KR101956616B1 - Polyketone tube and method of preparing the same - Google Patents

Abstract

The present invention relates to a polyketone tube and a production method thereof and, more specifically, to a two-layered fuel tube comprising: a linear alternating polyketone plasticizer consisting of carbon monoxide; and at least one olefinically unsaturated hydrocarbon and a polyketone composition including an ABS rubber. In addition the two-layered fuel tube consists of an inner layer and an outer laye respectively comprising the polyketone having excellent gas barrier properties as those of EvOH, a plasticizer having properties similar to those of nylon 12, and a polyketone composition added with the ABS rubber.

Description

TECHNICAL FIELD The present invention relates to a polyketone tube and a method of preparing the same,

The present invention relates to a two-layer fuel tube comprising a polyketone composition comprising a linear alternating polyketone consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon, and a plasticizer and an ABS rubber, characterized in that the gasketing is a poly Layer fuel tube composed of an inner layer and an outer layer each comprising a ketone, a plasticizer having properties similar to those of nylon 12, and a polyketone composition added with ABS rubber

Conventional automotive fuel tubes have evolved from the NY 12 (11) monolayer to NY 12 (11) / adhesive layer / EvOH / adhesive layer / NY 12 (11) according to enhanced environmental legislation. However, as the development progressed into a multi-layered structure, the manufacturing cost increased.

The following patent documents (Korean Patent Laid-Open Publication No. 2016-0031344) disclose hoses and tubes composed of two or more layers in order to withstand the chemical rupture, the gas barrier, and the physical rupture strength of a certain pressure or more. Discloses hollow articles composed of an inner layer composed of a nylon layer, an adhesion promoter layer, an EVOH intermediate layer, an adhesion promoter layer, and an outermost layer of a nylon layer and carrying a liquid or gaseous medium.

On the other hand, there has recently been a growing interest in line-by-line alternatives 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 >

Korea Patent Publication No. 2016-0031344

It is an object of the present invention to provide a two-layered fuel tube having the same physical properties as a fuel tube developed in a multilayer structure according to an enhanced environmental regulation and ensuring cost competitiveness.

According to a preferred embodiment of the present invention, there is provided a method for producing a polyketone comprising the steps of: preparing a first pellet comprising a polyketone;

Preparing a second pellet using a polyketone composition comprising a polyketone, a sulfonamide based plasticizer, and an acrylonitrile butadiene styrene rubber; And

And co-extruding the first pellet and the second pellet to produce a fuel tube.

According to another preferred embodiment of the present invention, in the step of producing the second pellet, the polyketone composition comprises 70 to 90% by weight of the polyketone based on 100% by weight of the total polyketone composition, 5 to 15% by weight of a plasticizer and 5 to 15% by weight of the acrylonitrile butadiene styrene rubber (ABS Rubber).

According to another preferred embodiment of the present invention, in a two-layer fuel tube composed of an inner layer and an outer layer, the inner layer is made of a first pellet composed of polyketone and the outer layer is made of a polyketone, a sulfonamide- And a second pellet composed of a polyketone composition containing nitrile butadiene styrene rubber.

Specifically, the fuel permeability of the two-layer fuel tube is 0.1 g / m 2 / day or less for Fuel C, 0.5 g / m 2 / day or less for CM15 and 0.3 g / m 2 / day or less for CE10 according to SAE 2260, The chemical resistance of the fuel tube is 85 to 160 bar, the low temperature rupture is 80 to 90 bar, the normal temperature rupture is 90 to 160 bar, the high temperature rupture is 80 to 150 bar, and the torsional rupture is preferably 90 to 160 bar.

It is preferable that the fuel permeability is used as a fuel tube when Fuel C exceeds 0.1 g / m 2 / day, CM 15 exceeds 0.5 g / m 2 / day, or CE 10 exceeds 0.3 g / m 2 / day not. In the present invention, as the fuel tube having flexibility, more preferably, the chemical resistance is 85 to 95 bar, the normal temperature rupture is 90 to 100 bar, the high temperature rupture Preferably 80 to 90 bar, and torsional rupture of 90 to 95 bar.

The two-layer fuel tube of the present invention has the effect of reducing the manufacturing cost while maintaining fuel permeability, chemical resistance, rupture pressure and flexibility at low / normal / high temperature.

The present invention relates to a method for producing polyketone comprising the steps of: preparing a first pellet comprising a polyketone; Preparing a second pellet using a polyketone composition comprising a polyketone, a sulfonamide based plasticizer, and an acrylonitrile butadiene styrene rubber; And co-extruding the first pellet and the second pellet to produce a two-layer fuel tube.

The manufacturing method for producing the polyketone used in the first pellet and the second pellet of the present invention includes the following steps.

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 polyketone terpolymer of carbon monoxide, ethylene and propylene; And removing the remaining catalyst composition from the linear terpolymer with a solvent (e.g., alcohol and acetone) and extruding it into a pellet.

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

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

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

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

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

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

Particularly preferred are polyketone polymers having a number average molecular weight of from 100 to 200,000, especially from 20,000 to 90,000, as measured by gel permeation chromatography. The physical properties of the polymer are determined according to the molecular weight, depending on whether the polymer is a copolymer or a terpolymer and, in the case of a terpolymer, the properties of the second hydrocarbon part. The melting point of the total of the polymers used in the present invention is 175 ° C to 300 ° C, and generally 210 ° C to 270 ° C. The intrinsic viscosity (IV) 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, more preferably 0.8 dl / g to 4 dl / g, And preferably 1.0 dl / g to 2.5 dl / g. When the intrinsic viscosity is less than 0.5 dl / g, the mechanical properties are deteriorated. When the intrinsic viscosity exceeds 10 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 2.5 or more, 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.

As a method of producing the polyketone polymer, liquid phase polymerization in which carbon monoxide and olefin are carried out in an alcohol solvent through a catalyst composition composed of a palladium compound, an acid having 6 or less of PKa, and a ligand compound of phosphorus can be employed. The polymerization temperature is preferably from 50 to 100 ° C. and the reaction pressure is from 40 to 60 bar. The 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.

As the palladium compound, palladium acetate is preferable, and the amount of the palladium compound to be used is preferably 10 ^-3 to 10 ^-1 mole. Specific examples of the acid having a pKa value of 6 or less include trifluoroacetic acid, p-toluenesulfonic acid, sulfuric acid, and sulfonic acid. In the present invention, trifluoroacetic acid is used and its amount is preferably 6 to 20 equivalents based on palladium. The bis (2-methoxyphenyl) phosphine (cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) phosphine is preferably used as the two- .

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

The repeating unit derived from carbon monoxide, an ethylenically unsaturated compound and one or more olefinically unsaturated hydrocarbon compounds, three or more copolymers, particularly repeating units derived from carbon monoxide, and ethylenically unsaturated compounds and repeating units derived from propylenically unsaturated compounds are substantially Are excellent in mechanical properties and thermal properties, excellent in processability, high in abrasion resistance, chemical resistance and gas barrier property, and are useful materials for various applications. It is considered that the high molecular weight product of the copolymerized polyketone having three or more members is more useful as an engineering plastic material having higher workability and thermal properties and having excellent economy. Particularly, it has high abrasion resistance and can be used in light gasoline tanks because of high gas barrier properties such as parts of gears of automobiles, high chemical resistance, and lining materials of chemical transport pipes.

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

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

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

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

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

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

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

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

[Chemical Formula 1]

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

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

The above (cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) phosphine ligand can be synthesized through the following four steps. First, diethyl malonate, After 5-dibromopentane was boiled with sodium ethoxide and ethanol, 1,1-cyclohexane dimethanol was synthesized by reduction under lithium aluminum hydride and tetrahydrofuran, and then reacted with tosyl chloride in pyridine to yield The ligand can be obtained by reacting it with 2-methoxyphenylphosphine and sodium hydride under dimethylsulfoxide. Each step is subjected to purification steps such as column chromatography and recrystallization, Purity can be confirmed by nuclear magnetic resonance analysis.

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

(2)

As the model of the multi-site polymerization catalyst, the ligand preferably used is 1,3-bis [non-2- (methoxyphenyl) phosphino] propane, (2,2- Polyketone polymerization comprising a ligand having a multi-site structure of one or two kinds selected from the group consisting of bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) A specific example of the model of the multi-site polymerization catalyst may be represented by the following formula 3. However, the present invention is not limited to this. The use of a ligand having the effect of reducing the fouling that occurs after adhesion on the inner wall of the reactor during polyketone polymerization is effective.

(3)

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, and most preferably ethylene.

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

In the present invention, conventionally known additives such as an antioxidant, a stabilizer, a filler, a refractory material, a releasing agent, a coloring agent, and other materials may be further added to improve the processability and physical properties of the polymer.

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 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.

The content of the Pd element in the polyketone of the present invention is preferably 50 ppm or less. When the content of the Pd element exceeds 50 ppm, thermal denaturation and chemical denaturation due to the residual Pd element are liable to occur. In the melt-molding, the melt viscosity increases and the viscosity of the dopant increases when dissolved in a solvent , The workability is poor. In addition, since a large amount of Pd element remains in the polyketone molded body obtained after molding, the heat resistance of the molded body also deteriorates. The content of the Pd element in the polyketone is preferably as small as possible from the viewpoint of processability and heat resistance of the molded article, more preferably 10 ppm or less, still more preferably 5 ppm or less, and most preferably 0 ppm.

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

After removal of the remaining catalyst composition from the polyketone terpolymer prepared as described above with a solvent such as an alcohol and acetone, the polyketone composition was applied on a twin-screw extruder having a diameter of 2.5 cm L / D = 32 operating at 100-300 rpm Lt; RTI ID = 0.0 > 260 C < / RTI > and then pelletized. In the present invention, this is used as the first pellet.

A manufacturing method for producing the second pellet of the present invention includes the following steps.

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 polyketone 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; And 70 to 90% by weight of the polyketone; 5 to 15% by weight of a plasticizer; And 5 to 15% by weight of acrylonitrile butadiene styrene rubber (ABS Rubber) in the form of a pellet. In the present invention, this is used as a second pellet.

Preparing the catalyst composition; And removing the catalyst composition with a solvent to obtain a polyketone is the same as the method for producing the first pellet.

The polyketone composition constituting the second pellet of the present invention may contain one or more sulfonamide type plasticizers in the polyketone so as to be flexible so as to be usable as an outer layer in a two- .

The content of the plasticizer is 5 to 15% by weight, preferably 7 to 13% by weight, more preferably 9 to 11% by weight, based on 100% by weight of the total polyketone composition constituting the second pellets. When the content of the plasticizer is less than 5% by weight, the flexible property is not sufficient. When the plasticizer content is more than 15% by weight, extrusion workability may be deteriorated.

Meanwhile, the polyketone composition constituting the second pellet of the present invention may further comprise acrylonitrile butadiene styrene rubber (ABS Rubber). The ABS rubber is a type ABS rubber having a butadiene content of, for example, 65% or more and a high content of butadiene, 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 100% by weight of the polyketone composition constituting the second pellet. If the content of the ABS rubber is less than 5 wt%, the impact strength is lowered. If the ABS rubber is more than 15 wt%, the burst pressure and mechanical properties may be deteriorated.

In the present invention, the polyketone composition constituting the second pellet is melt-blended at a temperature of 210 to 260 ° C on a twin-screw extruder having a diameter of 2.5 cm and L / D = 32 operating at 100 to 300 rpm and then pellet- do.

The polyketone first pellets and the second pellets obtained above are co-extruded using an extruder, preferably a 220 占 폚 multi-tube extruder, to prepare a two-layer tube.

The first pellet forms a rigid grade layer excellent in gas-ducting property, and the second pellet forms a flexible grade layer having properties similar to nylon 12, wherein the rigid- Layer fuel tube and the flexible layer having similar properties to nylon 12 form the outer layer of the two-layer fuel tube.

Hereinafter, the constitution and effects of the present invention will be described in detail with reference to specific examples and comparative examples, but these examples are merely for the purpose of understanding the present invention more clearly and do not limit the scope of the present invention. The present invention will be described in detail with reference to the following non-limiting examples.

Example 1

(Preparation of first pellet)

The linear alternating polyketone terpolymer of carbon monoxide and ethylene and propene is prepared by reacting palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene) Bis (2-methoxyphenyl) phosphine). The molar ratio of ethylene to propene in the polyketone terpolymer prepared above was 46 to 4. The melting point of the polyketone terpolymer was 220 DEG C, and the I.V measured by HFIP (hexa-fluoroisopropano) at 25 DEG C was 2.3 dl / g, and the MI index was 6 g / 10 min. Blended at a temperature of 230 ° C on a twin-screw extruder with a diameter of 2.5 cm, operating at 250 rpm and L / D = 32, and then pelletized.

(Preparation of second pellet)

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 polyketone terpolymer prepared above had a melting point of 195 ° C, a viscosity IV of 2.4 dl / g as measured by HFIP (hexa-fluoroisopropano) at 25 ° C, and a melt index ) Was 4 g / 10 min. To 80 wt% of the polyketone terpolymer prepared above, 10 wt% of KF-4 as a plasticizer and 10 wt% of Blendex 338 (ABS Rubber, Galata Chemical Co.) as an ABS rubber were added to prepare a composition , Which was melt-blended at a temperature of 210 DEG C on a twin-screw extruder having a diameter of 2.5 cm and operating at 250 rpm and having an L / D of 32, and then pelletized.

The first pellet and the second pellet were prepared by using a multi-tube extruder at 220 ° C to prepare a two-layer tube having an OD of 8 mm and an ID of 6 mm. The gas barrier property test, the chemical resistance test and the falling hammer test were carried out. The first pellet consisted of an inner layer of a two-ply fuel tube and the second pellet consisted of an outer layer of a two-ply fuel tube.

In addition, two layer (flexible grade & rigid grade) sheets were manufactured using sheet coextrusion equipment and the adhesion test was conducted according to ASTM D1865-95.

Example 2

In the preparation of the second pellet, a composition consisting of 70% by weight of polyketone terpolymer, 15% by weight of KF-4 as plasticizer and 15% by weight of Blendex 338 (ABS Rubber, Galata Chemical) as ABS rubber was used A two-layer fuel tube was prepared in the same manner as in Example 1.

Example 3

In the preparation of the second pellet, a composition consisting of 90% by weight of polyketone terpolymer, 5% by weight of KF-4 as plasticizer and 5% by weight of Blendex 338 (ABS Rubber, Galata Chemical) as ABS rubber was used A two-layer fuel tube was prepared in the same manner as in Example 1.

Comparative Example 1

The first layer is composed of nylon 12 and the second layer is composed of EvOH and has a third layer of nylon 12 surrounding the outer surface of the second layer and between the first layer and the second layer, A five-layered fuel tube and sheet made of an adhesive layer between layers were prepared and subjected to the same test.

Comparative Example 2

The linear alternating polyketone terpolymer of carbon monoxide and ethylene and propene is prepared by reacting palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene) Bis (2-methoxyphenyl) phosphine). The molar ratio of ethylene to propene in the polyketone terpolymer prepared above was 46 to 4. The melting point of the polyketone terpolymer was 220 占 폚, the I.V measured by HFIP (hexa-fluoroisopropano) at 25 占 폚 was 2.3 dl / g, and the MI (Melt index) was 6 g / 10 min. Using the polyketone terpolymer prepared above as a first layer, a tube having an outer diameter of 8 mm and an inner diameter of 6 mm was manufactured using a tube extruder, and gas barrier properties, chemical resistance test for ZnCl 2, dropping hammer test and the like were carried out.

The fuel tubes of Examples 1 to 3 and Comparative Examples 1 and 2 were prepared and measured as follows.

1) Adhesion test: Two layer (flexible grade & rigid grade) sheet was manufactured using the coextrusion equipment of sheet and the adhesion test was conducted according to ASTM D1865-95.

2) Fuel permeability: Determine how much fuel passes through tube (m ² ) per tube inner surface (m ² ) for one day through the fuel line during storage at 23 ° C, through fuel permeability measurement according to SAE 2260 Respectively. In this case, a tube segment having a length of 300 mm was weighed in each case and Fuel C (composition: 50 wt% toluene, 50 wt% isooctane), CM15 (composition: 42.5 wt% toluene, 42.5 wt% Isooctane and 15 wt% methanol), 6 ml of CE10 (composition: 45 wt% toluene, 45 wt% isooctane and 10 wt% ethanol) and sealing the ends. The filled pipe was weighed again at specific time intervals to determine the mass of the permeated fuel in accordance with the mass loss. The effective transmission length is 290 mm.

3) Chemical resistance test in ZnCl2: Proceed according to Hyundai Motor Spec ES31310-20-6.1.15

4) Low temperature impact evaluation: Proceed according to Hyundai Motor Spec ES31310-20-6.1.7

5) Confidentiality performance: Proceed according to Hyundai Motor Spec ES31310-20-6.1.1

6) Normal temperature rupture: Proceed according to Hyundai Spec ES31310-20-6.1.2

7) High temperature rupture: Proceed according to Hyundai Motor Spec ES31310-20-6.1.3

8) Evaluation of torsional rupture: Proceed according to Hyundai Motor Spec ES31310-20-6.1.6

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Furtherance Flexible PK / Rigid PK Flexible PK / Rigid PK Flexible PK / Rigid PK NY12 / adhesive layer / EvOH / adhesive layer / NY12 Rigid PK Adhesion Inseparable Inseparable Inseparable Inseparable - Fuel C permeability
(g / m ² / day) 0.1 0.1 0.1 0.2 0.1 CM15 permeability
(g / m ² / day) 0.5 0.5 0.5 0.7 0.3 CE10 permeability
(g / m ² / day) 0.3 0.3 0.3 0.5 0.2 ZnCl ₂ Chemical resistance test (bar) 90 85 95 65 165 Low temperature impact evaluation (bar) 85 80 90 75 - Confidential Performance No leak No leak No leak No leak No leak Room temperature rupture (bar) 95 90 100 75 170 High temperature rupture (bar) 85 80 90 60 160 Torsional Rupture Evaluation (bar) 90 95 95 75 165

Referring to Table 1, Examples 1 to 3 of the present invention are compared with Comparative Example 1, and the layer structure of the fuel tube is a two-layer structure, whereas the Comparative Example 1 is a five-layer structure, The fuel tube of the two-layer structure is capable of shortening the manufacturing process and reducing the manufacturing cost compared with the fuel tube of the conventional comparative example 1, but exhibiting better characteristics at the permeability.

In Examples 1 to 3 of the present invention, the two-layer fuel tube had excellent permeability and at the same time had flexibility due to the use of a flexible second pellet, and the comparison was made using rigid polyketone (first pellet) The fuel tube of Example 2 was not flexible and thus difficult to use as a stand-alone fuel tube.

Therefore, Examples 1 to 3 of the present invention show improved fuel permeability, chemical resistance, low temperature rupture, normal temperature rupture, high temperature rupture and torsion rupture properties as compared with Comparative Example 1 which is a conventional five-layer fuel tube. Accordingly, the two-layer fuel tube including the flexible grade polyketone and the rigid grade polyketone according to the present invention can secure high physical properties against fuel permeability, chemical resistance, low temperature / normal temperature / high temperature rupture and torsion rupture It can be seen that there is an advantage in that.

Claims (4)

Producing a first pellet comprising a polyketone;
Preparing a second pellet using a polyketone composition comprising a polyketone, a sulfonamide based plasticizer, and an acrylonitrile butadiene styrene rubber; And
And co-extruding said first pellet and said second pellet to produce a fuel tube. The method according to claim 1,
Wherein the polyketone composition comprises 70 to 90 wt% of the polyketone, 5 to 15 wt% of the sulfonamide based plasticizer, and 5 to 15 wt% of the polyketone composition, based on 100 wt% And 5 to 15% by weight of rhenitrile butadiene styrene rubber (ABS Rubber). In a two-layer fuel tube comprising an inner layer and an outer layer,
Characterized in that the inner layer is made of a first pellet made of polyketone and the outer layer is made of a second pellet composed of a polyketone composition comprising a polyketone, a sulfonamide based plasticizer and acrylonitrile butadiene styrene rubber. Floor fuel tubes. The method of claim 3,
The fuel permeability of the two-layer fuel tube is 0.1 g / m 2 / day or less for Fuel C, 0.5 g / m 2 / day or less for CM15 and 0.3 g / m 2 / day or less for CE10 according to SAE 2260,
Wherein the two-layer fuel tube has a chemical resistance of 85 to 160 bar, a low temperature rupture of 80 to 90 bar, a normal temperature rupture of 90 to 160 bar, a high temperature rupture of 80 to 150 bar and a torsional rupture of 90 to 160 bar. tube.