KR102278150B1 - Polyketone flexible tube improved low temperature impact strength and flexibility - Google Patents

Abstract

The present invention relates to a polyketone flexible tube manufactured by extrusion molding a polyketone composition containing: polyketone; a cold-resistant plasticizer; ABS rubber; and a processing stabilizer, and more specifically, to a polyketone flexible tube that can be mass-produced with excellent low-temperature impact properties and high flexibility by adding tricalcium phosphate and fluorine-based processing stabilizer as the processing stabilizer.

Description

Polyketone flexible tube with excellent low-temperature impact and flexibility {POLYKETONE FLEXIBLE TUBE IMPROVED LOW TEMPERATURE IMPACT STRENGTH AND FLEXIBILITY}

The present invention relates to a polyketone flexible tube having excellent low-temperature impact properties and high flexibility.

Polyketone (PK) is a material that has a lower raw material and polymerization process cost compared to general engineering plastic materials such as polyamide, polyester, and polycarbonate, and has excellent heat resistance, chemical resistance, impact resistance, and fuel permeability resistance. Polyketone with these properties is included in general-purpose high-performance plastics and has a strength comparable to that of conventional engineering plastics.

On the other hand, the flexible (flexible) tube is flexible and is made of a material having good pressure resistance and chemical resistance. In using a flexible tube, a plasticizer can be applied to realize sufficient flexibility, but when the plasticizer is applied, the impact resistance at low temperature (low temperature impact resistance) is deteriorated. Accordingly, there was an attempt to apply acrylonitrile butadiene styrene rubber (ABS Rubber) to supplement low-temperature impact properties.

Recently, a method for supplementing low-temperature impact properties by reducing the content of a plasticizer used in the manufacture of flexible tubes and applying a cold-resistant plasticizer has also been proposed. However, this method did not have a problem in manufacturing the flexible tube in a laboratory, but when mass production is applied to the mass production stage, there is a problem that the processing stability is lowered.

Accordingly, there is a demand for the development of a polyketone flexible tube with improved processing stability so that it can be mass-produced while having excellent low-temperature impact properties.

Korean Patent No. 1928869 Korean Patent No. 1664925 Japanese Patent Laid-Open No. 2001-200154 Korean Patent No. 1558692

An object of the present invention is to provide a polyketone flexible tube having excellent low-temperature impact properties, high flexibility, and improved processing stability for mass production.

Polyketone flexible tube according to an embodiment of the present invention 70.0 to 89.0% by weight of polyketone consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon; Cold-resistant plasticizer 5.0-15.0 wt%; 5.0 to 15.0 wt% of acrylonitrile butadiene styrene rubber; 0.1 to 1.0% by weight of tricalcium phosphate; And it may include a polyketone composition comprising 0.01 to 0.4% by weight of a fluorine-based processing stabilizer.

In this case, the cold-resistant plasticizer is 2,2,4-trimethyl-1,3-pentadiol diisobutyrate (2,2,4-Trimethyl-1,3-pentanediol diisobutyrate), and the fluorine-based processing stabilizer is hexafluoro It may be a copolymer of propylene and vinylidene fluoride.

In addition, the temperature change of the molten resin of the polyketone composition may be 1 ~ 3 ℃ / hr.

In addition, the polyketone flexible tube may have a low-temperature impact strength of 9kJ/m ² or more measured at -40° C., a flexural modulus of 500 to 800 MPa, and a room temperature rupture of 60 bar or more.

According to an embodiment of the present invention, the polyketone flexible tube can secure processing stability capable of mass production without changing basic physical properties by applying a processing stabilizer to improve processing stability for mass production.

In addition, the polyketone flexible tube according to the present invention has the effect of greatly improving the impact properties at low temperatures such as minus 40 degrees while maintaining the burst pressure and flexibility.

Since the present invention can have various changes and can have various forms, specific embodiments are illustrated in the drawings and described in detail in the text. However, this is not intended to limit the present invention to the specific disclosed form, it should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention.

In the present application, terms such as “comprise” or “have” are intended to designate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, but one or more other features It is to be understood that it does not preclude the possibility of the presence or addition of numbers, steps, operations, components, parts, or combinations thereof.

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

Polyketone flexible tube according to an embodiment includes a polyketone consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon; cold-resistant plasticizer; acrylonitrile butadiene styrene rubber; tricalcium phosphate; And it may include a polyketone composition comprising a fluorine-based processing stabilizer.

First, the polyketone of the present invention is a linear alternating structure, and substantially contains carbon monoxide for each molecule of unsaturated hydrocarbons. Suitable ethylenically unsaturated hydrocarbons for use as precursors of polyketone polymers have up to 20, preferably up to 10 carbon atoms. In addition, ethylenically unsaturated hydrocarbons include ethene and α-olefins such as propene, 1-butene, iso-butene, 1-hexene, and 1-octene. ) or aryl aliphatic containing an aryl substituent on another aliphatic molecule, in particular an aryl substituent on an ethylenically unsaturated carbon atom. Examples of the aryl aliphatic hydrocarbon among the 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 at least 3 carbon atoms with carbon monoxide and ethene, particularly an α-olefin such as propene. It is a terpolymer of the family.

When the polyketone terpolymer is used as the main polymer component of the composition according to the present invention, there are at least two units containing an ethylene moiety for each unit containing the second hydrocarbon moiety in the terpolymer. It is preferred that there are 10 to 100 units comprising a second hydrocarbon moiety.

The polymer ring of the polyketone polymer preferred in the present invention may be represented by the following Structural Formula 1.

[Structural Formula 1]

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

In Structural Formula 1, G is an ethylenically unsaturated hydrocarbon, particularly a moiety obtained from an ethylenically unsaturated hydrocarbon having at least 3 carbon atoms, and x:y is preferably at least 1:0.01.

In another embodiment, the polyketone polymer is a copolymer comprising repeating units represented by formulas (1) and (2), and y/x is preferably 0.03 to 0.3. When the numerical value of the y/x value is less than 0.03, there is a limitation in that meltability and processability are deteriorated, and when it exceeds 0.3, mechanical properties are deteriorated. 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 adjusting the ratio of ethylene and propylene of 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, but when the molar ratio is adjusted to 47.3: 2.7: 50, the melting point is 235 °C.

Polyketone polymers having a number average molecular weight of 100 to 200,000, particularly 20,000 to 90,000 as measured by gel permeation chromatography are particularly preferred. The physical properties of a polymer depend on its molecular weight, on whether the polymer is a copolymer or terpolymer, and in the case of a terpolymer, on the nature of the secondary hydrocarbon moieties present. The general melting point of the polymer used in the present invention is 175°C to 300°C, and generally 210°C to 270°C. The intrinsic viscosity (IV) of the polymer measured at 60 ° 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, and more Preferably, it is 1.0 dl/g - 1.4 dl/g. At this time, if the intrinsic viscosity number is less than 1.0 dl/g, the mechanical properties are deteriorated, and when it exceeds 1.4 dl/g, the processability 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. If it is less than 1.5, the polymerization yield is poor, and if it is 2.5 or more, there is a problem in that the moldability is poor. In order to control the molecular weight distribution, it is possible to control in proportion to the amount of the palladium catalyst and the polymerization temperature. That is, if the amount of the palladium catalyst is increased or the polymerization temperature is 100° C. or higher, the molecular weight distribution is increased.

Liquid polymerization carried out in an alcohol solvent through a catalyst composition comprising carbon monoxide and an olefin as a palladium compound, an acid having a PKa of 6 or less, and a diligand compound of phosphorus can be employed as a method for preparing the polyketone polymer. The polymerization reaction temperature is preferably 50 ~ 100 ℃ and the reaction pressure is 40 ~ 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.

This is preferred as palladium acetate and a palladium compound in the amount of 10 ^-3 to ^10-2 1mole preferred. Specific examples of the acid having 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. In addition, as the bidentate compound of phosphorus, 1,3-bis[di(2-methoxyphenylphosphino)]propane is preferable, and the amount used is preferably 1 to 1.2 equivalents relative to palladium.

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

Carbon monoxide, an ethylenically unsaturated compound and one or more olefinically unsaturated hydrocarbon compounds, three or more copolymers, in particular a repeating unit derived from carbon monoxide and a repeating unit derived from an ethylenically unsaturated compound, and a repeating unit derived from a propylene unsaturated compound are substantially Polyketones with a structure alternately connected with each other have excellent mechanical and thermal properties, excellent processability, and high abrasion resistance, chemical resistance, and gas barrier properties, making it a useful material for various purposes. The high molecular weight of this ternary or higher copolymerized polyketone has higher processability and thermal properties, and is considered useful as an engineering plastic material with excellent economic efficiency. In particular, it can be used for parts such as gears of automobiles because of its high wear resistance, as a lining material for chemical transport pipes because of its high chemical resistance, and for lightweight gasoline tanks because of its high gas barrier properties. In addition, when ultra-high molecular weight polyketone having an intrinsic viscosity of 2 or more is used for the fiber, it is possible to draw at a high magnification, and as a fiber having high strength and high modulus of elasticity oriented in the stretching direction, it is a reinforcing material for belts and rubber hoses, tire cords, and concrete reinforcing materials. It is a very suitable material for building materials and industrial materials.

The method for producing polyketones comprises carbon monoxide and carbon monoxide in a liquid medium in the presence of an organometallic complex catalyst comprising (a) a group 9, group 10 or group 11 transition metal compound, and (b) a ligand having a group 15 element. In the method for producing a polyketone by terpolymerizing an ethylenic and propylene unsaturated compound, the carbon monoxide, ethylene and propylene are liquid-polymerized in a mixed solvent of alcohol (eg, methanol) and water to produce a linear terpolymer, the mixture 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, ketal may be formed and thermal stability may be reduced during the process, and if it exceeds 10 parts by weight, mechanical properties of the product may be reduced.

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

Examples of the Group 9 transition metal compound among the Group 9, Group 10, or Group 11 transition metal compounds (a) include a complex of cobalt or ruthenium, carbonate, phosphate, carbamate, sulfonate, and the like, Specific examples thereof include cobalt acetate, cobalt acetylacetate, ruthenium acetate, ruthenium trifluoroacetate, ruthenium acetylacetate, and ruthenium trifluoromethanesulfonate.

Examples of the Group 10 transition metal compound include nickel or palladium complexes, carbonates, phosphates, carbamates, and sulfonates, and specific examples thereof include nickel acetate, nickel acetyl acetate, palladium acetate, and 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 acetyl acetate, silver acetate, tri Silver fluoroacetic acid, silver acetyl acetate, trifluoromethane sulfonic acid silver, etc. are mentioned.

Among them, the inexpensive and economically preferable transition metal compound (a) is nickel and copper compound, and the preferable transition metal compound (a) in terms of the yield and molecular weight of polyketone is a palladium compound, in terms of catalytic activity and intrinsic viscosity improvement. It is most preferable to use palladium acetate in

Examples of the ligand (b) having a group 15 atom include 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 2,2'-bi-4-picoline , nitrogen ligands such as 2,2'-biquinoline, 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 sulfonate-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 and the like.

Among these, the ligand (b) having a group 15 element is preferred is a phosphorus ligand having a group 15 atom, and in particular, a preferred phosphorus ligand in terms of the yield of polyketone is 1,3-bis[di(2-) Methoxyphenyl) phosphino] propane, 1,2-bis [[di (2-methoxyphenyl) phosphino] methyl] benzene, in terms of the molecular weight of the polyketone, 2-hydroxy-1,3-bis [ They are di(2-methoxyphenyl)phosphino]propane and 2,2-dimethyl-1,3-bis[di(2-methoxyphenyl)phosphino]propane, and in terms of safety, they do not require an organic solvent. Water-soluble 1,3-bis[di(2-methoxy-4-sodium sulfonate-phenyl)phosphino]propane, 1,2-bis[[di(2-methoxy-4-sodium sulfonate-phenyl)phosphino ]methyl]benzene, which is easy to synthesize, can be obtained in large quantities, and is preferably 1,3-bis(diphenylphosphino)propane and 1,4-bis(diphenylphosphino)butane from the viewpoint of economy. A 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 1]

((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine) of Formula 1 is a polyketone introduced so far Expression of activity equivalent to 3,3-bis-[bis-(2-methoxyphenyl)phosphanylmethyl]-1,5-dioxa-spiro[5,5]undecane, which is known to show the highest activity among polymerization catalysts However, the structure is simpler and the molecular weight is also lower. As a result, the present invention has been able to provide a novel polyketone polymerization catalyst that has the highest activity as a polyketone polymerization catalyst in the art, while further reducing its manufacturing cost and cost. A method for preparing a ligand for a polyketone polymerization catalyst is as follows. ((2,2-dimethyl) using bis(2-methoxyphenyl)phosphine, 5,5-bis(bromomethyl)-2,2-dimethyl-1,3-dioxane and sodium hydride (NaH) Provided is a method for preparing a ligand for a polyketone polymerization catalyst, characterized in that -1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine) is obtained . The method for preparing a ligand for a polyketone polymerization catalyst of the present invention is conventional 3,3-bis-[bis-(2-methoxyphenyl)phosphanylmethyl]-1,5-dioxa-spiro[5,5]undecane Unlike the synthesis method of ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2- Methoxyphenyl) phosphine) can be synthesized in large quantities commercially.

On the other hand, 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 for 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, After boiling 5-dibromopentane in sodium ethoxide and ethanol, it is reduced under lithium aluminum hydride and tetrahydrofuran to synthesize 1,1-cyclohexanedimethanol, and then reacted with tosyl chloride under pyridine to release By reacting this with 2-methoxyphenylphosphine with sodium hydride and dimethyl sulfoxide, the ligand can be obtained. Each step undergoes purification steps such as column chromatography and recrystallization, and the The purity can be confirmed through nuclear magnetic resonance analysis.

In a preferred embodiment, in the method for preparing a ligand for a polyketone polymerization catalyst of the present invention, (a) bis(2-methoxyphenyl)phosphine and dimethylsulfoxide (DMSO) are added to a reaction vessel under a nitrogen atmosphere and hydrogenated at room temperature Stirring after adding sodium; (b) adding 5,5-bis(bromomethyl)-2,2-dimethyl-1,3-dioxane and dimethylsulfoxide to the obtained mixture, followed by stirring to react; (c) adding methanol after completion of the reaction and stirring; (d) adding toluene and water, washing the oil layer with water after layer separation, drying over anhydrous sodium sulfate, filtration under reduced pressure, and concentration under reduced pressure; and (e) recrystallizing the residue in methanol to obtain ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis(2-methoxyphenyl)phosphine) It can be carried out through the step of obtaining

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

In addition, it is another feature to add benzophenone during polymerization of polyketone. In the present invention, the effect of improving the intrinsic viscosity of the polyketone can be achieved by adding benzophenone during polymerization of the polyketone. The molar ratio of the (a) Group 9, Group 10, or Group 11 transition metal compound to benzophenone is 1:5-100, preferably 1:40-60. 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 tends to decrease, so it is undesirable

Examples of the ethylenically unsaturated compound copolymerized with carbon monoxide include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 - ?-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 ester, such as ethyl acrylate and methyl acrylate, etc. are mentioned. Among these, a preferable ethylenically unsaturated compound is an ?-olefin, more preferably an ?-olefin having 2 to 4 carbon atoms, and most preferably ethylene.

The ternary copolymerization of carbon monoxide with the ethylenically unsaturated compound and the propylene unsaturated compound is an organometallic complex comprising the Group 9, Group 10 or Group 11 transition metal compound (a), and a ligand (b) having a Group 15 element. It is caused by a catalyst, wherein the catalyst is produced by contacting the two components. Arbitrary methods can be employ|adopted as a method of making contact. That is, the two components may be prepared as a solution in which the two components are mixed in advance in a suitable solvent and used, or the two components may be separately supplied to the polymerization system and brought into contact within the polymerization system.

As the polymerization method, a solution polymerization method using a liquid medium, a suspension polymerization method, a gas phase polymerization method in which a small amount of polymer is impregnated with a high concentration of a catalyst solution, and the like are used. Polymerization may be either batch or continuous. As a reactor used for polymerization, a well-known thing can be used as it is, or it can process and use it. There is no restriction|limiting in particular about the polymerization temperature, Generally 40-180 degreeC, Preferably 50-120 degreeC is employ|adopted. Although there is no restriction|limiting also about the pressure at the time of polymerization, Usually, it is normal pressure - 20 MPa, Preferably it is 4-15 MPa.

A linear alternating polyketone is formed by the polymerization method as described above.

The content of the polyketone may be the remaining amount such that the total weight of the polyketone composition is 100% by weight, preferably 70 to 89% by weight, more preferably 73 to 85% by weight, 77 to 81% by weight may be

When the content of polyketone is less than 70% by weight, mechanical properties, thermal stability and fluidity may be reduced, and when it exceeds 89% by weight, the content of specific substances added to the composition is relatively small, so low-temperature impact resistance and processing stability The improvement effect may be negligible.

In addition, the polyketone composition according to the present invention includes a cold-resistant plasticizer to improve low-temperature impact properties.

The present invention can improve low-temperature impact properties by applying a cold-resistant plasticizer to improve low-temperature impact properties, and can reduce the content of existing plasticizers. The cold-resistant plasticizer is preferably an ester-based plasticizer, and more specifically, 2,2,4-trimethyl-1,3-pentadiol diisobutyrate (2,2,4-Trimethyl-1,3-pentanediol diisobutyrate). It is preferable to use

The content of the cold-resistant plasticizer is 5 to 15% by weight, preferably 7 to 13% by weight, more preferably 9 to 11% by weight based on the total weight of the composition. If the content of the cold-resistant plasticizer is less than 5% by weight, low-temperature impact strength is not sufficient, and if it exceeds 15% by weight, extrusion workability may be deteriorated.

The cold-resistant plasticizer has a freezing point of about -70° C., and may maintain a plasticizing effect and reinforcement for impact properties at a low temperature. The viscosity of the cold-resistant plasticizer may be 20 cps or less, preferably 15 cps or less, and more preferably 12 cps or less. If the viscosity of the cold-resistant plasticizer exceeds 20 cps, it is not suitable for application as a flexible tube due to poor flexibility.

In addition, the polyketone composition according to the present invention may include acrylonitrile butadiene styrene rubber (ABS Rubber).

The ABS rubber has a butadiene content of, for example, 65% or more, and is a type of ABS rubber having a high butadiene content and is applied for impact reinforcement. The content of the ABS rubber may be 5 to 15% by weight, preferably 7 to 13% by weight, more preferably 9 to 11% by weight based on the total weight of the composition. When the content of the ABS rubber is less than 5% by weight, the impact strength is lowered, and when it exceeds 15% by weight, the burst pressure and mechanical properties may be reduced.

In addition, the polyketone composition according to the present invention includes tricalcium phosphate (TCP) and a fluorine-based processing stabilizer as a processing stabilizer to improve processing stability for mass production.

Tricalcium phosphate plays a role in maintaining the viscosity of polyketone. In detail, since polyketone has a disadvantage of increasing viscosity and gelling at high temperatures, tricalcium phosphate is added to maintain the viscosity of polyketone. Due to the addition of tricalcium phosphate, it is possible to obtain the effect of maintaining the viscosity of the polyketone uniformly, thereby minimizing damage to the molded part and maintaining low specific gravity.

Such tricalcium phosphate may include 0.1 to 1.0% by weight based on the total weight of the composition, preferably 0.3 to 1.0% by weight, and more preferably 0.3 to 0.8% by weight. When the content of tricalcium phosphate is less than 0.1% by weight, it is difficult to suppress the gelation of polyketone, so it is difficult to obtain the effect of reducing the physical properties of the molded part and improving the processing stability, resulting in a problem in mass production, exceeding 1.0% by weight In this case, the limit in performance expression is reached due to excessive input.

The fluorine-based processing stabilizer moves to the interface between the polymer and the die wall when the composition is extruded, and a lubricant layer is formed on the surface of the die wall, thereby improving processing stability.

The fluorine-based processing stabilizer is preferably a copolymer of hexafluoropropylene and vinylidene fluoride, and more specifically, 88 to 92 wt% of poly(vinylidene fluoride-co-hexafluoropropylene); 4 to 9 wt% of talc, 1 to 4 wt% of amorphous silica; and 0 to 5% by weight of calcium carbonate.

In addition, the fluorine-based processing stabilizer may be 0.01 to 0.4% by weight based on the total weight of the composition, preferably 0.1 to 0.4% by weight, more preferably 0.2 to 0.4% by weight. At this time, when the content of the fluorine-based processing stabilizer is less than 0.01% by weight, a lot of frictional heat is generated when preparing the composition, and the resin temperature rises, causing a problem in continuous processing, and when it exceeds 0.4% by weight, due to excessive input A migration problem occurs, and the side effect of increasing the price of the final product occurs.

As such, the polyketone composition according to the present invention includes tricalcium phosphate and fluorine-based processing stabilizer as processing stabilizers in an optimal content range, thereby enabling mass production of polyketone flexible tubes and having excellent low-temperature impact properties and high flexibility.

On the other hand, the polyketone composition of the present invention may additionally contain additional additives known in the prior art, for example, antioxidants, heat stabilizers, lubricants, fillers, fireproof materials, mold release agents, colorants and other materials to improve the processability or physical properties of the polymer. can The content of these additional additives may be 0 to 2% by weight based on the total weight of the polyketone composition.

Meanwhile, the method for preparing the polyketone composition of the present invention is as follows.

The method for producing a polyketone flexible tube of 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 phosphorus double ligand compound; Preparing a mixed solvent (polymerization solvent) containing alcohol (eg, methanol) and water; preparing a linear terpolymer of carbon monoxide, ethylene and propylene by performing polymerization in the presence of the catalyst composition and a mixed solvent; removing the catalyst composition remaining from the linear terpolymer with a solvent (eg, alcohol and acetone) to obtain a polyketone resin; and mixing the polyketone, a cold-resistant plasticizer, acrylonitrile butadiene styrene rubber, tricalcium phosphate, and a fluorine-based processing stabilizer to injection molding.

The carbon monoxide, ethylene and propylene are liquid-phase polymerized in a mixed solvent of alcohol (eg, methanol) and water to produce a linear terpolymer, and 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, ketal may be formed and thermal stability may be reduced during the process, and if it exceeds 10 parts by weight, mechanical properties of the product may be deteriorated.

In addition, during the polymerization, the reaction temperature is 50 ~ 100 ℃, the reaction pressure is suitable in the range of 40 ~ 60bar. 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 polyketone composition obtained above is extruded with an extruder to finally obtain a polyketone composition. The polyketone composition may be prepared by putting it into a twin-screw extruder, melt-kneading and extruding.

At this time, the extrusion temperature is 230 ~ 260 ℃, the screw rotation speed is preferably in the range of 100 ~ 300rpm. If the extrusion temperature is less than 230 ℃, kneading may not occur properly, and if it exceeds 260 ℃, problems related to the heat resistance of the resin may occur. In addition, if the screw rotation speed is less than 100 rpm, smooth kneading may not occur, and if it exceeds 300 rpm, mechanical properties may be deteriorated.

The polyketone composition prepared as described above has the advantage that continuous processing of 3 hours or more is possible as the temperature change of the molten resin is small at 1 to 3°C/hr.

In addition, the polyketone flexible tube of the present invention may be prepared by first preparing the composition in the form of pellets as described above, and then extruding the polyketone composition pellets using a single tube extruder.

The polyketone flexible tube according to the present invention has a low-temperature impact strength of 9 kJ/m ² or more measured at -40 ° C., a flexural modulus of 500 to 800 MPa, and a room temperature rupture of 60 bar or more. By using the polyketone composition with improved processing stability, there is an advantage that mass production is possible.

Hereinafter, the present invention will be described in detail through examples. However, the following examples are merely illustrative of the present invention, and the present invention is not limited by the following examples.

[Examples 1 to 3]

Linear alternating polyketones composed of carbon monoxide, ethylene and propene are palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl)bis(methylene))bis(bis( 2-methoxyphenyl)phosphine) prepared in the presence of a catalyst composition. In the above, the content of trifluoroacetic acid compared to palladium is 10 times the molar ratio, and the first step of polymerization temperature is 78°C and the second step is 84°C. In the polyketone prepared above, carbon monoxide was 50 mol%, ethylene was 46 mol%, and propylene was 4 mol%. In addition, the melting point of the polyketone was 220 °C, and the viscosity (I.V) measured at 25 °C using hexa-fluoroisopropano (HFIP) was 1.4 dl/g.

The prepared polyketone and cold-resistant plasticizer TXIB (Eastman), ABS rubber (Kumho), tricalcium phosphate (TCP), and fluorine-based processing stabilizer FX-9613 (Dynamar ^TM of 3M) were added in the amount shown in Table 1 Each was added to prepare a composition, and the prepared composition was melt-blended at a temperature of 210° C. using a co-directional twin-screw extruder to prepare pellets on the extruder, respectively. At this time, the time during which continuous operation of the prepared pellets is possible and the temperature change of the melt resin were measured. Thereafter, the prepared pellets were prepared using a single extruder at 200° C. to prepare OD: 8 mm, ID: 6 mm tubes, respectively.

[Comparative Examples 1 to 8]

Pellets and tubes were each prepared through the same procedure as in Example 1, except that the component content of the composition was adjusted as described in Table 2 below.

[Experimental example]

The physical properties of the polyketone pellets and tubes prepared in Examples and Comparative Examples, respectively, were evaluated using the following method, and the results are shown in Tables 1 and 2 below.

1) Room temperature rupture: Measured according to Hyundai Motor Spec ES31310-20-6.1.2.

2) Low-temperature impact: Measured at -40°C according to ISO 179.

3) Flexural modulus: measured according to ASTM D790.

4) Migration phenomenon: After extrusion of the polyketone flexible tube, it was observed with the naked eye one month later to check whether powder was generated.

5) Continuous processing time: The time during which a gel is not generated in the resin during extrusion so that the strand is not broken and the pellet can be produced continuously was measured.

6) Whether or not gel is generated: Check with the naked eye, and when gel is generated, the strand is broken and work is impossible. If a gel actually occurs, continuous processing is not possible.

7) Melt resin temperature change: It was measured through a thermocouple installed in the extruder, and the temperature change value was derived from the temperature difference at the start and end of the extrusion operation.

division Example 1 Example 2 Example 3 Polyketone (M510T) (wt%) 79.3 79 79 TXIB (wt%) 10 10 10 ABS (wt%) 10 10 10 TCP (wt%) 0.3 0.6 0.8 FX-9613 (wt%) 0.4 0.3 0.2 Extrusion mass production continuous machining time more than 7 hours more than 7 hours more than 7 hours Melt resin temperature change 2℃/hr 2℃/hr 2℃/hr Whether or not there is gel X X X tube properties Flexural modulus (MPa) 600 600 600 Room temperature rupture (bar) 75 75 75 -40℃ low temperature impact evaluation (kJ/m ² ) 10 10 10 migration phenomenon non-occurring non-occurring non-occurring

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 comparative example
8 Polyketone (M510T) (wt%) 80 79.2 79.8 78.5 79.5 78.7 78.3 78.0 TXIB (wt%) 10 10 10 10 10 10 10 10 ABS (wt%) 10 10 10 10 10 10 10 10 TCP (wt%) - 0.8 - 1.5 - 0.8 1.5 1.5 FX-9613 (wt%) - - 0.2 - 0.5 0.5 0.2 0.5 Extrusion mass production continuous machining time 30 minutes 3 hours 1 hours 3 hours 1 hours 3 hours 2 hours 2 hours Melt resin temperature change 5℃/hr 4℃/hr 3℃/hr 4℃/hr 1℃/hr 4℃/hr 4℃/hr 4℃/hr Whether or not there is gel O X O X O X X X tube properties Flexural modulus (MPa) 600 600 600 600 600 600 600 600 Room temperature rupture (bar) 75 75 75 75 75 75 75 75 -40℃ low temperature impact evaluation (kJ/m ² ) 10 10 10 10 10 10 10 10 migration phenomenon non-occurring non-occurring non-occurring non-occurring Occur Occur non-occurring Occur

Referring to Tables 1 and 2, it can be seen that the Examples and Comparative Examples all include a cold-resistant plasticizer and ABS rubber, and thus have excellent low-temperature impact strength and high flexibility.

However, Comparative Example 1 does not contain any of the processing stabilizers TCP and FX-9613, so it cannot suppress the gelation of polyketone, and when the composition is prepared, a lot of frictional heat is generated, and the resin temperature rises, so there is a limit to continuous processing. As it occurs, it can be seen that a problem occurs in mass production.

In addition, as in Comparative Example 2, when FX-9613 was not included, it was confirmed that a problem occurred in continuous processing due to a lot of frictional heat generated when the composition was prepared and the resin temperature increased, and TCP was included as in Comparative Example 3 If not, it can be seen that there is a problem in mass production with a continuous processing time of 1 hour as the gelation of polyketone cannot be suppressed.

On the other hand, as in Comparative Example 4, when the content of TCP exceeds 1.0% by weight, despite the high TCP content compared to Comparative Example 2, the same physical properties can be exhibited, but it can be seen that the same limit is reached with respect to extrusion mass productivity. can As in Comparative Example 5, when the content of FX-9613 exceeded 0.4% by weight, it was confirmed that a migration problem occurred due to excessive input.

In addition, as in Comparative Example 6, the TCP content is appropriate, but when the content of FX-9613 exceeds 0.4% by weight, it was confirmed that a migration problem occurred due to excessive input, and in Comparative Example 7, the content of FX-9613 was appropriate However, when the content of TCP exceeds 1.0% by weight, there is a problem in that the continuous processing time is only 2 hours, which reduces the mass productivity.

In addition, as in Comparative Example 8, when both the content of TCP and the content of FX-9613 are out of the scope of the present invention, it can be confirmed that the migration phenomenon occurs and the continuous processing time is also low.

On the other hand, when including the processing stabilizer as in the embodiment of the present invention, but the TCP content is 0.1 to 1.0% by weight, and the fluorine-based processing stabilizer content is included in the optimum content range in the range of 0.01 to 0.4% by weight (Examples 1 to 3) It has excellent low-temperature impact properties, high flexibility, and improved processing stability, so that continuous processing is possible for more than 7 hours (maximum per day), so there is an advantage in mass production.

Although the above has been described with reference to the preferred embodiment of the present invention, those skilled in the art or those having ordinary knowledge in the technical field will not depart from the spirit and technical scope of the present invention described in the claims to be described later. It will be understood that various modifications and variations of the present invention can be made without departing from the scope of the present invention.

Accordingly, the technical scope of the present invention should not be limited to the contents described in the detailed description of the specification, but should be defined by the claims.

Claims (5)

70.0-89.0 wt% of a polyketone consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon;
5.0 to 15.0 wt% of a cold-resistant plasticizer;
5.0 to 15.0 wt% of acrylonitrile butadiene styrene rubber;
0.3 to 0.8% by weight of tricalcium phosphate; and
A polyketone flexible tube comprising a polyketone composition containing 0.2 to 0.4% by weight of a fluorine-based processing stabilizer.
According to claim 1,
The cold-resistant plasticizer is 2,2,4-trimethyl-1,3-pentadiol diisobutyrate (2,2,4-Trimethyl-1,3-pentanediol diisobutyrate) polyketone flexible tube.
According to claim 1,
The fluorine-based processing stabilizer is a polyketone flexible tube that is a copolymer of hexafluoropropylene and vinylidene fluoride.
According to claim 1,
A polyketone flexible tube having a temperature change of the molten resin of the polyketone composition of 1 to 3°C/hr.
According to claim 1,
A polyketone flexible tube with a low-temperature impact strength of 9kJ/m ² or more measured at -40℃, a flexural modulus of 500-800MPa, and a rupture rate of 60bar or more at room temperature.