KR20120059869A - Conductive Polyketone and Method for Preparing the Same - Google Patents

Abstract

PURPOSE: A conductive polyketone blend is provided to have improved impact strength and electrical conductivity, thereby using for interior and exterior components of a vehicle, a bearing, a roller, a keyer, a connector, an external housing of a computer, etc. CONSTITUTION: A conductive polyketone blend comprises 97-99 weight% of linear alternating polyketone polymer, and 1-3 weight% of graphene based on total weight of the blend. The linear-exchange polyketone polymer consists of at least one of ethylene-based unsaturated hydrocarbon with carbon monoxide, has surface resistance of 10 - 10^5 angstrom/square, and has notched charpy impact strength of 12.5 KJ/m^2 or higher.

Description

Conductive Polyketone and Method for Preparing the Same

The present invention relates to a poly ketone polymer composition having improved electrical conductivity, and more particularly, a blend comprising a linear alternating polymer and graphene of carbon monoxide and at least one ethylene-based unsaturated hydrocarbon ( blend).

Since most polymers have insulating properties, in order to impart conductivity, they may be mixed with specific additives to impart electrical properties. Additives that can impart electrical properties include metal powder, carbon black, carbon tubes, and the like, and particularly, researches on carbon tubes capable of obtaining high conductivity have been actively conducted. However, due to the high price of carbon tubes, their use is limited.

Graphene is a combination of graphite (graphite), which means graphite, and ene, a suffix, which means molecules with double carbon bonds. It is a material that makes up. Graphene is made of thin, transparent, chemically stable carbon, which provides excellent electrical conductivity and 100 times more current than copper. In addition, graphene can be stretched or bent without changing its existing properties.

Graphene also moves electrons 100 times faster than silicon used in semiconductors and generates power by bending, pressing, or vibrating even without an external power supply. Therefore, in the case of dispersing in the polymer material, even with a small amount of addition, high conductivity and mechanical properties can be obtained.

There is a growing interest in linear alternating polymers consisting of carbon monoxide and at least one ethylenically unsaturated hydrocarbon, known as polyketones or polyketone polymers.

U.S. Patent No. 4,880,903 discloses a linear alternating polyketone terpolymer consisting of carbon monoxide, ethylene and a olefinic unsaturated hydrocarbon (for example propylene). In this patent, a compound of Group VIII metal selected from the group consisting of palladium, cobalt or nickel, anions of strong non-hydrohalogentic acid, phosphorus, arsenic or antimony Polyketone polymers are prepared using a catalyst composition resulting from the bidentate ligand of (Antimon).

U.S. Patent No. 4,843,144 describes a polymer of carbon monoxide with at least one ethylenically unsaturated hydrocarbon using a palladium compound, an anion of less than about 6 nonhydrohaloic acid anion, and a preferred catalyst consisting of a bidentate ligand of phosphorus. A manufacturing method is disclosed.

Further, Japanese Laid-Open Patent Publication No. 1996-337678 discloses a method for producing a polymer of a resin composition composed of 97 to 50% by weight of polyolefin-based polymer resin and 3 to 50% by weight of carbon black as an antistatic resin material.

The present invention aims to provide a polyketone blend imparted with conductivity. It is another object of the present invention to provide a polyketone blend having an improved impact strength, to provide a blend that can be used in the manufacture of exterior housings, such as automotive interior and exterior parts, bearings, rollers, keyers, connectors, computers.

In order to solve the above problems, according to a preferred embodiment of the present invention, 97 to 99% by weight of the linear alternating polyketone polymer composed of carbon monoxide and at least one ethylenically unsaturated hydrocarbon and 1-3% by weight of graphene It provides a conductive polyketone blend, characterized in that the% is mixed.

According to another suitable embodiment of the present invention, the polyketone blend provides a conductive polyketone blend, characterized in that the surface resistance is 10 to 10 ⁵ kW / square.

According to another suitable embodiment of the present invention, the polyketone blend provides a conductive polyketone blend, characterized in that the Charpy impact strength is at least 12.5 KJ / m ² .

The conductive polyketone blends of the present invention exhibit improved impact strength and electrical conductivity. The polyketone blend of the present invention can be used for the manufacture of exterior housings such as interior and exterior parts, bearings, rollers, keyers, connectors, computers, etc. of automobiles.

The present invention relates to a conductive polyketone composite resin, and in particular, provides a blend of linear alternating polymer and graphene consisting of carbon monoxide and at least one ethylenically unsaturated hydrocarbon.

Polyketone polymers are polymer materials whose usefulness as thermoplastics is excellent in the manufacture of molded articles such as food containers or parts for the automotive industry. However, in certain applications it is advantageous to have properties that are somewhat different from those of conventional polyketone polymers. It is therefore an object of the present invention to provide a polyketone blend with improved other properties, in particular conductivity, while maintaining the conventionally desirable properties.

In general, polyketones are insulators and therefore have a surface resistance of 10 ¹² to 10 ¹⁴ ohms / squre. However, the polymer must exhibit 10 ⁰ to 10 ⁵ ohms / squre to have constant conductivity.

The present invention provides a blend of polyketone polymer and graphene in order to make the polyketone have constant conductivity. In particular, the composite resin composition and electrically conductive blend which consist of 99-97 weight% of linear alternating polymers, and 1-3 weight% of graphene are provided. Blends of the present invention exhibit improved impact strength and electrical conductivity.

The polyketone polymer is a linear alternating structure and contains substantially carbon monoxide per molecule of unsaturated hydrocarbons. Suitable ethylenically unsaturated hydrocarbons for use as precursors of polyketone polymers have up to 20 carbon atoms, preferably up to 10 carbon atoms, and ethene and α-olefins (e.g. propene, 1-butene) ), Aryl substituents on aliphatic or other aliphatic molecules such as isobutene, 1-hexene, 1-octene, and especially ethylenically unsaturated carbon sources Examples of the aryl aliphatic hydrocarbons in ethylenically unsaturated hydrocarbons include styrene, p-methyl styrene, p-ethyl styrene, and m. -Isopropyl styrene.

Preferred polyketone polymers in the present invention are copolymers of carbon monoxide and ethene or α-olefins such as second ethylenically unsaturated hydrocarbons (especially propene) having at least three carbon atoms with carbon monoxide and ethene. Terpolymer.

When using the polyketone terpolymer as the main polymer component of the blend of the present invention, for each unit containing the second hydrocarbon moiety in the terpolymer, it is preferred that at least two units contain the ethylene moiety, It is more preferable that it is 10-100.

Particularly advantageous are polyketone polymers having a number average molecular weight of 100 to 200,000, in particular 20,000 to 90,000, as measured by gel permeation chromatography. The physical properties of the polymer depend on the molecular weight, whether the polymer is a copolymer or terpolymer, and in the case of the terpolymer, the properties of the second hydrocarbon moiety present. Melting | fusing point of a polymer is 175 degreeC-300 degreeC normally, and generally 210 degreeC-270 degreeC. The ultimate viscosity number (LVN) of the polymer measured at 60 ° C. using a standard tubular viscosity measuring device and HFIP (Hexafluoroisopropylalcohol) is 0.5 dl / g to 10 dl / g, more preferably 0.8 dl / g to 4 dl / g.

In the present invention, a method for preparing a polyketone polymer is referred to the contents disclosed in US Pat. No. 4,843,144. Polyketone polymers are prepared by contacting a carbon monoxide with a hydrocarbon monomer under polymerization conditions in the presence of a palladium compound and a catalyst composition suitably formed from an anion of phosphorus and a bidentate ligand of less than 2 pKa, preferably less than 2 do.

The second component of the polyketone blend of the present invention is graphene. Graphene was used for the purpose of imparting conductivity to polyketones and reducing the surface resistance of resin molded articles. Graphene (graphene) is added amount varies depending on the type of graphene (graphene), preferably 0.5 to 5% by weight based on the total blend weight. If the content of graphene is less than 0.5% by weight, the conductivity is insufficient. If the content of graphene is 5% by weight or more, it is difficult to form an appearance, resulting in a significant decrease in impact strength. Various stabilizers etc. can be added to the polyketone blend of this invention suitably in the range which does not impair the characteristic, and can be used. The method of making the polyketone blend is not critical, so long as a uniform blend is produced without causing the blend or blend component to produce excessive collapse. In a modification of the present invention, it is preferable to blend the polymer component in a mixing device exhibiting high shear stress. The blend can be processed by conventional methods such as extrusion and injection molding to produce sheets, films, plates and shaped articles. Examples of such applications include interior parts and exterior parts used in automobiles.

Hereinafter, the configuration and effects of the present invention will be described in more detail with specific examples, but these examples are merely intended to more clearly understand the present invention and are not intended to limit the scope of the present invention. The present invention is described in detail by the following non-limiting examples. The method for producing the polyketone blend of the present invention is not particularly limited, but can be carried out by a known method such as a single screw extruder or a twin screw extruder.

In the examples below, the physical properties of the polyketone blends were measured under the following conditions.

(1) Notched charpy Izod impact strength: Measured according to KS M ISO 179-1.

(2) Conductivity: Surface resistivity is measured according to ASTM D 257.

(3) Surface appearance: Extruded pellets and injection molded articles are molded and visually judged. Good things are represented by ◎, ○, some bad things are △, bad things are represented by Ⅹ.

Example 1

Linear alternating terpolymers consisting of carbon monoxide, ethylene and propene were prepared in the presence of a catalyst composition produced from palladium acetate, trifluoroacetic acid and 1,3-bis [bis (2-methoxyphenylphenyl-phosphino] propane. The polyketone polymer had a melting point of 215 ° C., a LVN of 1.20 dl / g measured at 25 ° C. with hexa-fluoroisopropanol (HFIP), and a Melt flow Index of 60 g / 10 min at 230 ° C. and 2.16 kg. Samples prepared together are pelletized on an extruder by using a 32 mm twin screw operating at 200 rpm to set the temperature to 240 ° C. The polyketone polymer is 0.2% by weight of Irganox 1010 from Ciba-Geigey and 0.2% by weight of Budenheim. 0.2 wt% of Calcium Hydroxyapatite and 0.1 wt% of a commercial copolymer of ethene and methacrylic acid (trade name Nucrel 1183C) were prepared.

Example 2

After mixing the polyketone pellets and graphene (graphene) prepared in Example 1 in the ratio of Table 1 below, by using a 32mm biaxial screw was set to a temperature at 240 ℃ extruded into pellets. The pellets were prepared into test pieces using an injection molding machine (Wujin Serex NT-80), and the physical properties of each test piece were evaluated.

Polyketone wt (%) Graphene wt (%) Surface resistance
(Ω / square) Surface appearance Charpy Impact Strength (KJ / m ² ) 100 0 10 ¹² ~ 10 ¹⁴ ◎ 12.5 99 One 10 ⁹ ○ 13.4 98 2 10 ³ ○ 15.8 97 3 10 ³ △ 15.0 95 4 10 ² X 9.5

Surface resistance, surface appearance, and Notched charpy impact strength of each sample are shown in Table 1. When the content of polyketone polymer was 100% by weight, the surface resistance was 10 ¹² ~ 10 ¹⁴ Ω / square and the Charpy impact strength was 12.5 KJ / m ^2, but the content of graphene increased to 1 to 3% by weight. The surface resistance was analyzed to have electrical conductance. However, when the graphene content is more than 3% by weight, the extrudability is poor, the surface appearance is not good, and the compounding itself is difficult. As a result, the Charpy impact strength did not increase but decreased. Therefore, the graphene (graphene) content of 1 to 3% by weight showed the best properties.

Claims (3)

A conductive polyketone blend comprising 97 to 99% by weight of a linear alternating polyketone polymer composed of carbon monoxide and at least one ethylenically unsaturated hydrocarbon and 1 to 3% by weight of graphene, based on the total blend weight. The method according to claim 1,
The polyketone blend is a conductive polyketone blend, characterized in that the surface resistance of 10 ~ 10 ⁵ Ω / square. The method according to claim 1,
The polyketone blend is a conductive polyketone blend, characterized in that the Charpy impact strength is 12.5KJ / m ² or more.