KR20180085374A - Cover component for brush cutter containing polyketone - Google Patents

Abstract

The present invention relates to a cover component for a brush cutter containing polyketone, and specifically, to a cover component for a brush cutter, which has excellent mechanical strength, particularly impact resistance at a low temperature by injecting a polyketone composition consisting of polyketone, polyamide and rubber, and has improved physical stability of products by solving a reliability problem in an outdoor environment.

Description

{Cover component for brush cutter containing polyketone}

The present invention relates to a cover part for a mower cover to which a polyketone is applied, more specifically, to a polyketone composition comprising a polyketone, a polyamide and a rubber, which is excellent in mechanical strength, The present invention relates to a cover part for a lawn mower having improved physical stability.

Mowers are used for mowing lawns, weeds or scarves, and are used for agricultural work, management of greenery in parks, and foreclosure in graveyards. Representative plastic materials used in garden management apparatuses such as lawn mowers include polyamide 66 (PA66) / rubber compound products and polyamide 6 (PA6) / rubber compound products. In general, polyamide products are problematic in material and dimensional deformation due to high water hygroscopicity, and product damage due to lack of mechanical strength may occur in outdoor use environments using lawn mowers, which has a problem in securing reliability in lawn mower parts .

On the other hand, polyketone (PK) is superior to general engineering plastic materials such as polyamide polyester and polycarbonate because of excellent heat resistance, chemical resistance, impact resistance and fuel permeability, and is widely applied to various industries.

The polyketone having the above characteristics can be produced by reacting carbon monoxide (CO) and an olefin such as ethylene or propylene as a catalyst with a transition metal complex such as palladium (Pd) or nickel (Ni) It is already known that carbon monoxide and olefin can be obtained by alternating bonding with each other by using a polymerization initiator (Industrial Materials, December issue, page 5, 1997)

In addition, the polyketone is included in general-purpose high-performance plastics and has an advantage in that it has high strength comparable to conventional engineering plastics and good affinity with rubber. Due to the characteristics of the polyketone, polyketone can be used for a tire cord or a rubber material in which paraffin-based aramid fibers are exclusively used.

Accordingly, in order to solve the above problems, the inventors of the present invention have studied polyketone resins, and as a result, they have been able to produce polyketone resin compositions and parts containing the same that have superior impact resistance and durability as compared with conventional engineering plastics.

Korean Patent Publication No. 2016-0056917 Korea Patent No. 2012-0118737 Japanese Patent Laid-Open No. 1999-256027 United States Patent No. 6180197

In order to solve the above problems, the present invention relates to a cover part for a mower cover to which a polyketone is applied, more particularly, to a cover part for a mower cover having excellent impact resistance and durability by injecting a polyketone composition comprising polyketone, To provide a cover part.

A preferred embodiment of the present invention comprises 35 to 70% by weight of a linear alternating polyketone consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon; 10 to 35% by weight of polyamide; And 20 to 30% by weight of rubber, and the notched impact strength at 23 DEG C measured by ISO 179 / 1eA is 82.0 to 88.4 kJ / m < 2 > It provides

In another preferred embodiment of the present invention, the notched impact strength of the cover part for lawnmower as measured at ISO 179 / 1eA at -10 캜 is 20.0 to 24.9 kJ / m 2, and the inherent viscosity of the polyketone (IV ) Is 1.0 to 2.0 dl / g, the molecular weight distribution is 1.5 to 2.5, and is composed of the repeating units represented by the following general formulas (1) and (2) and has a y / x value of 0.03 to 0.3 .

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

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

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

Further, the rubber may be a maleic anhydride-grafted rubber and may be one selected from the group consisting of ethylene-octene rubber (EOR), ethylene propylene diene monomer rubber (EPDM) and ethylene propylene rubber (EPM) Or two or more.

The cover part for a lawn mower including the polyketone composition according to the present invention is highly suitable for application as a cover part for a lawn mower due to the improvement of the reliability and durability of the product in a low temperature environment requiring a strong impact property because of excellent impact strength as mechanical property Do.

Hereinafter, the present invention will be described in detail.

The present invention relates to a linear alternating polyketone polymer consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon and having a viscosity (IV) of 1.0 to 2.0, a polyamide; And rubber, and the notched impact strength measured at 23 DEG C is 82.0 to 88.4 kJ / m < 2 >.

Hereinafter, the polyketone polymer will be described as follows.

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

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

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

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

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

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

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

Particularly preferred are polyketone polymers having a number average molecular weight of from 100 to 200,000, especially from 20,000 to 90,000, as measured by gel permeation chromatography. The physical properties of the polymer are determined according to the molecular weight, depending on whether the polymer is a copolymer or a terpolymer and, in the case of a terpolymer, the properties of the second hydrocarbon part. The melting point of the total of the polymers used in the present invention is 175 ° C to 300 ° C, and generally 210 ° C to 270 ° C. The intrinsic viscosity (LVN) of the polymer measured by HFIP (hexafluoroisopropyl alcohol) at 60 DEG C using a standard tubular viscosity measuring apparatus is 0.5 dl / g to 10 dl / g, preferably 0.8 dl / g to 4 dl / g, And more preferably 1.0 dl / g to 1.4 dl / g. If the intrinsic viscosity is less than 1.0 dl / g, the mechanical properties are deteriorated. If the intrinsic viscosity exceeds 1.4 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.

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-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. Also, 1,3-bis [di (2-methoxyphenylphosphino)] propane is preferably used as the left-handed compound of phosphorus, and the amount to be used is preferably 1 to 1.2 equivalents based on palladium.

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, especially 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. In the case of using an ultrahigh molecular weight polyketone having an intrinsic viscosity of 2 or more as the fiber, it is possible to conduct stretching at a high magnification and to have a high strength and a high modulus of elasticity oriented in the stretching direction as belts, reinforcements of rubber hoses, tire cords, And is suitable for use in building materials and industrial materials.

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).

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

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

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

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

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

Examples of the ethylenically unsaturated compound copolymerized with carbon monoxide include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, -Olefins such as hexadecene and vinylcyclohexane; Alkenyl aromatic compounds such as styrene and? -Methylstyrene; But are not limited to, cyclopentene, norbornene, 5-methylnorbornene, 5-phenylnorbornene, tetracyclododecene, tricyclododecene, tricyclo undecene, pentacyclopentadecene, pentacyclohexadecene, Cyclic olefins such as cyclododecene; Vinyl halides such as vinyl chloride; Ethyl acrylate, and acrylates such as methyl acrylate. Of these, preferred ethylenically unsaturated compounds are? -Olefins, more preferably? -Olefins having 2 to 4 carbon atoms, 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 vapor phase polymerization method in which a small amount of a polymer is impregnated with a high concentration catalyst solution, and the like are used. The polymerization may be either batchwise or continuous. The reactor used in the polymerization can be used as it is or in a known manner. The polymerization temperature is not particularly limited, and is generally 40 to 180 占 폚, preferably 50 to 120 占 폚. The pressure at the time of polymerization is not particularly limited, but is generally from normal pressure to 20 MPa, preferably from 4 to 15 MPa.

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.

The polyketone resin is preferably contained in an amount of 35 to 70% by weight based on the total weight of the composition.

The polyketone is preferably used in an amount of 35 to 70% by weight of the total composition. If it is less than 35% by weight, the moldability may be poor. When it exceeds 70% by weight, the impact resistance improving effect is reduced.

The polyamide of the present invention will be described.

The polyamide is excellent in compatibility with the polyketone because the -NH group and the -CO group in the polyketone can be hydrogen bonded. The polyamide is also excellent in compatibility with rubber by -NH 2 bonding at the chain terminal. Thus, the polyamide improves the compatibility of the polyketone with the rubber, thereby significantly improving the impact strength of the polyketone.

The polyamide may be selected from the group consisting of polyamide 6 (PA6), polyamide 66 (PA66), polyamide 6/66 copolymer (PA6 / 66), polyamide 610 (PA610), polyamide 612 ) And polyamide 12 (PA12), and the like.

It is preferable to use 10 to 35% by weight of the polyamide in the total composition. If less than 10% by weight is used, there is a problem that compatibility between polyketone and rubber is insufficient. When the polyamide is used in excess of 35% And the price increase.

The rubber of the present invention will be described. Examples of the rubber used in the present invention include maleic anhydride-grafted rubber composed of ethylene-octene rubber (EOR), ethylene propylene diene monomer rubber (EPDM) and ethylene propylene rubber (EPM) , And the like.

Preferred rubbers include ethylene propylene diene monomer (M-class) rubber, EPDM rubber. The EPDM rubber is a non-polar rubber material having no double bond in the main chain and has excellent weatherability, ozone resistance, stability and electrical properties.

EPDM rubber is a by-product extracted from crude oil and is produced by solution polymerization reaction. Since it is economical, it is widely used in automobile products, tubes, belts, electric wires and various industrial products. It is preferable to use maleic anhydride grafted ethylene-octene rubber (EOR-MAH), which is preferably grafted with maleic anhydride.

In the polyketone composition of the present invention, the rubber is preferably contained in an amount of 20 to 30% by weight based on the total weight of the composition. If the content of rubber is less than 20% by weight, it is difficult to expect an improvement in impact strength. If the content of rubber exceeds 30% by weight, physical properties inherent to polyketone are lost and ductility is decreased.

On the other hand, the composition of the present invention as described above is molded by a method such as extrusion and injection, and is manufactured as a cover part for a mower.

Hereinafter, a method for manufacturing a cover part for a lawn mower to which the polyketone of the present invention is applied is as follows.

A method of manufacturing a cover part for a lawn mower according to the present invention comprises the steps of: preparing a catalyst composition comprising a palladium compound, an acid having a pKa value of 6 or less, and a bidentate compound of phosphorus; Preparing a mixed solvent (polymerization solvent) containing an alcohol (for example, methanol) and water; Conducting the polymerization in the presence of the catalyst composition and the mixed solvent to prepare a linear 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 mixing and extruding 35 to 70% by weight of the polyketone, 10 to 35% by weight of polyamide and 20 to 30% by weight of rubber to produce a polyketone composition; And injection molding the composition. However, the present invention is not limited thereto.

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

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

Examples of the bidentate ligand compound constituting the catalyst composition include 1,3-bis [diphenylphosphino] propane (for example, 1,3-bis [di (2-methoxyphenylphosphino)] propane, , 3-bis [bis [anilyl] phosphinomethyl] -1,5-dioxaspiro [5,5] undecane and ((2,2-dimethyl-1,3-dioxane- ) Bis (bis (methylene)) bis (bis (2-methoxyphenyl) phosphine), and the amount thereof is suitably 1 to 20 (mol) relative to the palladium compound.

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

The polymerization temperature is preferably in the range of 50 to 100 ° C and the reaction pressure in the range of 40 to 60 bar. The resulting polymer is recovered through filtration and purification processes after polymerization, and the remaining catalyst composition is removed with a solvent such as alcohol or acetone.

In the present invention, the obtained polyketone polymer is mixed with polyamide and rubber containing nylon 6, nylon 66, and then extruded by an extruder to finally obtain a composition. The composition may be prepared by charging the mixture into a twin-screw extruder, and melt-kneading and extruding the mixture.

In this case, the extrusion temperature is preferably 230 to 260 ° C, and the screw rotation speed is preferably in the range of 100 to 300 rpm. If the extrusion temperature is less than 230 캜, kneading may not occur properly, and if the extrusion temperature exceeds 260 캜, problems related to the heat resistance of the resin may occur. If the screw rotational speed is less than 100 rpm, the kneading may not be smoothly performed, and if it exceeds 300 rpm, the mechanical properties may deteriorate.

A composition for a lawn mower can be produced by preparing a composition as described above and extrusion molding or injection molding the composition.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail with reference to specific embodiments. However, these embodiments are merely intended to clarify the present invention and are not intended to 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

Linear alternating polyketones composed of carbon monoxide and ethylene and propene are prepared by reacting palladium acetate, trifluoroacetic acid, and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene) 2-methoxyphenyl) phosphine) in the presence of a catalyst composition. In the above, the content of trifluoroacetic acid with respect to palladium is 10 times the molar ratio, and the two stages of the first stage at a polymerization temperature of 78 占 폚 and 84 占 폚 are carried out. In the polyketone prepared above, carbon monoxide was 50 mol%, ethylene was 46 mol%, and propylene was 4 mol%. The melting point of the polyketone was 220 占 폚 and the viscosity (IV) measured by HFIP (hexa-fluoroisopropano) at 25 占 폚 was 1.4 dl / g.

20% by weight of nylon 6 and 20% by weight of maleic anhydride-grafted ethylene-octene rubber (EOR-MAH) were added to the composition to prepare a composition, 40 cm in length and L / D = 32 in the form of pellets on an extruder, and then injection-molded to prepare specimens of cover parts for mowers.

Example 2

(Cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) phosphine was used as the catalyst composition for producing the polyketone in Example 1 and the viscosity was 1.6 dl / g of polyketone 65 wt%, nylon 6 10 wt%, and maleic anhydride grafted ethylene-octene rubber (EOR-MAH) 25 wt% were charged.

Comparative Example 1

A composition was prepared by adding 70% by weight of nylon 6 resin and 30% by weight of rubber. The composition thus prepared was pelletized on an extruder using a twin screw having a diameter of 40 cm and operating at 250 rpm and L / D = 32 And then injection molding was carried out to prepare specimens of cover parts for mowers.

Property evaluation

The properties of the specimens prepared in Examples 1 and 2 and Comparative Example 1 were evaluated, and the results are shown in Table 1 below.

division Impact strength (ISO 179 / 1eA) 23 ° C Notched
(kJ / m2) -10 ° C Notched
(kJ / m2) -10 ° C Unnothed
(kJ / m2) Comparative Example 1 14.2 7.6 58.8 Example 1 82.0 20.0 No Break Example 2 88.4 24.9 No Break

As can be seen from Table 1, the notched impact strength measured at 23 ° C in Examples 1 and 2 was superior to that of Comparative Example 1 by 7 times or more, and was measured at a low temperature of -10 ° C The notched impact strength was also two times or more superior to that of Comparative Example 1.

Therefore, the cover part for a lawn mower including the polyketone composition according to the present invention is excellent in impact strength as a mechanical property, so that it is applied as a covering part for lawn mower by improving the reliability and durability of the product in a low temperature environment requiring strong impact property It is very suitable.

Claims (2)

From 35 to 70% by weight of a linear alternating polyketone consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon;
10 to 35% by weight of polyamide; And
20 to 30% by weight of a rubber;
Wherein said linear alternating polyketone is prepared in the presence of a catalyst composition which is (cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) phosphine)
The rubber is a maleic anhydride grafted rubber, which is a rubber selected from the group consisting of ethylene-octene rubber (EOR), ethylene propylene diene monomer rubber (EPDM) and ethylene rubber of ethylene propylene rubber (EPM) Two or more species,
And ISO 179 / notched (Notched) impact strength at 23 ℃ measured by 1eA is 82.0 to 88.4kJ / m ^2, notched (Notched) impact strength measured at -10 ℃ 20.0 to 24.9kJ / m ² of And a cover part for a lawn mower.
The method according to claim 1,
Wherein the polyketone has an intrinsic viscosity (IV) of 1.0 to 2.0 dl / g, a molecular weight distribution of 1.5 to 2.5, and a repeating unit represented by the following general formulas (1) and (2) 0.03 to 0.3. ≪ / RTI >
- [- CH2CH2-CO] x- (1)
- [- CH2 --CH (CH3) - CO] y - (2)
(x and y represent mol% of each of the general formulas (1) and (2) in the polymer)