KR101867937B1

KR101867937B1 - Water Ball Valve containing polyketone composition with excellent water-resistance and heat resistance

Info

Publication number: KR101867937B1
Application number: KR1020160184110A
Authority: KR
Inventors: 이명녕
Original assignee: 주식회사 효성
Priority date: 2016-12-30
Filing date: 2016-12-30
Publication date: 2018-06-15

Abstract

The present invention relates to a composition comprising: a linear alternating polyketone comprising carbon monoxide and at least one olefinically unsaturated hydrocarbon; talc; a glass fiber; and the like, and a polyketone composition having excellent water resistance and mechanical property retention ratios, in comparison to brass and lead materials to be used for a water ball valve, can be developed and suitably applied to a water ball valve.

Description

[0001] The present invention relates to a water ball valve comprising a polyketone composition having excellent water resistance and heat resistance,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyketone resin for a ball valve for water use which replaces brass, and more particularly, to a polyketone resin for a water ball valve including a linear alternating polyketone composed of carbon monoxide and at least one olefinically unsaturated hydrocarbon, A polyketone resin suitable for application is provided.

BACKGROUND OF THE INVENTION [0002] Recently, there has been a growing interest in polyelectrolyte or polyketone polymers, a group of linear alternating polymers of carbon monoxide and at least one ethylenically unsaturated hydrocarbon. 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 >

On the other hand, water ball valves are mostly used as brass and lead. It is water-related parts, so it should have good water resistance and no discoloration. Brass and lead have been used in water ball valves because of their advantages. However, brass is a cast product, which is low in productivity and has a disadvantage of high cost compared to plastic. Lead has a drawback that molding is difficult and aging is required for one week have. Polyamide materials have been used as substitute materials, but polyketone materials having water resistance and excellent water retention in a water atmosphere have been considered for application to related applications.

Korean Patent No. 1664925 Korean Patent No. 1539680 Korean Patent No. 1664250 Japanese Patent Laid-Open No. 1996-253676

The present invention relates to a polyketone composition having excellent water resistance, dimensional stability and releasability by preparing a composition containing a talc, a glass fiber, a polyethylene wax and an antioxidant in a polyketone having water resistance, and to develop a ball valve for water using the same .

According to a preferred embodiment of the present invention, 45 to 65% by weight of a linear alternating polyketone consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon; 23 to 33% by weight of talc; And 12 to 22% by weight of glass fiber, wherein the impact strength in the water immersion condition measured for 23 to 500 hours is improved by 120 to 140% of the initial property value, and the tensile strength is maintained at 75 to 85% The present invention provides a ball valve for water use including a polyketone composition.

According to another preferred embodiment of the present invention, the polyketone composition further comprises 0.1 to 1.0 parts by weight of an antioxidant relative to the weight of the composition; And 0.1 to 1.0 parts by weight of polyethylene wax (PE wax).

According to another preferred embodiment of the present invention, the flexural strength and flexural modulus of the polyketone composition measured at 23 to 500 hours under water immersion conditions are maintained at 75 to 85% of the initial physical properties, 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)

The polyketone composition of the present invention is excellent in mechanical strength in the water immersion condition compared to the polyamide material used in the existing water ball valve and has an advantage of hardly showing the heat change color and is excellent in use for ball valves requiring water resistance and heat resistance It is effective.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a photograph showing the result of thermo-discoloration evaluation of a composition sample prepared by the present invention. FIG.

The present invention provides a water ball valve comprising a polyketone composition comprising polyketone, talc, glass fibers, polyethylene wax and an antioxidant.

The polyketone used in the water ball valve including the polyketone composition for a water valve ball valve of the present invention is a line-by-line alternating structure and substantially contains carbon monoxide per one molecule of the 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, tricyclodecene, 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 second component of the composition of the present invention is talc, and in the present invention, the talc is 23 to 33% by weight based on the total composition. When the content of the talc is less than 23 wt% based on the total weight of the composition, the effect is insufficient, and when it exceeds 33 wt%, the processability is poor.

As another composition of the present invention, glass fiber is used. The content of the glass fiber is 12 to 22% by weight. When the content of the glass fiber is less than 23% by weight based on the total composition, the effect is insufficient. When the glass fiber content is more than 33% by weight, the workability is poor.

The talc and glass fiber serve to prevent the warpage characteristics of the final product.

In the present invention, polyethylene wax and antioxidant may further be added to improve workability and physical properties.

The polyethylene wax is 0.1 to 1.0 part by weight relative to the total polyketone composition. When the amount is less than 0.1 part by weight, the moldability is poor. When the amount is more than 1.0 part by weight, the impact strength is decreased.

The polyethylene wax used in the present invention is a nonpolar type and is applied to a polar polyketone to improve releasability and fastness.

The polyethylene wax used in the present invention has a melting point of 135 占 폚, a density of 0.96 g / cm3, and a white color. In the present invention, 0.5 part by weight is preferably used.

As the antioxidant used in the present invention, CaO / P ₂ O ₅ can be used. CaO is 53 to 55%, P ₂ O ₅ is 40 to 42%, Medium particle size (d50) is 2.9 to 3.4 μm to be. Such an antioxidant has a deactivation effect of the metal catalyst used in the polymerization. The antioxidant is preferably contained in an amount of 0.1 to 1.0 part by weight based on 100 parts by weight of the polyketone composition. If the amount of the antioxidant is less than 0.1 parts by weight, the deactivation function of the metal catalyst may be deteriorated. If the amount of the antioxidant is more than 1.0 part by weight, the physical properties of the product may be deteriorated.

Hereinafter, the production method for producing the polyketone composition for a water valve for a water valve of the present invention is as follows.

First 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 2 to 40 wt% of the polyketone, 23 to 33 wt% of talc, and 12 to 22 wt% of the glass fiber were compounded together at 240 ° C. by employing two side feeders to prepare a composition. In addition to the composition, an antioxidant 0.1 And 0.1 to 1.0 part by weight of a polyethylene wax are mixed and extruded to prepare a final 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 resulting polyketone is compounded with talc and glass fibers at 240 캜 by using two side feeders to form a composition. In addition, 0.1 to 1.0 part by weight of an antioxidant and 0.1 to 1.0 part by weight of a polyethylene wax Polyketone compositions for water service valves of the present invention can be prepared by mixing and extrusion and injection molding.

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.

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

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 220 ° C, a viscosity IV of 1.3 dl / g as measured by HFIP (hexa-fluoroisopropano) at 25 ° C, and a melt index ) Was 60 g / 10 min. The polyketone terpolymer prepared above was mixed with talc and glass fibers using two side feeders to prepare a blend. The weight ratio of the blend to the polyketone terpolymer and a weight of 60%, talc 25% by weight, 15% by weight of glass fiber. since the total blend, based on the weight of the polyethylene wax, 0.5 parts by weight of the final polyketone composition by mixing CaO / P ₂ O ₅ 0.5 parts by weight of an antioxidant The pellets were then prepared on an extruder using a twin screw having a diameter of 2.5 cm and operating at 250 rpm and L / D = 32. The prepared test specimens were injection molded on a molding machine with a mold clamping force of 80 tons .

Examples 2 and 3

The above-mentioned Example 1 was subjected to a reproduction test two times under the same conditions, and these were represented by Examples 2 and 3, respectively.

Comparative Example 1

A composition was prepared by mixing nylon 6 60 wt.%, Talc 25 wt.%, And glass fiber 15 wt.% And then pelletizing on a extruder using a twin screw having a diameter of 2.5 cm and operating at 250 rpm and L / pellet). The prepared test pieces were injection molded on a molding machine having a mold clamping force of 80 tons.

The impact strength, tensile strength, flexural strength and flexural modulus of each of the above Examples 1 to 3 and Comparative Example 1 were measured under the conditions of 23 ° C for 0 hours and 100 hours and 500 hours, .

1. Impact strength: ASTM D638.

2. Tensile strength: ASTM D638.

3. Flexural Strength: The flexural strength was measured according to ASTM D790.

4. Flexural modulus: It was conducted according to ASTM D790.

Water immersion, 23 ℃ Example 1 Example 2 Example 3 Comparative Example 1 0hr Impact strength (kgf.cm/cm) 6.8 6.3 6.6 5.4 Tensile Strength (MPa) 85 85 85 109 Flexural Strength (MPa) 140 141 135 168 Flexural modulus (MPa) 7362 7469 7430 7498 100hr Impact strength (kgf.cm/cm) 9.2 9.7 10.6 8.6 Tensile Strength (MPa) 76 77 77 75 Flexural Strength (MPa) 133 129 123 125 Flexural modulus (MPa) 6528 6492 6594 4984 500 hr Impact strength (kgf.cm/cm) 8.1 9.1 9.2 21.5 Tensile Strength (MPa) 69 69 69 43 Flexural Strength (MPa) 123 122 123 85 Flexural modulus (MPa) 5808 5807 5927 2905

In addition, Example 1 was evaluated for thermal discoloration under the following conditions.

Thermal discoloration evaluation was performed for 290 hours at 90 deg. C, 100 deg. C and 125 deg. C, and the results are shown in Fig.

As a result of evaluation of thermal discoloration for 0 hours and 290 hours in the example, it was confirmed that there was little thermal discoloration as shown in FIG.

In Comparative Examples and Examples of the present invention, the impact strength was improved by 133% in the water immersion condition in Examples 1 to 3 as compared with Comparative Example 1, and the tensile strength, flexural strength and flexural modulus were maintained at 80% .

Also, it can be seen from Example 1 that the polyketone composition of the present invention shows almost no heat discoloration compared with the initial stage, and that it is also excellent in heat resistance.

Therefore, the polyketone composition prepared according to the present invention is excellent in water resistance and heat resistance, and thus is suitable for application as a water ball valve.

Claims

45 to 65 wt% of a linear alternating polyketone consisting of carbon monoxide and at least one olefinically unsaturated hydrocarbon;
23 to 33% by weight of talc; And
12 to 22% by weight of a glass fiber;
0.1 to 1.0 part by weight of an antioxidant relative to 100 parts by weight of the blend; And 0.1 to 1.0 part by weight of a polyethylene wax (PE wax)
The linear alternating 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) Value is 0.03 to 0.3,
The ligand of the catalyst composition used in the polymerization of the linear alternating polyketone is (cyclohexane-1,1-diylbis (methylene)) bis (bis (2-methoxyphenyl) phosphine)
The impact strength in water immersion conditions measured at 23 DEG C for 500 hours is improved by 120 to 140% of the initial property value, and the tensile strength, flexural strength, and flexural modulus maintain 75 to 85% of the initial property value A ball valve for water use comprising a polyketone composition.
- [- CH2CH2-CO] x- (1)
- [- CH2 --CH (CH3) - CO] y - (2)
(x and y represent mol% of each of the general formulas (1) and (2) in the polymer)

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