KR101928864B1 - Polyketone composition with excellent heat stability for long period - Google Patents

Abstract

The present invention relates to a polyketone composition having excellent long-term thermal stability, and more particularly, to a polyketone composition having excellent long-term thermal stability using a composition comprising polyketone, pentaerythritol, potassium iodide / potassium iodide and a polymer having an optional amide bond Lt; RTI ID = 0.0 > polyketone < / RTI >

Description

[0001] The present invention relates to a polyketone composition having excellent long-term thermal stability,

The present invention relates to a polyketone composition having excellent long-term thermal stability, and more particularly, to a polyketone composition having excellent long-term thermal stability using a composition comprising polyketone, pentaerythritol, potassium iodide / potassium iodide and a polymer having an optional amide bond Lt; RTI ID = 0.0 > polyketone < / RTI >

Thermoplastic polymers are predominantly processed in molten state. No polymer is resistant to changes associated with structure and state without any change in its chemical structure. Cross-linking, oxidation, molecular weight changes, and consequent changes in physical and industrial properties can also result. To reduce the stresses on the polymers during processing, different additives are added according to the polymer.

Different additives are often used at the same time, each of which takes on a particular task. For example, antioxidants and stabilizers can be used to allow the polymer to withstand processing without chemical damage and then to have stability for external effects such as heat, UV light, weathering, and oxygen (air) Is used. In addition to improved flow properties, the lubricant prevents the polymer melt from being excessively attached to high temperature mechanical parts and acts as a dispersant for pigments, fillers and reinforcing agents.

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. . However, in spite of the superiority of conventional polyketone materials, there is an increasing demand for strict environmental regulations, durability of products, and use temperatures, and accordingly, it is required to improve the long-term heat resistance of polyketone materials in accordance with these industrial trends.

On the other hand, 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 terephthalic 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 >

Accordingly, studies on a heat-resistant polyketone composition that secures long-term heat resistance are required for the polyketone polymer.

It is an object of the present invention to provide a heat-resistant polyketone composition having a long-term tensile strength retention even under a high temperature environment in order to solve the above problems.

In order to achieve the above technical object, the present invention is 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, (Pentaerythritol); Which is characterized by containing copper iodide / potassium iodide (CuI / KI).

- [- 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)

According to a preferred embodiment of the present invention, the pentaerythritol is contained in an amount of 1 to 7 phr, the copper iodide / potassium iodide is contained in an amount of 0.3 to 3.5 phr, and the polyketone composition further contains 50 wt% or less of a polymer having an amide bond .

The retention ratio of the tensile strength measured after allowing the polyketone composition to stand at a temperature of 145 캜 for 1000 hours relative to the initial tensile strength of the polyketone composition is 50% or more.

The polyketone composition having excellent heat resistance of the present invention has long-term mechanical stiffness retention in a high-temperature use environment that can satisfy a high heat resistance grade, and thus can be used as a junction block, a band cable, a chain guide, , A radiator end tank, an engine cover, a fuel valve, a frame for a battery transfer field, a frame for office equipment, and an industrial material, which can be widely applied to various industries such as electric / electronic parts.

Hereinafter, the present invention will be described in detail.

The present invention is characterized by providing a polyketone composition having pentaerythritol, copper iodide / potassium iodide and a polymer having an additional amide bond and having excellent long-term thermal stability.

First, 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 impact strength and molding characteristics, and is excellent in thermoplastic properties It is 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.

Polyketone resin has lower moisture absorption than polyamide material, so 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, A process for producing a polyketone by terephthalic copolymerization of an ethylenic and a propylenically unsaturated compound is characterized in that a mixed solvent of 70 to 90% by volume of acetic acid and 10 to 30% by volume of water is used as a liquid medium and benzophenone .

Here, the liquid medium is characterized in that a mixed solvent of acetic acid and water is used without using methanol, dichloromethane, or nitromethane, which has conventionally been used for producing polyketones. This is because the use of a mixed solvent of acetic acid and water as a liquid medium for the production of polyketone can improve the catalytic activity while reducing the manufacturing cost of the polyketone.

When a mixed solvent of acetic acid and water is used as a liquid medium, when the concentration of water is less than 10% by volume, the activity is less affected by the catalytic activity, but when the concentration is 10% by volume or more, the catalytic activity increases sharply. On the other hand, when the concentration of water exceeds 30% by volume, the catalytic activity tends to decrease. Therefore, it is preferable to use a mixed solvent comprising 70 to 90% by volume of acetic acid and 10 to 30% by volume of water as a liquid medium.

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).

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, tricyclo undecene, 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, most preferably ethylene, and 120 mol% propylene is added in the production of the terpolymerized polyketone.

Here, it is preferable to adjust the charging ratio of the carbon monoxide and the ethylenic unsaturated compound to 1: 1 to 2 (molar ratio) and to adjust the propylene to 1 to 20 mol% based on the total mixed gas. In the production of polyketones, it is general to set the mixing ratio of carbon monoxide and ethylenic unsaturated compound to 1: 1. However, in the present invention in which a mixed solvent of acetic acid and water is used as a liquid medium and benzophenone is added during polymerization, It has been found that when the feed ratio of the unsaturated compound is adjusted to 1: 1 to 2 and the propylene is adjusted to 1 to 20 mol% based on the total mixed gas, not only the processability but also the catalyst activity and the intrinsic viscosity can be simultaneously achieved. When the amount of propylene is less than 1 mol%, the effect of the ternary copolymerization to lower the melting temperature can not be obtained. When the amount exceeds 20 mol%, the intrinsic viscosity and the improvement of the catalytic activity are inhibited, so that the addition ratio is adjusted to 1 to 20 mol% .

In addition, in the process, a mixed solvent of acetic acid and water is used as a liquid medium, benzophenone is added during polymerization, and carbon monoxide, an ethylenically unsaturated compound and one or more olefinic unsaturated compounds are added to improve the catalytic activity and intrinsic viscosity of the polyketone In addition, in the prior art, it is possible to produce a terpolymer having a high intrinsic viscosity at a polymerization time of only about 12 hours, unlike the case where the polymerization time has to be set to at least 10 hours in order to improve the intrinsic viscosity.

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 composition of the present invention, at least two units containing an ethylene moiety are contained 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.

In one embodiment, the polyketone polymer may comprise a unit represented by the following general formula as a repeating unit.

-CO- (-CH2-CH2-) - x-CO- (G) -y-

In the above general formula, G is an ethylenically unsaturated hydrocarbon, particularly a portion obtained from an ethylenically unsaturated hydrocarbon having at least three carbon atoms, and x: y is at least 1: 0.01.

In another embodiment, the polyketone polymer is a copolymer comprising repeating units represented by the general formulas (1) and (2), and y / x is preferably 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 from 0.12 to 0.17.

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

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

On the other hand, the polyketone resin preferably has an intrinsic viscosity (LVN) of 0.5 to 10 dl / g, more preferably 0.8 to 4 dl / g, and most preferably 1 to 2 dl / g. If the intrinsic viscosity of the polyketone resin is less than 0.5 dl / g, the mechanical properties may be deteriorated. If the intrinsic viscosity exceeds 10 dl / g, the workability may be deteriorated.

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 content of the polyketone resin is 50 to 100% by weight based on the total composition. If the content of the polyketone resin is less than 50% by weight, the impact strength and moldability are decreased, and cracks due to an external impact are easily generated.

Pentaerythritol, which is a second component of the present invention, is a kind of organic compound and has the form of a white crystal solid and has the following formula (2) and has a formula of C5H12O4.

This should impart heat resistance to the polyketone resin, have good compatibility with the resin, and should not affect the mechanical properties of the molded product. In addition, even when left in a high temperature environment for a long time, the tensile strength retention ratio should be higher than that of the conventional polyketone base.

The pentaerythritol of the present invention is characterized by being 1 to 7 phr. If it is less than 1 phr, the heat resistance is lowered. If it exceeds 7 phr, the heat resistance is excellent, but the price may increase and the mechanical properties may be lowered relatively.

The present invention also has copper iodide / potassium iodide (CuI / KI) as a constituent, and copper iodide / potassium iodide is a heat stabilizer and affects long-term thermal stability.

The copper iodide / potassium iodide (CuI / KI) of the present invention is characterized by being 0.3 to 3.5 phr. If it is less than 0.3 phr, heat resistance is lowered. If it exceeds 3.5 phr, mechanical properties may be deteriorated.

In addition, the present invention may further include a polymer having an amide bond. If a polymer having an amide bond is added to the composition, the tensile strength retention ratio is further increased. In the present invention, By weight or less. If it exceeds 50% by weight, the adverse effect of lowering the tensile strength retention rate occurs.

The amide bond-containing polymer is typically a polyamide and a polyurethane.

Hereinafter, a method for producing a polyketone composition having excellent long-term heat stability of the present invention will be described.

The method for producing a heat resistant polyketone composition according to the present invention comprises the steps of: preparing a catalyst composition comprising a palladium compound, an acid having a pKa value of 6 or less, and a bidentate compound of phosphorus; Preparing a mixed solvent (polymerization solvent) containing an alcohol (for example, methanol) and water; Conducting the polymerization in the presence of the catalyst composition and the mixed solvent to prepare a linear terpolymer of carbon monoxide, ethylene and propylene; Removing the remaining catalyst composition from the linear terpolymer with a solvent (e.g., alcohol and acetone) to obtain a polyketone resin; And mixing and extruding the polyketone resin with tetraphenylphosphonium iodide to prepare a composition, but the present invention is not limited thereto.

As the palladium compound constituting the catalyst composition, palladium acetate can be used. The amount of the palladium compound to be used is preferably 10 ^-3 to 10 ^-1 mole, but is not limited thereto.

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, ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis Methylene)) bis (bis (2-methoxyphenyl) phosphine) and (cyclohexane-1,1-diylbis (methylene)) bis Or more, and the amount thereof to be used is suitably 1 to 1.2 (molar) equivalent based on 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 pentaerythritol, potassium iodide / potassium iodide and a polymer having an optional amide bond, and then extruded by an extruder to finally obtain a composition. The blend may be prepared by charging it into a twin-screw extruder and melt-kneading and extruding it.

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. If the extrusion temperature is less than 230 캜, kneading may not occur properly, and if the extrusion temperature exceeds 260 캜, problems related to the heat resistance of the resin may occur. If the screw rotation speed is less than 100 rpm, smooth kneading may not occur.

When a composition is prepared by the above-mentioned method and extrusion molding or injection molding is performed, a high heat-resistant part using the polyketone composition having excellent heat resistance can be produced.

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

Linear alternating polyketone terpolymers of carbon monoxide and ethylene and propene are prepared from palladium acetate, trifluoroacetic acid, and (cyclohexane-1,1-diylbis (methylene)) bis (bis (2- methoxyphenyl) The content of trifluoroacetic acid with respect to palladium is 10 times the molar ratio and is subjected to two steps of a first stage at a polymerization temperature of 78 ° C and a second stage at 84 ° C. The polyketone terpolymer The molar ratio of ethylene to propene was 85 to 15. The melting point of the polyketone terpolymer was 220 DEG C, the LVN measured at 25 DEG C using HFIP (hexa-fluoroisopropanol) was 1.4 dl / g, and the MWD was 2.0 .

A polyketone composition was prepared by blending 100 wt% of the prepared polyketone terpolymer, 4 phr of pentaerythritol and 2 phr of copper iodide / potassium iodide to prepare a polyketone composition. The prepared composition was operated at 250 rpm to have a diameter of 40 cm and L / D = 32 in a pellet on an extruder using a twin-screw.

Example 2

Except that 97.5% by weight of the polyketone terpolymer produced, 4 phr of pentaerythritol, 2 phr of copper iodide / potassium iodide and 2.5% by weight of thermoplastic polyurethane were used.

Example 3

Except that 90 wt% of the polyketone terpolymer produced, 4 phr of pentaerythritol, 2 phr of copper iodide / potassium iodide and 10 wt% of thermoplastic polyurethane were used.

Example 4

Except that 50 wt% of the polyketone terpolymer produced, 4 phr of pentaerythritol, 2 phr of copper iodide / potassium iodide and 50 wt% of nylon 6 were used.

Comparative Example 1

A pellet was formed on the extruder using a biaxial screw having a diameter of 40 cm and an L / D of 32, which was operated at 250 rpm using polyketone as a base resin.

Comparative Example 2

100 weight% of polyketone terpolymer, and 4 phr of pentaerythritol were used.

Property evaluation

The pellets prepared in Examples 1 and 2 and Comparative Examples 1 and 2 were prepared as specimens, and physical properties were evaluated by the following methods. The results are shown in Table 1 below.

1. Tensile strength: ASTM D638. Initial tensile strength and tensile strength after being left at 145 占 폚 for 1000 hours were measured.

division Initial tensile strength (MPa) 145 DEG C, tensile strength (MPa) after 1000 hours, Tensile strength retention (%) Example 1 65 48 74 Example 2 57 51 89 Example 3 51 54 105 Example 4 57 62 109 Comparative Example 1 63 18 28 Comparative Example 2 65 21 33

As shown in Table 1, the tensile strength values at 145 ° C were superior to the initial tensile strengths at 145 ° C in Examples 1 to 3, and excellent heat resistance was obtained.

Therefore, the polyketone composition prepared through the examples is used as components of the entire industry such as automobiles and electric / electronic industries which require excellent heat resistance and heat resistance by using pentaerythritol, copper iodide / potassium iodide and additionally amide bonding polymers .

Claims (4)

A polyketone copolymer comprising repeating units represented by the following general formulas (1) and (2), which is a linear alternating polyketone and pentaerythritol having a ratio y / x of 0.03 to 0.3; A polyketone composition comprising copper iodide / potassium iodide (CuI / KI)
The pentaerythritol is 1 to 7 phr, the copper iodide / potassium iodide is 0.3 to 3.5 phr,
Wherein the polyketone composition has a retention ratio of a tensile strength of 50% or more after being left at a temperature of 145 캜 for 1000 hours relative to an initial tensile strength of the polyketone composition.
- [- 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 The method according to claim 1,
Wherein the polyketone composition further comprises 50 wt% or less of a polymer having an amide bond in addition to the total weight of the polyketone composition.
delete