KR20240030227A - Resin composition and moled article comprising the same - Google Patents

Abstract

The present invention relates to a resin composition comprising 30 to 90% by weight of a polyketone resin and 10 to 70% by weight of a heat-resistant resin, wherein the heat-resistant resin is an acrylonitrile-alphamethyl styrene copolymer and an acrylonitrile-styrene-alphamethyl styrene. It is a resin composition containing at least one selected from the group consisting of copolymers, and molded articles containing the resin composition according to the present invention are excellent in mechanical properties, heat resistance, and extrusion molding processability. In particular, the resin composition according to the present invention has excellent mechanical properties, heat resistance, and extrusion molding processability, enough to replace high-impact PPS used as a mining pipe liner.

Description

Resin composition and molded article containing the same {RESIN COMPOSITION AND MOLED ARTICLE COMPRISING THE SAME}

The present invention relates to a resin composition with improved mechanical strength, heat resistance, and extrusion molding processability, and a molded article containing the same.

Polyketone (PK) has lower raw material and polymerization process costs compared to general engineering plastic materials such as polyamide, polyester, and polycarbonate, and has excellent physical properties such as heat resistance, chemical resistance, fuel permeability, and abrasion resistance, making it suitable for use in various industries. It is widely applied.

Polyketone with the above characteristics uses a transition metal complex such as palladium (Pd) or nickel (Ni) as a catalyst to produce carbon monoxide (CO) and olefins such as ethylene and propylene. It is already known that by polymerizing ), carbon monoxide and olefin can be obtained by combining them alternately (Industrial Materials, December issue, page 5, 1997).

Meanwhile, interest is growing in a group of linear alternating polymers made of carbon monoxide and at least one ethylenically unsaturated hydrocarbon, known as polyketones or polyketone polymers. U.S. Patent No. 4,880,903 discloses linear alternating polyketone terpolymers composed of carbon monoxide, ethylene, and other olefinically unsaturated hydrocarbons, such as propylene.

The method for producing linear alternating polyketone polymers usually involves the use of a Group IX or Group X metal compound selected from palladium, cobalt, or nickel, and a non-hydro halogen strong acid. A catalyst composition produced from an anion of hydrohalogentic acid and a bidentate ligand of phosphorus, arsenic, or antimony is used. U.S. Patent No. 4,843,144 discloses a process for preparing a polymer from carbon monoxide and at least one ethylenically unsaturated hydrocarbon using a catalyst produced from a paltium compound, an anion of a nonhydrohalogen acid with a pKa of less than 2, and a bidentate ligand of phosphorus, there is.

Meanwhile, high-impact ^{polyphenylene} sulfide (PPS), such as DSM's There is a need to replace it with materials.

Accordingly, attempts have been made to replace high-impact polyphenylene sulfide with polyketone, which has relatively low raw material and polymerization process costs and excellent physical properties, but polyketone lacks mechanical strength and heat resistance to be used as a mining pipe liner, and requires long-term extrusion molding. There was a problem of poor extrusion molding processability due to gel generation during the process. In the past, heat resistance was partially improved by adding high heat resistance additives to polyketone, but it was still insufficient to replace high impact polyphenylene sulfide.

Therefore, there is a need for a resin composition with improved mechanical strength, heat resistance, and extrusion molding processability that can replace high-impact polyphenylene sulfide.

Korean Patent No. 10-1867939

The purpose of the present invention is to provide a resin composition with improved mechanical strength, heat resistance, and extrusion molding processability.

Another object of the present invention is to provide a molded article containing the above resin composition, particularly a mining pipe liner.

In order to achieve the above object, the present invention provides a resin composition comprising 30 to 90% by weight of a polyketone resin and 10 to 70% by weight of a heat-resistant resin, wherein the heat-resistant resin is acrylonitrile-alphamethyl styrene copolymer and acrylonitrile. A resin composition comprising at least one selected from the group consisting of nitrile-styrene-alphamethyl styrene copolymer is provided.

The glass transition temperature of the heat-resistant resin may be 115°C or higher.

The average molecular weight of the heat-resistant resin may be 70,000 to 300,000 g/mol.

The present invention provides a molded article containing the above resin composition.

The present invention provides a mining pipe liner containing the above resin composition.

The resin composition according to the present invention has excellent mechanical strength, heat resistance, and extrusion molding processability.

Hereinafter, the present invention will be described in detail.

The resin composition according to the present invention may include a polyketone resin and a heat-resistant resin.

polyketone resin

First, the polyketone of the present invention is a linear alternating structure, and substantially contains carbon monoxide for every molecule of unsaturated hydrocarbon. Ethylenically unsaturated hydrocarbons suitable for use as precursors for polyketone polymers have 20 or fewer carbon atoms, preferably 10 or fewer. In addition, ethylenically unsaturated hydrocarbons include ethene and α-olefins, such as propene, 1-butene, isobutene, 1-hexene, and 1-octene. ), or may be an aryl aliphatic containing an aryl substituent on another aliphatic molecule, and especially an aryl substituent on an ethylenically unsaturated carbon atom. Examples of aryl aliphatic hydrocarbons among 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 copolymer of carbon monoxide, ethene, and a second ethylenically unsaturated hydrocarbon having at least 3 carbon atoms, especially an α-olefin such as propene. It is a terpolymer of the family.

The polymer ring of the polyketone polymer preferred in the present invention can be represented by the following formula (1).

[Formula 1]

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

In structural formula 1, G is an ethylenically unsaturated hydrocarbon, especially at least three

It is a portion obtained from an ethylenically unsaturated hydrocarbon having a carbon atom, and x:y is preferably at least 1:0.01.

In another specific example, the polyketone polymer is a copolymer composed of repeating units represented by the following formula (2), and y/x is preferably 0.03 to 0.3. If the y/x value is less than 0.03, there is a limit to poor meltability and processability, and if it exceeds 0.3, mechanical properties are poor. Additionally, y/x is more preferably 0.03 to 0.1.

[Formula 2]

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

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

Additionally, the melting point of the polymer can be adjusted by adjusting the ratio of ethylene and 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 adjusted to about 220°C, but when the molar ratio is adjusted to 47.3:2.7:50, the melting point is adjusted to 235°C.

A polyketone polymer having a number average molecular weight of 100 to 200,000, especially 90,000 to 120,000, as measured by gel permeation chromatography, is particularly preferable. The physical properties of a polymer are determined by its molecular weight, whether the polymer is a copolymer or a terpolymer, and, in the case of a terpolymer, the nature of the secondary hydrocarbon moiety present. The overall melting point of the polymer used in the present invention is 175°C to 300°C, and generally is 210°C to 270°C. The intrinsic viscosity (I.V) of the polymer measured at 25°C with HFIP (Hexafluoroisopropylalcohol) using a standard tubular viscosity measuring device is 0.5 dl/g to 10 dl/g, and preferably 0.8 dl/g to 4 dl/g. Preferably, it is 2.1 dl/g to 2.6 dl/g. At this time, if the intrinsic viscosity is less than 0.5dl/g, the mechanical properties deteriorate, and if it exceeds 10dl/g, the processability decreases.

On the other hand, the molecular weight distribution of polyketone is preferably 2.0 to 4.0, and more preferably 3.2 to 3.8. If it is less than 2.0, the polymerization yield is low, and if it is more than 4.0, there is a problem of poor moldability. In order to control the molecular weight distribution, it can be adjusted proportionally according to the amount of palladium catalyst and the polymerization temperature. In other words, when the amount of palladium catalyst increases or the polymerization temperature is above 100°C, the molecular weight distribution increases.

The method for producing polyketone polymer can be liquid polymerization carried out in an alcohol solvent using a catalyst composition consisting of carbon monoxide and olefin, a palladium compound, an acid with a pKa of 6 or less, and a phosphorus diligand compound. The polymerization reaction temperature is preferably 50 to 100 °C and the reaction pressure is 40 to 60 bar. After polymerization, the polymer is recovered through filtration and purification processes, and the remaining catalyst composition is removed with a solvent such as alcohol or acetone.

Here, the palladium compound is preferably palladium acetate, and the amount used is preferably 10 ^-3 to 10 ^-1 mole. Specific examples of acids with a pKa value of 6 or less include trifluoroacetic acid, p-tolyenesulfonic acid, sulfuric acid, and sulfonic acid. In the present invention, trifluoroacetic acid was used, and the amount used is preferably 6 to 20 equivalents compared to palladium. Also, the preferred bidentate coordination compound of phosphorus is (cyclohexane-1,1-diylbis(methylene))bis(bis(2-methoxyphenyl)phosphine)).

Hereinafter, the polymerization process of the polyketone polymer will be described in detail.

Carbon monoxide, ethylenically unsaturated compounds and one or more olefinically unsaturated hydrocarbon compounds, three or more copolymers, in particular repeating units derived from carbon monoxide and repeating units derived from ethylenically unsaturated compounds and repeating units derived from propylenically unsaturated compounds are substantially Polyketone, which has an alternating structure, has excellent mechanical and thermal properties, excellent processability, and high wear resistance, chemical resistance, and gas barrier properties, making it a useful material for various purposes. This high molecular weight body of ternary or more copolymerized polyketone has higher processability and thermal properties and is considered useful as an engineering plastic material with excellent economic efficiency. In particular, it has excellent water resistance and is suitable for use in applications exposed to moisture for a long period of time. In addition, when ultra-high molecular weight polyketone with an intrinsic viscosity of 2 or more is used in the fiber, stretching at a high magnification becomes possible, and it is a fiber with high strength and high elastic modulus oriented in the stretching direction, which can be used as a reinforcing material for belts, rubber hoses, tire cords, and concrete reinforcing materials. It is a material that is very suitable for use as building materials or industrial materials.

The method for producing polyketone is a method of producing a polyketone using carbon monoxide and carbon monoxide in a liquid medium in the presence of an organometallic complex catalyst consisting of (a) a Group 9, Group 10, or Group 11 transition metal compound, and (b) a ligand having a Group 15 element. In the method of producing polyketone by ternary copolymerization of ethylenically and propylenically unsaturated compounds, 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, wherein the mixture As a solvent, a mixture of 100 parts by weight of methanol and 2 to 10 parts by weight of water can be used. If the water content in the mixed solvent is less than 2 parts by weight, ketal may be formed and heat stability may be reduced during the process, and if it exceeds 10 parts by weight, the mechanical properties of the product may be reduced.

Here, the catalyst consists of (a) a transition metal compound from Group 9, Group 10, or Group 11 of the Periodic Table (IUPAC Inorganic Chemistry Nomenclature, Revised Edition, 1989), and (b) a ligand having an element from Group 15.

Examples of Group 9 transition metal compounds among Group 9, Group 10, or Group 11 transition metal compounds (a) include complexes of cobalt or ruthenium, carbonates, phosphates, carbamates, sulfonates, etc.; Specific examples include cobalt acetate, cobalt acetylacetate, ruthenium acetate, ruthenium trifluoroacetate, ruthenium acetylacetate, and ruthenium trifluoromethane sulfonate.

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

Examples of Group 11 transition metal compounds include complexes of copper or silver, carbonates, phosphates, carbamates, and sulfonates, and specific examples thereof include copper acetate, trifluoroacetate copper, copper acetylacetate, silver acetate, and trifluoroacetate. Examples include silver fluoroacetate, silver acetylacetate, and silver trifluoromethane sulfonic acid.

Among these, transition metal compounds (a) that are inexpensive and economically preferable are nickel and copper compounds, and transition metal compounds (a) that are preferable in terms of polyketone yield and molecular weight are palladium compounds, and in terms of improving catalytic activity and intrinsic viscosity. It is most preferable to use palladium acetate.

Examples of the ligand (b) having an atom of group 15 include 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 2,2'-bi-4-picolin. , nitrogen ligands such as 2,2'-bichinoline, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino) Butane, 1,3-bis[di(2-methyl)phosphino]propane, 1,3-bis[di(2-isopropyl)phosphino]propane, 1,3-bis[di(2-methoxyphenyl) ) Phosphino] propane, 1,3-bis[di(2-methoxy-4-sodium sulfonate-phenyl)phosphino]propane, 1,2-bis(diphenylphosphino)cyclohexane, 1,2-bis (diphenylphosphino)benzene, 1,2-bis[(diphenylphosphino)methyl]benzene, 1,2-bis[[di(2-methoxyphenyl)phosphino]methyl]benzene, 1,2- Bis[[di(2-methoxy-4-sodium phenyl)phosphino]methyl]benzene, 1,1'-bis(diphenylphosphino)ferrocene, 2-hydroxy-1,3-bis[di (2-methoxyphenyl)phosphino]propane, 2,2-dimethyl-1,3-bis[di(2-methoxyphenyl)phosphino]propane, ((2,2-dimethyl-1,3-di Phosphorus ligands such as oxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine), (cyclohexane-1,1-diylbis(methylene))bis(bis( 2-methoxyphenyl)phosphine, etc. are mentioned.

Among these, the preferable ligand (b) having a Group 15 element is a phosphorus ligand having a Group 15 atom. In particular, the preferable phosphorus ligand from the viewpoint of polyketone yield is 1,3-bis[di(2- Methoxyphenyl)phosphino]propane, 1,2-bis[[di(2-methoxyphenyl)phosphino]methyl]benzene, and in terms of molecular weight of polyketone, 2-hydroxy-1,3-bis[ Di(2-methoxyphenyl)phosphino]propane, 2,2-dimethyl-1,3-bis[di(2-methoxyphenyl)phosphino]propane, does not require organic solvents and is safe. Water-soluble 1,3-bis[di(2-methoxy-4-sodium-phenyl)phosphino]propane, 1,2-bis[[di(2-methoxy-4-sodium-phenyl)phosphino ]methyl]benzene, and the ones that are easy to synthesize, available in large quantities, and economically preferable are 1,3-bis(diphenylphosphino)propane and 1,4-bis(diphenylphosphino)butane. The preferred ligand (b) having an atom of group 15 is 1,3-bis[di(2-methoxyphenyl)phosphino]propane or 1,3-bis(diphenylphosphino)propane, most preferably 1,3-bis[di(2-methoxyphenyl)phosphino]propane, ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2 -methoxyphenyl)phosphine) or (cyclohexane-1,1-diylbis(methylene))bis(bis(2-methoxyphenyl)phosphine.

[Formula 3]

((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine) of Chemical Formula 3 is a polyketone introduced to date. Expresses activity equivalent to 3,3-bis-[bis-(2-methoxyphenyl)phosphanylmethyl]-1,5-dioxa-spiro[5,5]undecane, which is known to have the highest activity among polymerization catalysts. However, its structure is simpler and its molecular weight is also lower. As a result, the present invention has been able to provide a novel polyketone polymerization catalyst that secures the highest activity as a polyketone polymerization catalyst in the field, while further reducing manufacturing costs and production costs. The method for producing the ligand for polyketone polymerization catalyst is as follows. Using bis(2-methoxyphenyl)phosphine, 5,5-bis(bromomethyl)-2,2-dimethyl-1,3-dioxane and sodium hydride (NaH) A method for producing a ligand for a polyketone polymerization catalyst is provided, characterized in that obtaining -1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine). . The method for producing a ligand for a polyketone polymerization catalyst of the present invention is a conventional method of 3,3-bis-[bis-(2-methoxyphenyl)phosphanylmethyl]-1,5-dioxa-spiro[5,5]undecane. Unlike the synthesis method, ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2- Methoxyphenyl)phosphine) can be commercially synthesized in large quantities.

Meanwhile, it is also preferable to use (cyclohexane-1,1-diylbis(methylene))bis(bis(2-methoxyphenyl)phosphine as the ligand used in the polymerization catalyst. The method of synthesizing the ligand is as follows. It is the same as the reaction equation.

[Reaction formula]

The (cyclohexane-1,1-diylbis(methylene))bis(bis(2-methoxyphenyl)phosphine ligand can be synthesized through the following four steps. First, diethylmalonate and 1, 5-Dibromopentane is boiled in sodium ethoxide and ethanol, then reduced in lithium aluminum hydride and tetrahydrofuran to synthesize 1,1-cyclohexanedimethanol, and then reacted in tosyl chloride and pyridine to remove it. It can be made to have a group. The above ligand can be obtained by reacting 2-methoxyphenylphosphine with sodium hydride and dimethyl sulfoxide. Each step goes through purification steps such as column chromatography and recrystallization, and each step Purity can be confirmed through nuclear magnetic resonance analysis.

Meanwhile, the above ligand is preferably used alone as a single site, but it is also preferable to have a multi-site.

[Formula 4]

Formula 4 is a model of a multi-site polymerization catalyst, and preferably used ligands include 1,3-bis[bi(2-methoxyphenyl)phosphino]propane, (2,2-dimethyl-1,3- Polyketone polymerization containing a ligand having a multi-site of one or two types of structures selected from the group consisting of dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine It is preferable to use a catalyst. In addition, a specific example of the model of the multi-site polymerization catalyst can be represented by the following formula 5, but is not limited to this. On the other hand, compared to using a single-site ligand, multi-site When a ligand having a site is used, there is an effect of reducing the occurrence of fouling that grows after attaching to the inner wall of the reactor during polyketone polymerization.

[Formula 5]

In a preferred embodiment, the method for producing a ligand for a polyketone polymerization catalyst of the present invention is (a) adding bis(2-methoxyphenyl)phosphine and dimethyl sulfoxide (DMSO) to a reaction vessel under a nitrogen atmosphere and hydrogenating them at room temperature. Adding sodium and stirring; (b) adding 5,5-bis(bromomethyl)-2,2-dimethyl-1,3-dioxane and dimethyl sulfoxide to the resulting mixed solution and stirring to react; (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 it with anhydrous sodium sulfate, filtering it under reduced pressure, and concentrating it under reduced pressure; and (e) recrystallizing the residue under methanol to obtain ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine) It can be performed through the steps of obtaining.

The amount of the Group 9, 10, or 11 transition metal compound (a) to be used varies depending on the type of ethylenically and propylenically unsaturated compound selected and other polymerization conditions, so it is uniformly within the range. It cannot be limited, but is usually 0.01 to 100 mmol, preferably 0.01 to 10 mmol, per 1 liter of reaction zone capacity. The capacity of the reaction zone refers to the capacity of the liquid phase of the reactor. The amount of ligand (b) used is also not particularly limited, but is usually 0.1 to 3 mol, preferably 1 to 3 mol, per mole of transition metal compound (a).

In addition, another feature is that benzophenone is added during polymerization of polyketone. In the present invention, the intrinsic viscosity of polyketone can be improved by adding benzophenone during polymerization of polyketone. The molar ratio of (a) the Group 9, Group 10 or Group 11 transition metal compound and benzophenone is 1:5 to 100, preferably 1:40 to 60. If the molar ratio of the transition metal to benzophenone is less than 1:5, the effect of improving the intrinsic viscosity of the produced polyketone is not satisfactory, and if the molar ratio of the transition metal to benzophenone exceeds 1:100, the catalytic activity of the produced polyketone is rather poor. It is undesirable because it tends to decrease

Examples of ethylenically unsaturated compounds copolymerized with carbon monoxide include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 -α-olefins such as hexadecene and vinylcyclohexane; Alkenyl aromatic compounds such as styrene and α-methylstyrene; Cyclopentene, norbornene, 5-methylnorbornene, 5-phenylnorbornene, tetracyclododecene, tricyclododecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-ethyltetra Cyclic olefins such as cyclododecene; Vinyl halides such as vinyl chloride; Acrylic acid esters such as ethyl acrylate and methyl acrylate can be mentioned. Among these, preferred ethylenically unsaturated compounds are α-olefins, more preferably α-olefins having 2 to 4 carbon atoms, and most preferably ethylene.

The ternary copolymerization of carbon monoxide with the ethylenically unsaturated compound and the propylenically unsaturated compound is an organometallic complex consisting of the Group 9, Group 10, or Group 11 transition metal compound (a) and a ligand (b) having a Group 15 element. This occurs due to a catalyst, and the catalyst is produced by bringing the two components into contact. As a method of contacting, any method can be adopted. That is, the two components may be prepared as a premixed solution in a suitable solvent and used, or the two components may be supplied separately to the polymerization system and brought into contact within the polymerization system.

In the present invention, in order to improve the processability or physical properties of the polymer, conventionally known additives such as antioxidants, stabilizers, fillers, refractory materials, mold release agents, colorants, and other materials may be additionally included.

Polymerization methods include solution polymerization using a liquid medium, suspension polymerization, and vapor phase polymerization in which a small amount of polymer is impregnated with a high concentration of catalyst solution. Polymerization may be either batch or continuous. The reactor used for polymerization can be a known reactor as is or after processing. There is no particular limitation on the polymerization temperature, and is generally 40 to 180°C, preferably 50 to 120°C. There are no restrictions on the pressure during polymerization, but it is generally normal pressure to 20 MPa, preferably 4 to 15 MPa.

Linear alternating polyketones are formed through the polymerization method described above.

heat resistant resin

The present inventor discovered that mechanical properties, heat resistance, and extrusion molding processability can be improved by appropriately mixing polyketone resin with heat-resistant resin.

The heat-resistant resin is one of heat-resistant SAN (Styrene-co-AcryloNitrile), which includes a copolymer containing alpha-methyl styrene and has superior heat resistance compared to styrene-acrylo nitrile resin.

The heat-resistant resin may include at least one selected from the group consisting of acrylonitrile-alphamethyl styrene copolymer and acrylonitrile-styrene-alphamethyl styrene copolymer.

The glass transition temperature of the heat-resistant resin is preferably 115°C or higher, HDT (Heat Deflection Temperature) is preferably 100°C or higher, and the weight average molecular weight is preferably 70,000 to 300,000 g/mol.

If the glass transition temperature of the heat-resistant resin is less than 115°C or the HDT is less than 100°C, it may be insufficient to improve the mechanical properties and heat resistance of the resin composition. In particular, if the glass transition temperature of the heat-resistant resin is less than 115°C, a problem may arise in which dry blending with the polyketone resin of the present invention is not performed smoothly. When the weight average molecular weight of the heat-resistant resin is 70,000 to 300,000 g/mol, the mechanical properties, heat resistance, and extrusion molding processability of the resin composition can all be improved.

Resin composition

A mixture is prepared by dry blending the polyketone resin and the heat-resistant resin.

The polyketone resin may preferably be contained in an amount of 30 to 90% by weight, and more preferably in an amount of 40 to 60% by weight. If the polyketone resin is contained in less than 30% by weight, strand breakage occurs continuously when extruding the mixture, making it impossible to pelletize it. If the polyketone resin is contained in excess of 90% by weight, the mechanical properties and heat resistance are affected. And extrusion molding processability is not improved.

The heat-resistant resin may preferably be contained in an amount of 10 to 70% by weight, and more preferably in an amount of 40 to 60% by weight. If the heat-resistant resin is included in less than 10% by weight, the mechanical properties, heat resistance, and extrusion molding processability of the resin composition are not improved, and if the heat-resistant resin is included in more than 70% by weight, strand breakage occurs continuously when extruding the mixture. It cannot be formed into pellets.

Next, the mixture is put into an extruder (Twin-Screw Extrude) and melt-kneaded and extruded. At this time, the extrusion temperature is preferably 230 to 250°C, and the screw rotation speed is preferably in the range of 100 to 300 rpm. If the extrusion temperature is less than 230°C, kneading may not occur properly, and if it exceeds 250°C, problems may occur in the heat resistance of the resin composition. If the screw rotation speed is less than 100 rpm, kneading may not occur properly, and if it exceeds 300 rpm, the mechanical properties of the resin composition may deteriorate.

Sheets, films, plates, and molded products can be manufactured by preparing a resin composition using the above method and extruding or injection molding it.

Examples and Comparative Examples

Hereinafter, the present invention will be described in more detail through examples, but this does not limit the scope of the present invention.

Example 1

(1) Polyketone resin

Alternating linear polyketones consisting of carbon monoxide, ethylene, and propene are produced from palladium acetate, trifluoroacetic acid, and (cyclohexane-1,1-diylbis(methylene))bis(bis(2-methoxyphenyl)phosphine. It was prepared through liquid polymerization in the presence of a catalyst composition. The mixed solvent of alcohol and water, which is the liquid medium used in liquid polymerization, was 6 parts by weight of water per 100 parts by weight of metal alcohol. The linear alternating polyketone prepared in this way It is called "730 powder." In the above, the content of trifluoroacetic acid is 10 times the molar ratio of palladium, and the polymerization temperature is 70 ℃ in the first stage and 76 ℃ in the second stage. In the "730 powder", carbon monoxide is 50 mol%. , ethylene is 46.2 mol%, and propylene is 3.8 mol%. In addition, the melting point of "730 powder" is 220 ℃, the molecular weight measured by GPC (Gel Permeation Chromatography) is Mn = 118,000, Mw = 409,000, molecular weight dispersion PDI = 3.5.

97.6% by weight of the "730 powder", 0.8% by weight of Hydroxylapatite (TCP) as a heat stabilizer, and 2,2'-oxalyldiamidobis[ethyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate as an antioxidant. (XL-1) at 1.0% by weight, ethylene-methacrylic acid resin (Dupont's Nucrel N1108C resin) at 0.3% by weight as an internal lubricant, and 2-(4,6-Bis-(2,4-dimethylphenyl)- as a UV stabilizer. The polyketone resin produced by dry mixing 0.3% by weight of 1,3,5-triazin-2-yl)-5-(octyloxy)-phenol (UV1164) and melt-kneading and extruding it with a twin-screw extruder is called "M730R". .

(2) Heat-resistant resin

HM-810 from the manufacturer Hannatech was used. The glass transition temperature of HM-810 is 11 5 ℃, HDT is 106 ℃, and the weight average molecular weight is 70,000 to 300,000 g/mol. HM-810 contains at least one selected from the group consisting of acrylonitrile-alphamethyl styrene copolymer and acrylonitrile-styrene-alphamethyl styrene copolymer.

(3) Resin composition and specimen

90% by weight of M730R and 10% by weight of HM-810 were dry blended, melt-kneaded and extruded (extrusion temperature 240°C) in an extruder to prepare a resin composition, and injection molded to prepare a specimen for measurement. did.

Examples 2 to 7

As shown in Table 1 below, a specimen for measurement was produced in the same manner as in Example 1, except that the weight percent of M730R and HM-810 was different.

Comparative Example 1 and Comparative Example 2

As shown in Table 1 below, a specimen for measurement was produced in the same manner as in Example 1, except that the weight percent of M730R and HM-810 was different.

Experiment example

The mechanical properties, heat resistance, and extrusion molding processability of the measurement specimens of Examples 1 to 7, Comparative Example 1, and Comparative Example 2 were measured as follows. The measurement results are shown in Table 2 below.

<Mechanical properties>

(1) Tensile modulus: Measured according to ASTM D638.

(2) Flexural strength and flexural modulus: Measured according to ASTM D256.

<Heat resistance>

(1) HDT (Heat Deflection Temperature): Measured at 1.82MPa according to ASTM D648.

<Extrusion molding processability>

(1) COT (Cross Over Time): COT (Cross Over Time, Gel point) was measured using a rheometer {Physica MCR 301 by Anton Paar, Inc.}. At this time, the gel point was determined by the time when G'=G'' (sol-gel transition time point), and the storage modulus and loss modulus over time were measured at 240 ℃. The point where the two curves meet is called COT.

(2) Injection residence retention rate: To evaluate the injection machine retention, the injection machine was stopped with the heater of the injection machine maintained at 240°C for 30 minutes after weighing. After reaching a certain injection retention time, injection was performed at a time of 10 shots.

(3) Continuous extrusion usable time: Continuous extrusion was performed using an extrusion extruder, and the time for continuous extrusion without gel generation was measured.

As can be seen in Table 2, Example is superior to Comparative Example 2 in mechanical properties, heat resistance, and extrusion molding processability. In particular, in the case of Comparative Example 1, strand breakage occurred continuously during extrusion and the material could not be pelletized, making it impossible to measure physical properties.

Claims (5)

30 to 90% by weight of polyketone resin and
In a resin composition containing 10 to 70% by weight of a heat-resistant resin,
The heat-resistant resin is a resin composition comprising at least one selected from the group consisting of acrylonitrile-alphamethyl styrene copolymer and acrylonitrile-styrene-alphamethyl styrene copolymer.
According to paragraph 1,
A resin composition wherein the heat-resistant resin has a glass transition temperature of 115°C or higher.
According to paragraph 1,
A resin composition wherein the heat-resistant resin has an average molecular weight of 70,000 to 300,000 g/mol.
A molded article containing the resin composition according to claim 1.
A mining pipe liner comprising the resin composition according to claim 1.