KR101849193B1 - Polyketone composite material with improved thermal conductivity and electromagnetic wave shield - Google Patents

Abstract

The present invention is a polyketone copolymer comprising repeating units represented by the following general formulas (1) and (2), characterized by containing a linear alternating polyketone having a y / x of 0.03 to 0.3, a carbon fiber and a nano carbon material To provide a polyketone composite material. Accordingly, the polyketone composition of the present invention not only has excellent thermal conductivity, but also exhibits an effect of realizing an electromagnetic shielding function.
- [- CH2CH2-CO] x- (1)
- [- CH2 --CH (CH3) - CO] y - (2)
(x and y represent mol% of each of the general formulas (1) and (2) in the polymer).

Description

TECHNICAL FIELD The present invention relates to a polyketone composite material having improved thermal conductivity and electromagnetic wave shielding,

TECHNICAL FIELD The present invention relates to a polyketone composite material, and more particularly, to a polyketone composite material that simultaneously implements thermal conductivity and electromagnetic wave shielding function.

 Polyketone (PK) is a low-cost material for general engineering plastic materials such as polyamide, polyester, and polycarbonate, and has excellent properties such as heat resistance, chemical resistance, fuel permeability and abrasion resistance. . For this reason, there is a growing interest in a family of linear alternating polymers 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 other finely divided unsaturated hydrocarbons such as propylene.

The process for preparing the polyketone polymer is generally carried out by reacting a compound of a Group VIII metal selected from among palladium, cobalt or nickel with an anion of a strong halogen-hydrohalogentic acid, , Phosphorus, arsenic, or antimony (Antimon). U.S. Patent No. 4,843,144 discloses a method for producing a polymer of carbon monoxide and at least one ethylenically unsaturated hydrocarbon using a palladium compound, an anion of a nonhydrohalogen acid having a pKa of less than 6, and a catalyst that is a bidentate ligand Lt; / RTI >

Recently, polyketone has been used with various fillers in high value added plastics, high performance, and progress in the high-tech industry. The role of the filler can be seen as cost reduction, improvement of physical properties or properties, functionalization and improvement of processability.

In recent years, not only electric and electronic components but also the inside of the vehicle are influenced by electromagnetic waves, so that demand for simultaneously demanding the function of electromagnetic wave shielding in thermally conductive composite materials is also increasing. Composite materials that can realize both electromagnetic shielding and thermal conductivity can be manufactured in general, but composite materials that realize both functions simultaneously are required to be studied.

Korean Patent Publication No. 2014-0099996

In order to solve the above problems, the present invention aims to develop a filler composition of a composite material that implements thermal and electromagnetic shielding functions, and aims to manufacture a high thermal conductive composite material using a polyketone resin as a base resin.

According to a preferred embodiment of the present invention, there is provided a polyketone copolymer comprising repeating units represented by the following general formulas (1) and (2), wherein the ratio of y / x is 0.03 to 0.3, The present invention also provides a polyketone composite material.

- [- CH2CH2-CO] x- (1)

- [- CH2 --CH (CH3) - CO] y - (2)

(x and y represent mol% of each of the general formulas (1) and (2) in the polymer).

The carbon fiber is 30 to 70% by weight based on the total weight of the carbon fiber, and 0.25 to 0.5% by weight of the nano carbon material.

The polyketone composition of the present invention exhibits not only an excellent thermal conductivity but also an effect of realizing an electromagnetic shielding function.

Hereinafter, the present invention will be described in detail.

The present invention is characterized by providing a composite material that implements thermal and electromagnetic shielding functions by containing a carbon-based filler and a nano carbon material in a polyketone.

First, the polyketone as a main component of the present invention will be described. The polyketone resin used in the present invention is an engineering plastic and recently developed as a new resin, it is excellent in mechanical properties such as electrical conductivity and rebound resilience and molding property, and thus is usefully used as a material of various molded products and parts It is a thermoplastic synthetic resin. The mechanical properties of the polyketone resin belong to the category of high performance plastics, and they are attracting much attention as eco-friendly materials because they are polymeric materials synthesized from carbon monoxide as a raw material.

The polyketone resin is less hygroscopic than nylon, and it is possible to design various products with less changes in dimensions and physical properties due to moisture absorption. Especially, polyketone resin is more suitable for weight reduction because it has lower density than aluminum material.

Hereinafter, the process for producing the polyketone will be described.

The production process of polyketone is carried out in the presence of an organometallic complex catalyst comprising (a) a Group 9, 10 or 11 transition metal compound, and (b) a ligand having an element of Group 15, Wherein the carbon monoxide, ethylene and propylene are subjected to liquid phase polymerization in a mixed solvent of an alcohol (e.g., methanol) and water to produce a linear terpolymer, As the solvent, a mixture of 100 parts by weight of methanol and 2 to 10 parts by weight of water may be used. If the content of water in the mixed solvent is less than 2 parts by weight, a ketal may be formed to lower the heat stability in the process. If the amount is more than 10 parts by weight, the mechanical properties of the product may be deteriorated.

Wherein the catalyst comprises (a) a Group 9, 10 or 11 transition metal compound of the Periodic Table of the Elements (IUPAC Inorganic Chemical Nomenclature, 1989) and (b) a ligand having an element of Group 15 elements.

Examples of the Group 9 transition metal compound in the ninth, tenth, or eleventh group transition metal compound (a) include complexes of cobalt or ruthenium, carbonates, phosphates, carbamates, and sulfonates, Specific examples thereof include cobalt acetate, cobalt acetylacetate, ruthenium acetate, ruthenium trifluoroacetate, ruthenium acetylacetate, and ruthenium trifluoromethanesulfonate.

Examples of the Group 10 transition metal compounds include complexes of nickel or palladium, carbonates, phosphates, carbamates, sulfonates and the like. Specific examples thereof include nickel acetate, nickel acetylacetate, palladium acetate, palladium trifluoroacetate , Palladium acetylacetate, palladium chloride, bis (N, N-diethylcarbamate) bis (diethylamine) palladium and palladium sulfate.

Examples of the Group 11 transition metal compound include copper or silver complexes, carbonates, phosphates, carbamates, and sulfonates, and specific examples thereof include copper acetate, copper trifluoroacetate, copper acetylacetate, Examples of the fluoroacetic acid include silver acetyl acetate, trifluoromethanesulfonic acid and the like.

Of these, the transition metal compound (a), which is preferable inexpensively and economically, is nickel and copper compounds, and the preferable transition metal compound (a) in terms of the yield of the polyketone and the molecular weight is the palladium compound, It is most preferable to use palladium acetate.

Examples of the ligands (b) having an atom of Group XIII include 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 2,2'- Bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) (2-methoxyphenyl) propane, 1,3-bis [di (2-isopropyl) Bis (diphenylphosphino) cyclohexane, 1,2-bis (diphenylphosphino) phosphine] propane, (Diphenylphosphino) methyl] benzene, 1,2-bis [[di (2-methoxyphenyl) (Diphenylphosphino) ferrocene, 2-hydroxy-1,3-bis [di (2-methoxy- (2-methoxyphenyl) phosphino] propane, 2,2-dimethyl-1,3-bis [di (2- Spinosyns; there may be mentioned a ligand, such as propane.

Among these ligands, preferred ligands (b) having a Group 15 element are phosphorus ligands having an atom of Group 15, and particularly preferred ligands in terms of yield of polyketone are 1,3-bis [di (2- Methoxyphenyl) phosphino] propane and 1,2-bis [[di (2-methoxyphenyl) phosphino] methyl] benzene, Di (2-methoxyphenyl) phosphino] propane, and it is safe in that it does not require an organic solvent. Soluble sodium salts such as 1,3-bis [di (2-methoxy-4-sulfonic acid sodium-phenyl) phosphino] propane, 1,2- ] Methyl] benzene, and 1,3-bis (diphenylphosphino) propane and 1,4-bis (diphenylphosphino) butane are preferred for ease of synthesis and availability in large quantities and economically. The preferred ligand (b) having a Group 15 atom is 1,3-bis [di (2-methoxyphenyl) phosphino] propane or 1,3-bis (diphenylphosphino) Bis (di (2-methoxyphenyl) phosphino] propane or ((2,2-dimethyl-1,3-dioxane-5,5- -Methoxyphenyl) phosphine).

[Chemical Formula 1]

Bis (bis (2-methoxyphenyl) phosphine) bis ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis Activity equivalent to that of 3,3-bis- [bis- (2-methoxyphenyl) phosphanylmethyl] -1,5-dioxa-spiro [5,5] undecane, which is known to exhibit the highest activity among polymerization catalysts The structure is simpler and has a lower molecular weight. As a result, the present invention has been able to provide a novel polyketone polymerization catalyst having the highest activity as a polyketone polymerization catalyst of the present invention, while further reducing its manufacturing cost and cost. A method for producing a ligand for a polyketone polymerization catalyst is as follows. ((2,2-dimethyl) -2,3-dioxolane was obtained by using bis (2-methoxyphenyl) phosphine, 5,5-bis (bromomethyl) Bis (bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) is obtained by reacting a bis (methylene) . The process for preparing a ligand for a polyketone polymerization catalyst according to the present invention is a process for producing a ligand for a polyketone polymerization catalyst which comprises reacting 3,3-bis- [bis- (2-methoxyphenyl) phosphanylmethyl] -1,5-dioxa-spiro [5,5] ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2- Methoxyphenyl) phosphine) can be commercially synthesized in a large amount.

It is also preferable to use bis (bis (2-methoxyphenyl) phosphine as the ligand (cyclohexane-1,1-diylbis (methylene)) bis Respectively.

In a preferred embodiment, the process for preparing a ligand for a polyketone polymerization catalyst of the present invention comprises: (a) introducing bis (2-methoxyphenyl) phosphine and dimethylsulfoxide (DMSO) into a reaction vessel under nitrogen atmosphere, Adding sodium and stirring; (b) adding 5,5-bis (bromomethyl) -2,2-dimethyl-1,3-dioxane and dimethylsulfoxide to the resulting mixture, followed by stirring and reacting; (c) adding methanol and stirring after completion of the reaction; (d) adding toluene and water, separating the layers, washing the oil layer with water, drying with anhydrous sodium sulfate, filtering under reduced pressure, and concentrating under reduced pressure; And (e) the residue was recrystallized from methanol to obtain ((2,2-dimethyl-1,3-dioxane-5,5- diyl) bis (methylene)) bis (bis (2- methoxyphenyl) And a step of acquiring the image data.

The amount of the Group 9, Group 10 or Group 11 transition metal compound (a) to be used varies depending on the kinds of the ethylenic and propylenically unsaturated compounds to be selected and other polymerization conditions. Therefore, But it is usually from 0.01 to 100 mmol, preferably from 0.01 to 10 mmol, per 1 liter of the reaction zone. The capacity of the reaction zone means the liquid phase capacity of the reactor. The amount of the ligand (b) to be used is not particularly limited, but is usually 0.1 to 3 mol, preferably 1 to 3 mol, per 1 mol of the transition metal compound (a).

Further, the addition of benzophenone in the polymerization of the polyketone is another characteristic. In the present invention, an effect of improving the intrinsic viscosity of the polyketone can be achieved by adding benzophenone in the polymerization of the polyketone. The molar ratio of (a) the ninth, tenth, or eleventh transition metal compound to benzophenone is 1: 5-100, preferably 1:40-60. If the molar ratio of the transition metal to the benzophenone is less than 1: 5, the effect of improving the intrinsic viscosity of the produced polyketone is unsatisfactory. If the molar ratio of the transition metal to the benzophenone exceeds 1: 100, It is not preferable because it tends to decrease

Examples of the ethylenically unsaturated compound copolymerized with carbon monoxide include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, -Olefins such as hexadecene and vinylcyclohexane; Alkenyl aromatic compounds such as styrene and? -Methylstyrene; But are not limited to, cyclopentene, norbornene, 5-methylnorbornene, 5-phenylnorbornene, tetracyclododecene, tricyclododecene, tricyclodecene, pentacyclopentadecene, pentacyclohexadecene, Cyclic olefins such as cyclododecene; Vinyl halides such as vinyl chloride; Ethyl acrylate, and acrylates such as methyl acrylate. Of these, preferred ethylenically unsaturated compounds are? -Olefins, more preferably? -Olefins having 2 to 4 carbon atoms, and most preferably ethylene.

Wherein the carbon monoxide and the ethylenically unsaturated compound and the propylenically unsaturated compound are copolymerized with an organometallic complex comprising a ligand (b) having an element of group 9, group 10 or group 11 transition metal compound (a) or group 15 Catalyzed, the catalyst is produced by contacting the two components. Any method may be employed as the method of contacting. That is, the solution may be prepared as a solution in which two components are premixed in a suitable solvent, or the two components may be supplied separately to the polymerization system and contacted in the polymerization system.

As the polymerization method, a solution polymerization method using a liquid medium, a suspension polymerization method, a vapor phase polymerization method in which a small amount of a polymer is impregnated with a high concentration catalyst solution, and the like are used. The polymerization may be either batchwise or continuous. The reactor used in the polymerization can be used as it is or in a known manner. The polymerization temperature is not particularly limited, and is generally 40 to 180 占 폚, preferably 50 to 120 占 폚. The pressure at the time of polymerization is not particularly limited, but is generally from normal pressure to 20 MPa, preferably from 4 to 15 MPa.

As described above, the polyketone is produced through a polymerization process according to the above-described production process.

On the other hand, the polyketone polymer of the present invention is a line-by-line alternating structure and substantially contains carbon monoxide per one molecule of unsaturated hydrocarbon. Ethylenically unsaturated hydrocarbons suitable for use as precursors of polyketone polymers have up to 20 carbon atoms, preferably up to 10 carbon atoms. Ethylenically unsaturated hydrocarbons can also be selected from the group consisting of ethene and alpha-olefins such as propene, 1-butene, iso-butene, 1- hexene, 1- octene, , Or an aryl aliphatic group containing an aryl substituent on another aliphatic molecule, particularly containing an aryl substituent on an ethylenically unsaturated carbon atom. Examples of aryl aliphatic hydrocarbons in ethylenically unsaturated hydrocarbons include styrene, p-methyl styrene, p-ethyl styrene and m-isopropyl styrene. The polyketone polymer preferably used in the present invention is a copolymer of carbon monoxide and ethene or a second ethylenically unsaturated hydrocarbon having carbon monoxide, ethene and at least three carbon atoms, in particular alpha-olefins such as propene Is a terpolymer.

When the polyketone terpolymer is used as the main polymer component of the blend of the present invention, there are at least two units containing an ethylene moiety in each unit containing the second hydrocarbon moiety in the terpolymer. It is preferable that the number of units containing the second hydrocarbon moiety is from 10 to 100.

The polyketone polymer is a copolymer composed of repeating units represented by the general formulas (1) and (2), and it is preferable that y / x is 0.03 to 0.3. When the value of the y / x value is less than 0.03, there is a limit in that the meltability and processability are inferior. When the value of y / x is more than 0.3, the mechanical properties are poor. Further, y / x is more preferably 0.03 to 0.1.

- [- CH2CH2-CO] x- (1)

- [- CH2 --CH (CH3) - CO] y - (2)

In addition, the melting point of the polymer can be controlled by controlling the ratio of ethylene to propylene in the polyketone polymer. For example, when the molar ratio of ethylene: propylene: carbon monoxide is adjusted to 46: 4: 50, the melting point is about 220 ° C, while the melting point is adjusted to 235 ° C when the molar ratio is adjusted to 47.3: 2.7: 50.

Particularly preferred are polyketone polymers having a number average molecular weight of from 100 to 200,000, especially from 20,000 to 90,000, as measured by gel permeation chromatography. The physical properties of the polymer are determined according to the molecular weight, depending on whether the polymer is a copolymer or a terpolymer and, in the case of a terpolymer, the properties of the second hydrocarbon part. The melting point of the total of the polymers used in the present invention is 175 ° C to 300 ° C, and generally 210 ° C to 270 ° C. The intrinsic viscosity (LVN) of the polymer measured by HFIP (hexafluoroisopropyl alcohol) at 60 DEG C using a standard tubular viscosity measuring apparatus is 0.5 dl / g to 10 dl / g, preferably 0.8 dl / g to 4 dl / g, And more preferably 1.0 dl / g to 2.0 dl / g. If the intrinsic viscosity is less than 1.0 dl / g, the mechanical properties are deteriorated. If the intrinsic viscosity exceeds 2.0 dl / g, the workability is deteriorated.

On the other hand, the molecular weight distribution of the polyketone is preferably 1.5 to 2.5, more preferably 1.8 to 2.2. When the ratio is less than 1.5, the polymerization yield decreases. When the ratio is more than 2.5, the moldability is poor. In order to control the molecular weight distribution, it is possible to adjust proportionally according to the amount of the palladium catalyst and the polymerization temperature. That is, when the amount of the palladium catalyst is increased or when the polymerization temperature is 100 ° C or higher, the molecular weight distribution becomes larger.

The carbon fiber which is another component of the composite material of the present invention will be described. The carbon fiber was first known about 100 years ago when T. A. Edison carbonized bamboo fiber and used it as a filament in the bulb. The industrial production began in 1959 based on cellulose fiber. In 1990, Taekwang Industrial succeeded in producing it in Korea. Cellulose, acrylic fiber, vinylon, pitch, etc. are used as raw materials, and molecular arrangement and crystallization are changed according to raw materials or process temperature. Generally, the hexagonal rings of carbon form a layered lattice, with metallic luster and black or gray. It is excellent in heat resistance and impact resistance, strong in chemicals, and resistant to pests. In the heating process, molecules such as oxygen, hydrogen, and nitrogen escape and lose weight, so they are lighter than metal (aluminum) while they are more elastic and stronger than metal (iron). These characteristics have made it possible to produce sports goods (fishing rods, golf clubs, tennis racquets), aerospace industries (heat-resistant materials, aircraft fuselages), automobiles, civil engineering constructions (lightweight materials, interior materials) , Water purifier) and so on.

In Korea, the research team of the Chungbuk National University, Department of Safety Engineering started to develop a malodor removing device using activated carbon fiber. The adsorption capacity of adsorbent is much higher than that of using activated carbon as adsorbent. Therefore, it has a merit that it can treat a large amount at once, thereby reducing facility cost and effectively removing harmful substances, thereby greatly improving workplace environment

Specifically, the polyketone composition of the present invention is composed of a composite material composed of a combination of a polyketone, a carbon fiber, and a nano carbon material.

The weight of the carbon fiber is contained in an amount of 30 to 70% by weight based on the weight of the polyketone. If the content of the carbon fiber exceeds 70% by weight, the mechanical strength, dimensional stability and molding characteristics of the composite material decrease, . If it is less than 30%, the physical properties of the final composite material deteriorate.

Also, the present invention can use one or two kinds selected from the group consisting of carbon nanotubes and graphene, which are nano carbon materials, and the content is preferably 0.25 to 0.5 wt%. If the content is more than 0.5% by weight, the mechanical strength, dimensional stability and molding properties of the composite material may deteriorate and practicality may be lost. If it is less than 0.25%, the physical properties of the final composite material are deteriorated.

Hereinafter, the production method for producing the polyketone composite material is as follows.

The method for producing a polyketone composite material of the present invention comprises: 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 of methanol and water (polymerization solvent); 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 to obtain a polyketone resin; And mixing the polyketone resin with the carbon fiber and the nano carbon material.

The carbon fiber is preferably 30 to 70% by weight based on the total weight of the entire composite material, and the nano carbon material is preferably 0.25 to 0.5% by weight based on the total weight of the composite material.

The nano carbon material is preferably one or two selected from the group consisting of carbon nanotubes and graphene.

On the other hand, as the palladium compound constituting the catalyst composition, palladium acetate can be used, and the amount of the palladium compound used is suitably 10 ^-3 to 10 ^-1 mole.

As the acid having a pKa value of 6 or less constituting the catalyst composition, at least one selected from the group consisting of trifluoroacetic acid, p-toluenesulfonic acid, sulfuric acid and sulfonic acid, preferably trifluoroacetic acid, may be used. 6 to 20 (mol) equivalents relative to the compound is appropriate.

Examples of the bidentate ligand compound constituting the catalyst composition include 1,3-bis [diphenylphosphino] propane (e.g., 1,3-bis [di (2-methoxyphenylphosphino)] propane, Bis [bis [anisyl] phosphinomethyl] -1,5-dioxaspiro [5,5] undecane and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis Methylene)) bis (bis (2-methoxyphenyl) phosphine) may be used, and the amount thereof is suitably 1 to 1.2 (mol) relative to the palladium compound.

The carbon monoxide, ethylene and propylene are liquid phase polymerized in a mixed solvent of alcohol (e.g. methanol) and water to produce a linear terpolymer. As the mixed solvent, a mixture of 100 parts by weight of methanol and 2 to 10 parts by weight of water may be used. If the content of water in the mixed solvent is less than 2 parts by weight, a ketal may be formed to lower the heat stability in the process. If the amount is more than 10 parts by weight, the mechanical properties of the product may be deteriorated.

The polymerization temperature is preferably 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.

In the present invention, the obtained polyketone resin is mixed with the conductive carbon black and the elastic polyurethane, and then extruded by an extruder to finally obtain a composite material. The composite material is produced by putting into a twin-screw extruder, melt-kneading and extruding.

At this time, the resin may be fed into the main hopper of the extruder, the filler may be fed into the side feeder, or the feed may be simultaneously carried out.

In this case, the extrusion temperature is preferably 230 to 260 ° C, and the screw rotation speed is preferably in the range of 100 to 300 rpm. More preferably, the extrusion temperature is 240 to 250 ° C, and the screw rotating speed is 150 to 250 rpm. If the extrusion temperature is less than 230 캜, kneading may not occur properly. If the extrusion temperature is higher than 260 캜, problems related to the heat resistance of the resin may occur. If the screw rotation speed is less than 100 rpm, smooth kneading may not occur.

Hereinafter, the present invention will be described in detail 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

(2, 2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) anion of trifluoroacetic acid. Linear propylene terpolymer of carbon monoxide, ethylene and propylene was polymerized at 80 DEG C in a mixed solvent of 5 parts by weight of water with respect to 100 parts by weight of methanol. The molar ratio of ethylene to propene in the polyketone terpolymer prepared above was 46 to 4. On the other hand, the melting point of the polyketone terpolymer was 220 DEG C, and the intrinsic viscosity (LVN) measured on 1,1,1,3,3,3-HFIP was 1.5 dl / g.

69.5 wt% of the polyketone terpolymer prepared above, 30 wt% of carbon fiber, and 0.5 wt% of carbon nanotubes were blended to prepare a polyketone composite material.

Example 2

A polyketone composite material was prepared by blending 69.5 wt% of the polyketone terpolymer produced by the method of Example 1, 30 wt% of carbon fiber, and 0.5 wt% of graphene.

Example 3

A polyketone composite material was prepared by blending 69.5 wt% of the polyketone terpolymer produced by the method of Example 1, 30 wt% of carbon fibers, 0.25 wt% of carbon nanotubes, and 0.25 wt% of graphene.

Comparative Example 1

(2, 2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) anion of trifluoroacetic acid. Linear propylene terpolymer of carbon monoxide, ethylene and propylene was polymerized at 80 DEG C in a mixed solvent of 5 parts by weight of water with respect to 100 parts by weight of methanol. The molar ratio of ethylene to propene in the polyketone terpolymer prepared above was 46 to 4. On the other hand, the melting point of the polyketone terpolymer was 220 DEG C, and the intrinsic viscosity (LVN) measured on 1,1,1,3,3,3-HFIP was 1.5 dl / g.

70 wt% of the polyketone terpolymer prepared above and 30 wt% of carbon fiber were blended to prepare a polyketone composite material.

Property evaluation

The above Examples 1 to 3 and Comparative Example 1 were prepared as specimens and evaluated. The results are shown in Table 1 below.

1) Thermal conductivity: Measured according to ASTM E1461 method, and measured in plane of laser flash method.

2) Electromagnetic Wave Shielding: After giving the product to each area of DC / AC current, noise was checked. (CE emission noise area: + volts ~ -volt (0.1 ~ 108M), RE conduction noise area: Hor 30M ~ 2.5G, Ver 100k ~ 2.5G)

We confirmed the level of ng almost similar to that of conventional aluminum metal. Other material ng is high.

Example 1 Example 2 Example 3 Comparative Example 1 Thermal conductivity performance O O O X EMI shielding performance
(Ng comparison with aluminum metal) Similarity Similarity Similarity height

As shown in Table 1, it can be seen that thermal conductivity and electromagnetic wave shielding characteristics are simultaneously realized in comparison with Comparative Example 1 in Examples 1 to 3. Particularly, in the case of the embodiment, the ng level was almost the same as that of the conventional aluminum metal, and the ng level in the comparative example was high.

Claims (4)

A polyketone copolymer comprising repeating units represented by the following general formulas (1) and (2), which comprises a linear alternating polyketone having a y / x of 0.03 to 0.3, a carbon fiber and a nano carbon material,
Wherein the carbon fiber is 30 wt% based on the total weight of the composite material, the nano carbon material is 0.5 wt%
Wherein the nano carbon material is one or two selected from the group consisting of graphene and carbon nanotube,
Wherein the polyketone copolymer has a molecular weight distribution of 1.5 to 2.5 and an intrinsic viscosity of 1.0 to 2.0 dl / g.
- [- CH2CH2-CO] x- (1)
- [- CH2 --CH (CH3) - CO] y - (2)
(x and y represent mol% of each of the general formulas (1) and (2) in the polymer).
delete delete delete