductive polyphenylene ether / polyamide-based resin composition according to the present invention is an unsaturated carboxylic acid obtained by grafting a reactive monomer containing an unsaturated carboxylic acid or anhydride group thereof in the polyphenylene ether resin in the presence of an organic peroxide or It is obtained by adding a predetermined amount of carbon nanotubes to a resin mixture containing the anhydride group graft polyphenylene ether resin and polyamide resin.

Hereinafter, each component used in the composition will be described.

(I) polyphenylene ether resin

Non-limiting examples of the polyphenylene ether resins to form graft polyphenylene ether resins in the composition include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-di Ethyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-ethyl-6-ethyl-1,4-phenylene) ether, poly ( 2-methyl-6-propyl-1,4-phenylene) ether, poly (2-ethyl-6-propyl-1,4-phenylene) ether, poly (2,6-dimethyl-1,4-phenyl Lene) ether or two or more copolymers thereof, and poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3,6-trimethyl-1,4 as the copolymer Copolymer of -phenylene) ether and copolymer of poly (2,6-dimethyl-1,4-phenylene) ether with poly (2,3,6-triethyl-1,4-phenylene) ether For example. Among these, copolymers of poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3,6-trimethyl-1,4-phenylene) ether, and poly (2,6- Dimethyl-1,4-phenylene) ether is preferred, and poly (2,6-dimethyl-1,4-phenylene) ether is more preferred.

The degree of polymerization of the polyphenylene ether is not particularly limited, but considering the thermal stability and workability of the resin composition, the intrinsic viscosity is preferably 0.2 to 0.8 dl / g when measured in a 25 ° C. chloroform solvent. The polyphenylene ether may be used alone, or may be used by mixing two or more kinds of compounds in an appropriate ratio.

(II) vinyl aromatic polymer

The polyphenylene ether resins have good compatibility with vinyl aromatic polymers. Therefore, also in this invention, the mixture of a polyphenylene ether resin and a vinyl aromatic polymer can be used. The vinyl aromatic polymers include polystyrene, high impact polystyrene, polychlorostyrene, poly alpha-methylstyrene, and poly t-butylstyrene, which may be used alone or as a mixture of two or more thereof. Of these, polystyrene or high impact polystyrene is preferred. Although the molecular weight of the said vinyl aromatic polymer is not specifically limited, When the thermal stability and workability of a resin composition are considered, it is preferable that weight average molecular weights are 20,000-100,000.

In forming the graft polyphenylene ether resin as described above, a polyphenylene ether resin alone or a mixture of the polyphenylene ether resin and the vinyl aromatic polymer may be used. The vinyl aromatic polymer may be used in a ratio of 0.1 to 30 parts by weight based on 100 parts by weight of the polyphenylene ether resin. If the content of the vinyl aromatic polymer is less than 0.1 part by weight, it is not particularly a problem, but it is difficult to obtain a sufficient effect due to the addition of the vinyl aromatic polymer, and if it exceeds 30 parts by weight, there is a problem such as lowering of heat resistance, which is not preferable.

(III) organic peroxides

The unsaturated carboxylic acid or its anhydride group graft polyphenylene ether resin is obtained by grafting a reactive monomer containing an unsaturated carboxylic acid or its anhydride group in the presence of an organic peroxide, wherein the organic peroxide that can be used is diisopropyl Benzenehydroperoxide, di-t-butylperoxide, p-ethane hydroperoxide, t-butylcumylperoxide, dicumylperoxide, 2,5-dimethyl 2,5-di (t-butylperoxy) hexane, Di-t-butyl diperoxy phthalate, succinic acid peroxide, t-butyl diperoxy benzoate, t-butyl peroxy maleate, t-butyl peroxy isopropyl carbonate, methyl ethyl ketone peroxide, cyclohexa Nonperoxide, or a mixture of two or more thereof may be used, and dicumylperoxide is preferably used in consideration of reactivity and processability.

The content of the organic peroxide is preferably 0.01 to 2 parts by weight based on 100 parts by weight of the polyphenylene ether resin alone or a mixture of the vinylaromatic polymer and the polyphenylene ether resin. If the content of the organic peroxide is less than 0.01 part by weight, there is a problem in that the reactive unsaturated carboxylic acid or its anhydride group monomer is not grafted. If the content is more than 2 parts by weight, thermal stability and physical properties of the final resin composition are remarkably increased due to decomposition of the resin. It is not preferable because there is a problem of deterioration.

(IV) unsaturated carboxylic acids or anhydride groups thereof

Examples of the unsaturated carboxylic acid or the anhydride group thereof, and the reactive monomer having an unsaturated carboxylic acid or an anhydride group thereof used in the preparation of the graft polyphenylene ether resin may include maleic anhydride, maleic acid, itaconic anhydride, fumaric acid, acrylic acid, Methacrylic acid esters or mixtures of two or more thereof may be used, of which maleic anhydride is preferably used.

The content of the unsaturated carboxylic acid or anhydride group thereof is preferably 0.01 to 3 parts by weight based on 100 parts by weight of the polyphenylene ether resin alone or a mixture of the vinylaromatic polymer and the polyphenylene ether resin. When the content of the unsaturated carboxylic acid or its anhydride group is less than 0.01 parts by weight, there is little effect of improving the compatibility of the final resin composition, and when the content exceeds 3 parts by weight, the unsaturated carboxylic acid or anhydride is grafted. The production process of the polyphenylene ether becomes difficult, and due to the excessive reaction, there is a disadvantage that the physical properties of the final resin composition is sharply lowered.

(V) unsaturated carboxylic acid or its anhydride group graft polyphenylene ether resin

The method for producing the polyphenylene ether resin grafted with the unsaturated carboxylic acid or anhydride is not particularly limited, but considering the relatively high working temperature, the polyphenylene ether or the above-mentioned (I) may be used. The mixture of the vinyl aromatic polymer described in (II) and the polyphenylene ether, the organic peroxide described in (III) above, and the reactive monomer described in (IV) above are mixed, and then a balm mixer or vented extruder is used. It is preferable to carry out the graft reaction in the melt kneading state.

(VI) polyamide resin

Non-limiting examples of the polyamide resin used to form the resin mixture comprising the unsaturated carboxylic acid or anhydride graft polyphenylene ether resin and the polyamide resin described in (V) above are polycaprolactam (nylon 6). , Poly (11-aminocatecanoic acid) (nylon 11), polylauryllactam (nylon 12), poly hexamethylene adipamide (nylon 6,6), polyhexamethylene dodecanoodiamide (nylon 6, 9) and nylon 6 / 6,10 which is a copolymer thereof. Nylons such as nylon 6 / 6,6 and nylon 6/12 may be used alone or in combination of two or more thereof in an appropriate ratio.

Considering the mechanical properties and heat resistance of the desired resin composition, a polyamide resin having a melting point of 200 ° C. or more and a relative viscosity (measured at 25 ° C. by adding 1% by weight of polyamide resin to m-cresol) of 2.0 dl / g or more It is preferable to use.

(VII) carbon nanotubes

The conductive polyphenylene ether / polyamide-based thermoplastic resin composition according to the present invention may include carbon nanotubes to impart conductivity, and the carbon nanotubes may be dispersed in a large area even with a small content because of their large surface area. The dispersed carbon nanotubes may be electrically connected by their ends contacting each other to form one large conductor mesh.

As examples of the carbon nanotubes, acid-treated multi-walled carbon nanotubes may be used. The multi-walled carbon nanotubes used in the present invention preferably have a density of 1.0 ± 0.2 g / cm 3, electrical resistance of 10 ⁴ to 10 ⁵ ohm / cm, length to diameter ratio of 10,000 or more, and diameter of 5 to 50 nm.

The carbon nanotubes may be used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the resin mixture containing the polyphenylene ether resin and the polyamide resin, and when the content is less than 0.1 parts by weight, the effect of imparting electrical conductivity. If the content is more than 10 parts by weight, the effect of increasing the content is inferior, and it may adversely affect the physical properties of the thermoplastic resin, which is a target material such as tensile strength and hardness, and the price is less competitive than other products. There is.

The acid treated carbon nanotubes are obtained by acid treatment of carbon nanotubes, and such a process refers to a process of acid treating the carbon nanotubes so that a large amount of carboxylate groups are present on the surface thereof.

The acid treatment is preferably performed by treating carbon nanotubes with reflux strong acid, for example, nitric acid, sulfuric acid, or a mixture thereof, but is not limited thereto and may introduce a carboxylate group to the surface of the carbon nanotubes. All known acid treatment methods suitable for the purpose are included in the present invention. The acid treated carbon nanotubes form a random network to form a conducting bridge channel, and a plurality of carboxylate groups exist on the surface thereof. In more detail, the acid treatment method according to an embodiment of the present invention is as follows:

First, the carbon nanotubes are refluxed in a mixed acid solution of nitric acid and sulfuric acid at a volume ratio of 1: 9 to 9: 1, preferably 2: 8 to 8: 2 for 72 to 120 hours, and preferably 0.1 to 0.4 μm, preferably After filtration with a 0.2 μm polycarbonate filter, the filtrate was again immersed in nitric acid and refluxed at 90 to 120 ° C. for 45 to 60 hours, followed by centrifugation. After centrifugation, the supernatant was recovered, filtered through a polycarbonate filter, the filtrate was completely dried, the dried carboxylated carbon nanotubes were dispersed in distilled water or dimethylformaldehyde (DMF), and again filtered through a polycarbonate filter. To screen only carbon nanotubes with a certain size. When the obtained carbon nanotubes are added to a solvent and sonicated, the carbon nanotube particles may be evenly dispersed. In the present invention, carboxylation of the surface of the carbon nanotubes can be confirmed by Raman spectrum, etc., and the acid-treated carbon nanotubes are present as a uniform slurry having a constant viscosity because of the carboxylate present on the surface.

(VIII) Mixing of Unsaturated Carboxylic Acid or Anhydride Group Graft Polyphenylene Ether Resin, Polyamide Resin, and Carbon Nanotube

In the present invention, in order to impart better physical properties to the resin composition, it is preferable to uniformly melt-mix the unsaturated carboxylic acid or its anhydride group graft polyphenylene ether resin with the polyamide resin.

When the unsaturated carboxylic acid or its anhydride group graft polyphenylene ether resin is mixed with the polyamide resin, the content ratio is 5 to 95 weight of the unsaturated carboxylic acid or its anhydride group graft polyphenylene ether resin. %, Preferably 20 to 80% by weight, and 5 to 95% by weight of the polyamide resin, preferably 20 to 80% by weight. If it is out of the above range, there is a problem that the moisture resistance and heat resistance are weak, which is not preferable.

In the resin composition according to the present invention, as an example of a production method capable of increasing the compatibility between the polyphenylene ether resin and the polyamide resin, the reaction extrusion method is carried out in the presence of the organic peroxide described in the above (III). To a polyphenylene ether resin as described in the above (I) to graf the reactive monomer having the unsaturated carboxylic acid or its anhydride group as described in the above (IV). Melting and kneading the tube produces a conductive polyphenylene ether / polyamide alloy resin having excellent physical properties.

As another example of the method, in order to shorten the process, a reactive monomer having an unsaturated carboxylic acid or its anhydride group as described in the above (IV) is reacted by reaction extrusion in the presence of the organic peroxide as described in the above (III). When the polyamide and acid-treated carbon nanotubes are introduced into the polyphenylene ether resin described in the above (I) while being grafted, the reactive monomer having the unsaturated carboxylic acid or its anhydride group The grafted polyphenylene ether and polyamide may react to prepare a conductive polyphenylene ether / polyamide alloy resin having excellent physical properties.

 (IX) Impact modifier

The conductive polyphenylene ether / polyamide-based thermoplastic resin composition according to the present invention may further include an impact modifier to enhance impact resistance, and examples thereof may include a styrene impact modifier.

Such an impact modifier may be used in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the conductive polyphenylene ether / polyamide-based thermoplastic resin composition according to the present invention, and if the content of the impact modifier is less than 0.1 part by weight, The impact improvement is insufficient, and if it exceeds 20 parts by weight there is a problem that the heat resistance is weak, which is not preferable.

The styrene-based impact modifiers usable in the resin composition of the present invention are derived from vinyl aromatic monomers, and block or radial triblock copolymers in the form of AB or ABA may be used. Blocks or radial triblock copolymers in the form of AB or ABA can be used copolymers composed of vinyl aromatic monomers and blocks of hydrogenated, partially hydrogenated or unsaturated hydrogenated hydrogenated, block copolymers of AB diblock type. Examples are polystyrene-polybutadiene (SBR), polystyrene-polyisoprene, polyalphamethylstyrene-polybutadiene copolymers and their hydrogenated forms. Such AB diblock type copolymers are widely known commercially, and are representative of the trade names SOLPRENED and K-RESIN from PHILLIPS, and the KRATON D and KRATON G from SHELL. Examples of the ABA triblock type block copolymers include polystyrene-polybutadiene-polystyrene (SBS), polystyrene-polyisoprene-polystyrene (SIS), polyalphamethylstyrene-polybutadiene-polyalphamethylstyrene, and polyalphamethylstyrene- Copolymers of polyisoprene-polyalphamethylstyrene and their hydrogenated forms. Such ABA triblock type copolymers are also widely known commercially, and examples thereof include SHF trade names CARFLEX, KRATON D, and KRATON G and KURARAY trade name SEPTON.

 (X) dispersant

The conductive polyphenylene ether / polyamide-based thermoplastic resin composition according to the present invention may further include a dispersant to enhance the dispersibility of each component, for example, aliphatic polyester wax or carbon number of 6 to 30 carbon atoms Turbine oil etc. which are 6-30 synthetic oils can be used.

Such a dispersant may be used in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the conductive polyphenylene ether / polyamide-based thermoplastic resin composition according to the present invention, and when the content of the impact modifier is less than 0.1 part by weight, The improvement is insufficient, and when it exceeds 2 parts by weight, there is a problem that the mechanical properties are lowered, which is not preferable.

(XI) other additives

Other components included in the conductive polyphenylene ether / polyamide-based thermoplastic resin composition according to the present invention, for example, surfactants, nucleating agents, coupling agents, fillers, plasticizers, shock absorbers, admixtures, colorants, lubricants, antistatic agents, pigments , Flame retardants, glass fibers, talc, zinc oxide, stearic acid, antioxidants, waxes, etc. are additives of known polyphenylene ether / polyamide-based thermoplastic resin compositions, each of which is selected at least one according to a range of known addition amounts It is enough to carry out by, so detailed description thereof will be omitted.

Hereinafter, the content of the present invention will be described in detail through Examples and Comparative Examples. However, the following examples are intended to illustrate the present invention in more detail, and the scope of the present invention is not intended to be limited thereto.

Example

Various components used in the examples of the present invention are as follows.

(A) polyphenylene ether resin

The polyphenylene ether resin used in the following examples of the present invention is a polyphenylene ether of Asahi Kasei Co., Ltd., Japan, and a high impact polystyrene resin, which is a vinyl aromatic polymer, used 65H manufactured by LG Chem.

(B) Maleic anhydride graft polyphenylene ether resin

In the embodiment of the present invention, maleic anhydride graft polyphenylene ether resin was prepared and used as follows.

(C) Sterrene impact modifier

The styrenic impact modifier used in the present invention is a styrene-ethylene-butadiene-styrene copolymer (SEBS) manufactured by US Shell Corporation under the trade name KRATION G 1651.

After mixing the polyphenylene ether resin, high impact polystyrene, styrene-based impact modifier, maleic anhydride, and dicumyl peroxide in the composition shown in Table 1, using a twin screw extruder L / D = 40, Φ = 40 mm Pellet maleic anhydride graft polyphenylene ether resin (P1 to P4) was prepared. At this time, the temperature of the cylinder was set to 270 to 310 ℃, the screw speed was set to 250rpm.

The graft rate of maleic anhydride among the results shown in Table 1 was calculated by reprecipitating the prepared pellets with chloroform / methanol solution, and measuring the area of the characteristic band (1780 cm ⁻¹ ) of maleic anhydride with an infrared spectrometer.

 division P1 P2 P3 P4 (A) polyphenylene ether 80 80 80 80 (B) high impact polystyrene 10 10 10 10 (C) styrene impact modifier 10 10 10 10 Maleic anhydride 0.5 1.0 1.5 2.0 Dicumyl peroxide 0.025 0.05 0.075 0.1 Grafted Content of Maleic Anhydride 0.45 0.89 1.35 1.72

(D) polyamide

Polyamide resin is the trade name polyamide 66 of Rhodia, France.

(E) Acid-treated multiwalled carbon nanotubes

Acid-treated multi-walled carbon nanotubes used in the embodiment of the present invention is a vacuum after CM-95 multi-walled carbon nanotubes prepared by chemical vapor deposition method at ILJIN Nanotech Co., Ltd. with 40% nitric acid at 80 ° C. for 2 hours. It is dried for 10 hours at 100 ℃ in the oven.

Examples 1-4

In order to uniformly disperse each component shown in Table 2, first, the component (D) maleic anhydride graft polyphenylene ether, (E) polyamide 66, and (F) acid-treated multiwall carbon nanotubes and esters Conductive polyphenylene was mixed with a wax or turbine oil and an antioxidant using a Henschel mixer, and extruded at an extrusion temperature of 280 to 310 ° C. and a screw speed of 350 rpm using a twin screw extruder having L / D = 40 and Φ = 40 mm. Ether / polyamide-based thermoplastic resin compositions were prepared in pellets. The prepared pellets were dried at 80 ° C. for 6 hours and then injected into molding conditions at a molding temperature of 270 to 280 ° C. and a mold temperature of 60 to 90 ° C. to prepare a physical specimen.

 division Example 1 Example 2 Example 3 Example 4 (D) Maleic anhydride graft polyphenylene ether (P2) 50 50 50 50 (E) polyamide 66 50 50 50 50 (F) Acid-treated multiwalled carbon nanotubes 0.5 1.0 2.0 3.0

Examples 5-8

In order to uniformly disperse the resin of each component shown in Table 3, first, the components (A) polyphenylene ether, (B) high impact polystyrene, (C) styrene-based impact modifier, maleic anhydride, and dicumylperoxide While mixing with a Henschel mixer and melt kneading at an extrusion temperature of 280 to 310 ° C. and a screw speed of 250 rpm using a twin screw extruder having L / D = 40 and Φ = 40 mm to prepare maleic anhydride graft polyphenylene ether resin, (E) polyamide 66 (F) acid-treated multi-walled carbon nanotube, and ester-based wax or turbine oil and antioxidants were mixed with Henschel mixer in the # 6 zone, which is the middle point of the twin screw extruder, By side feeding, a conductive polyphenylene ether / polyamide-based nanocomposite resin composition was prepared into pellets in a one step process. The prepared pellets were dried at 100 ° C. for 6 hours, and then injection-molded at a molding temperature of 270 to 280 ° C. and a mold temperature of 60 to 90 ° C. to prepare a physical specimen.

 division Example 5 Example 6 Example 7 Example 8 (A) polyphenylene ether 40 40 40 40 (B) high impact polystyrene 5 5 5 5 (C) styrene impact modifier 5 5 5 5 Maleic anhydride 0.5 0.5 0.5 0.5 Dicumyl peroxide 0.025 0.025 0.025 0.025 (E) polyamide 66 50 50 50 50 (F) Acid-treated multiwalled carbon nanotubes 0.5 1.0 2.0 3.0

Comparative Examples 1 to 4

Comparative Examples 1 to 4 are components (A) maleic anhydride graft polyphenylene ether, (B) polyamide 66, (C) styrene impact modifier and (D) acid treated multiwall carbon of the thermoplastic resin composition of the present invention. Nanotubes and ester waxes or turbine oils and antioxidants are made of a resin composition having a composition of maleic anhydride graft polyphenylene ether (P4) having a high content of maleic anhydride as shown in Table 4.

 division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 (D) Maleic anhydride graft polyphenylene ether (P4) 50 50 50 50 (E) Polyamide 66 50 50 50 50 (F) Acid-treated multiwalled carbon nanotubes 0.5 0.5 1.0 2.0

Experimental Example: Measurement of Physical Properties

Physical properties of the specimens prepared according to Examples 1 to 8 and Comparative Examples 1 to 4 were measured, and the results are shown in Tables 5 to 7 below. Various characteristics were measured by the following method.

(1) Tensile strength and elongation: ASTM D638

(2) Izod impact strength (1/4 and 1/8 notch): ASTM D256

(3) Heat Deflection Temperature (1/4, 4.6㎏ Load): ASTM D648

(4) Melt flow index: JIS K 7210 (Example 320 ° C., 5 kg load; Comparative Example 280 ° C., 5 kg load)

(5) Surface Resistance: ASTM D257

division Example 1 Example 2 Example 3 Example 4 Tensile Strength (kg / cm ² ) 680 675 666 658 % Elongation 55 47 42 38 Izod impact strength (kgcm / cm) 25 22 20 17 Heat deflection temperature 174 176 177 180 Melt flow index (g / 10 min) 43 42 40 38 Surface resistance (ohm-cm) 1 × 10 ⁹ 1 × 10 ⁵ 1 × 10 ⁴ 1 × 10 ³

As shown in Table 5, as the content of the acid-treated multi-walled carbon nanotubes increases, the surface resistance and the heat deformation temperature increase, but the mechanical properties decrease.

 division Example 5 Example 6 Example 7 Example 8 Tensile Strength (kg / cm ² ) 677 672 663 655 % Elongation 53 45 40 37 Izod impact strength (kgcm / cm) 24 21 19 14 Heat deflection temperature 174 176 177 180 Melt flow index (g / 10 min) 43 42 40 38 Surface resistance (ohm-cm) 1 × 10 ⁹ 1 × 10 ⁵ 1 × 10 ⁴ 1 × 10 ³

As shown in Table 6, as the content of the acid-treated multi-walled carbon nanotubes increased, the surface resistance and heat deformation temperature increased, but the mechanical properties were lowered. It can be seen that the physical properties of the conductive polyphenylene ether / polyamide-based nanocomposite thermoplastic resin prepared by the process and the one-step process of Examples 5 to 8 are similar.

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Tensile Strength (kg / cm ² ) 683 678 669 661 % Elongation 80 77 72 68 Izod impact strength (kgcm / cm) 47 44 42 39 Heat deflection temperature 174 176 177 180 Melt flow index (g / 10 min) 30 27 25 20 Surface resistance (ohm-cm) 1 × 10 ⁹ 1 × 10 ⁵ 1 × 10 ⁴ 1 × 10 ³

As shown in Table 7, when the content of maleic anhydride is high, the tensile strength does not show a big difference, and elongation and Izod impact strength are increased, but injection processability is deteriorated as the melt flow index is lowered.

The present invention is a resin composition composed of polyphenylene ether, polyamide, high impact polystyrene, styrene-based impact agent and acid-treated multi-walled carbon nanotubes and other additives. The compatibility with the multi-walled carbon nanotubes is improved to have the effect of the invention to provide a conductive polyphenylene ether / polyamide-based thermoplastic resin composition having excellent mechanical properties, heat resistance, electrical properties, and good workability.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (8)

100 parts by weight of polyphenylene ether resin, unsaturated carboxylic acid or anhydride group graft polyphenylene ether resin obtained by grafting 0.01 to 3 parts by weight of a reactive monomer containing an unsaturated carboxylic acid or an anhydride group thereof in the presence of an organic peroxide. 5 to 95% by weight; And 100 parts by weight of a resin mixture comprising 5 to 95% by weight of a polyamide resin; And A conductive polyphenylene ether / polyamide-based thermoplastic resin composition containing 0.1 to 10 parts by weight of acid treated carbon nanotubes. The method of claim 1, A conductive polyphenylene ether / polyamide-based thermoplastic resin composition, wherein the polyphenylene ether resin is a mixture of a vinyl aromatic polymer and a polyphenylene ether resin. delete The method of claim 1, Conductive polyphenylene ether / polyamide-based thermoplastic resin composition further comprises 0.1 to 20 parts by weight of the impact modifier with respect to 100 parts by weight of the resin mixture. The method of claim 1, The acid-treated carbon nanotubes have a density of 1.0 ± 0.2 g / cm 3, electrical resistance of 10 ⁴ to 10 ⁵ ohm / cm, length to diameter ratio of 10,000 or more, and diameter of 5 to 50 nm. Polyamide-based thermoplastic resin composition. In the presence of an organic peroxide, 0.01 to 3 parts by weight of a reactive monomer having an unsaturated carboxylic acid or an anhydride group is grafted to 100 parts by weight of a polyphenylene ether resin by a reaction extrusion method to unsaturated carboxylic acid or an anhydride group graft poly Obtaining a phenylene ether resin; And A method for producing a conductive polyphenylene ether / polyamide-based thermoplastic resin comprising melt kneading a polyamide and an acid treated carbon nanotube to an obtained unsaturated carboxylic acid or anhydride group graft polyphenylene ether resin. Polyamide and acid in the middle region of the twin screw extruder, while grafting 0.01 to 3 parts by weight of a reactive monomer having an unsaturated carboxylic acid or its anhydride group by 100 parts by weight of a polyphenylene ether resin by reaction extrusion in the presence of an organic peroxide. Method of producing a conductive polyphenylene ether / polyamide-based thermoplastic resin comprising the step of injecting the treated carbon nanotubes. The method according to claim 6 or 7, The polyphenylene ether resin is a mixture of a vinyl aromatic polymer and a polyphenylene ether resin, characterized in that the method for producing a conductive polyphenylene ether / polyamide-based thermoplastic resin.

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