KR101646034B1 - Poly ketone connector - Google Patents

Abstract

The present invention relates to a polyketone connector which is produced by injection molding a linear alternating polyketone composed of carbon monoxide and at least one ethylenically unsaturated hydrocarbon. More particularly, the present invention relates to a polyketone connector having a rate of decrease in flexural modulus and a wear resistance And a step of steam-forming at the time of manufacture is omitted.

Description

Polyketone connector

The present invention relates to a polyketone connector, which is produced by injection molding polyketone. More particularly, the polyketone connector is excellent in impact strength at room temperature, cold resistance and thin film formability, To a polyketone connector having a specific molar ratio.

Thermoplastic polyesters typified by polyethylene terephthalate and polybutylene terephthalate and thermoplastic polyamides typified by nylon 6 and nylon 66 are excellent in mechanical properties, heat resistance, chemical resistance, weather resistance, and electrical properties, Is used in a wide range of fields. The thermoplastic polyester and the thermoplastic polyamide can be continuously used at a high temperature from an excellent heat resistance. However, when exposed at a high temperature for a long time, the crystallization and thermal deterioration gradually progress and the toughness is lowered, especially the hinge characteristic is greatly lowered, and the molded article is easily broken due to bending.

For this reason, the use thereof is limited in applications where bending resistance (hinge characteristic) is required. As a method for improving such required characteristics, Japanese Patent Application Laid-Open No. 60-231757 discloses a method of blending an aromatic carbonate or glycidyl group-containing copolymer into a polyester resin, a method of blending a vinyl polymer or glycidyl Containing vinyl-based copolymer to a polyester resin, and the like.

However, at the time of evaluating the breakdown of the cold-weather product exposed to low temperature, the product was broken, the thin-film formability was poor, and the impact strength at room temperature was sufficient but sufficient.

Korean Patent No. 1006685720000 Korean Patent No. 1004453540000 Korean Patent No. 1008108650000

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made to solve the above problems of the prior art, and it is an object of the present invention to provide a polyketone connector having a sufficient impact strength at room temperature,

In order to accomplish the above object, the present invention relates to a method of producing a polyurethane resin by injection molding of a linear alternating polyketone comprising carbon monoxide and at least one ethylenically unsaturated hydrocarbon, and a reduction rate of a flexural modulus of 30% And an abrasion resistance of 1.0 mm < 3 > / kg / km or less.

Specifically, the step of forming a polyketone connector is omitted.

The polyketone connector of the present invention is excellent in impact resistance, cold resistance, and thin film formability as compared with conventional connectors made of thermoplastic polyester or thermoplastic polyamide. Further, in the production of the polyketone connector, the stepping process is omitted, the process is simple, and thus the manufacturing cost can be reduced.

Hereinafter, the present invention will be described in detail.

1. Polyketone polymer

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, Is an aliphatic group or an 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, Of 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.

Preferred polymeric rings of the polyketone polymers in the present invention can be represented by the following formula (1).

[Chemical Formula 1]

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

In the above formula (1), G is an ethylenically unsaturated hydrocarbon, particularly 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 2.0 dl / g. If the intrinsic viscosity is less than 0.5 dl / g, the mechanical properties are deteriorated. If 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.

A preferred process for producing a polyketone polymer is disclosed in U.S. Patent No. 4,843,144. Palladium compounds and (measured in water at 18 DEG C) Carbon monoxide and hydrocarbon monomers in the presence of a catalyst composition suitably produced from anions of non-hydrohalogenic acids with pKa less than 6 or preferably less than pKa2 and phosphorus bidentate ligands And then contacted under polymerization conditions to prepare a polyketone polymer.

2. Polymerization of polyketones

Hereinafter, a polymerization method of a polyketone will be described.

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. 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).

(2)

.

.

      Bis (bis (2-methoxyphenyl) phosphine) bis ((2,2-dimethyl-1,3-dioxane-5,5- 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.

      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.

 In addition, in the process, a mixed solvent of acetic acid and water is used as a liquid medium, benzophenone is added during polymerization, and carbon monoxide, an ethylenically unsaturated compound and one or more olefinic unsaturated compounds are added to improve the catalytic activity and intrinsic viscosity of the polyketone In addition, in the prior art, it is possible to produce a terpolymer having a high intrinsic viscosity at a polymerization time of about 1 to 2 hours, unlike the case where the polymerization time has to be at least 10 hours or more for the purpose of improving the intrinsic viscosity.

 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.

 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.

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

Hereinafter, the polyketone polymerization method will be described in detail with specific polymerization examples, but these polymerization examples are merely intended to make the present invention more clearly understood, and are not intended to limit the scope of the present invention. The polyketone polymerization method of the present invention will be described in detail by way of non-limiting examples of polymerization examples below.

 The intrinsic viscosity and catalytic activity of the polyketone were evaluated in the following manner.

(1) intrinsic viscosity

The polymerized resin is dissolved in a concentration of 0.01 g / 100 ml to 1 g / 100 ml (m-cresol) in a 60 ° C thermostat for about 1 to 5 hours, and the viscosity is measured at 30 ° C. using a Ubelode viscometer. The viscosity according to the concentration is plotted and extrapolated to obtain the intrinsic viscosity.

(2) Catalytic activity

Weight of polymerized resin / weight / hour of palladium (kg / g-Pd · hr).

[Polymerization Example 1]

0.0399 g of ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) g and dissolved in 100 ml of acetone. This mixed solution was dissolved in a mixed solvent of 2,249 ml of methanol and 417 ml of water, and the solution was evacuated by vacuum and charged into a nitrogen-substituted stainless steel autoclave. Ethylene / propylene / carbon monoxide (partial pressure = 46/4/50) was added to the autoclave until the autoclave internal pressure reached 80 bar at the time when the internal temperature reached 70 DEG C, and the contents were heated with stirring at a speed of 800 rpm. He said. Stirring was continued for 2 hours while keeping the inner temperature at 70 ° C and the internal pressure at 80 bar. After cooling, the gas in the autoclave was purged and the contents were taken out. The reaction solution was filtered, washed several times with acetone, ethanol and methanol, and then dried under reduced pressure at room temperature to 80 ° C to obtain 168.4 g of a polymer.

^{From the 13} C-NMR and IR results, it was confirmed that the polymer was substantially a polyketone comprising repeating units derived from carbon monoxide and repeating units derived from ethylene and propylene. The catalyst activity was equivalent to 12.5 kg / gPd · hr and the intrinsic viscosity was 1.4 dl / g. The melt index measurement result was 33 g / 10 min, and the melting temperature was 220 ° C.

3. Remove the steaming process when manufacturing polyketone connectors

NY66, which is used as a material for existing connectors, has a higher impact strength than that of dry (10kJ / m2, dry: 5KJ / m2). In order to improve the impact of the connector, the NY material has a high impact strength due to forced wetting process, but the polyketone has a high self-impact strength, thus eliminating the wetting process. Therefore, in the present invention, it is possible to reduce the manufacturing process of the connector by eliminating the wetting process, thereby ensuring economical efficiency in the connector manufacturing process.

4. Comparative Example and Example

Hereinafter, the present invention will be described in detail through comparative examples and examples. However, it should be understood that the present invention is not limited to these examples.

Example 1

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). In the above, the content of trifluoroacetic acid with respect to palladium is 11 times the molar ratio, and the two stages of the first stage at a polymerization temperature of 80 ° C and the second stage at 84 ° C are carried out. 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 LVN measured at 25 占 폚 by HFIP (hexa-fluoroisopropano) was 1.2 dl / g, the MI index was 60 g / 10 min and the MWD was 2.0. The polyketone terpolymer prepared above was molded into a pellet on an extruder using a twin screw having a diameter of 40 mm and L / D = 32, which was operated at 250 rpm, and then injection molded to prepare a connector specimen.

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). 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. 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 LVN measured at 25 占 폚 by HFIP (hexa-fluoroisopropano) was 1.4 dl / g, the MI index was 60 g / 10 min and the MWD was 2.0. The polyketone terpolymer prepared above was molded into a pellet on an extruder using a twin screw having a diameter of 40 mm and L / D = 32, which was operated at 250 rpm, and injection molded to prepare a connector specimen.

Example 3

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). In the above, the content of trifluoroacetic acid with respect to palladium is 9 times the molar ratio, and the two stages of the first stage at a polymerization temperature of 74 deg. C and the second stage at 84 deg. 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 LVN measured at 25 占 폚 by HFIP (hexa-fluoroisopropano) was 1.6 dl / g, the MI index was 60 g / 10 min and the MWD was 2.0. The polyketone terpolymer prepared above was molded into a pellet on an extruder using a twin screw having a diameter of 40 mm and L / D = 32, which was operated at 250 rpm, and injection molded to prepare a connector specimen.

Example 4

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). 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. 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 LVN measured at 25 占 폚 by HFIP (hexa-fluoroisopropano) was 1.4 dl / g, the MI index was 60 g / 10 min and the MWD was 1.8. The polyketone terpolymer prepared above was molded into a pellet on an extruder using a twin screw having a diameter of 40 mm and L / D = 32, which was operated at 250 rpm, and injection molded to prepare a connector specimen.

Example 5

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). 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. 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 LVN measured at 25 占 폚 by HFIP (hexa-fluoroisopropano) was 1.4 dl / g, the MI index was 60 g / 10 min and the MWD was 2.2. The polyketone terpolymer prepared above was molded into a pellet on an extruder using a twin screw having a diameter of 40 mm and L / D = 32, which was operated at 250 rpm, and injection molded to prepare a connector specimen.

Comparative Example 1

A specimen was prepared in the same manner as in Example 1 except that Polyamide 66 (PA 66) was used as a material of DuPont.

Comparative Example 2

Specimens were prepared in the same manner as in Comparative Example 1 except that polybutylene terephthalate (PBT) was used as a material of Samyang Corporation.

Property evaluation

The pellets prepared in Examples and Comparative Examples 1 and 2 were injection molded to prepare connector specimens, and the properties were evaluated in the following manner. The results are shown in Table 1 below.

1. Flexural modulus: It was performed according to ASTM D790 under the forced wet condition of USCAR CLASS III.

USCAR CLASS III Forced wetting conditions: 95% RH, 145 ° C × 1008hr (ambient temp. Range from -40 ° C to 125 ° C, potential peak temp.

2. Ring-on-Ring Type (Resin): A through-type test piece having an outer diameter of 25.6 mm, an inner diameter of 20 mm and a height of 15 mm was injection-molded and fixed to a testing machine. A press load of 6.6 kgf The test is carried out under the driving conditions of a speed of 10 cm / s. At this time, the non-abrasion amount was calculated using the following formula to evaluate the abrasion resistance. The smaller the amount of non-abrasion obtained, the better the abrasion resistance.

Non-wear amount = Wear weight (mg) / [Density (mg / mm3) X Pressure load (kgf) X Travel distance (km)]

* Test equipment: Trust type (Friction type abrasion tester)

Evaluation items Comparative Example 1 Comparative Example 2 Example 1 Example 2 Example 3 Example 4 Example 5 Decrease rate of flexural modulus (%) 73 62 21 23 22 21 22 Wear resistance (mm3 / kg / km) 10.2 11.2 0.60 0.62 0.63 0.61 0.60

As shown in Table 1, the lowering rate of the flexural modulus in the case of the Examples 1 and 2 was lower than that in Comparative Examples 1 and 2, and the wear resistance was lower than the Comparative Examples 1 and 2, .

Claims (4)

A method for producing a polyphenylene ether by prepolymerizing a linear alternating polyketone comprising carbon monoxide and at least one ethylenically unsaturated hydrocarbon,
The ligand of the catalyst composition in the polymerization of the linear alternating polyketone may be selected from the group consisting of bis (2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene) Pin), the intrinsic viscosity of the linear alternating polyketone is 1.0 to 2.0 dl / g,
Wherein the rate of decrease in the flexural modulus is 30% or less and the abrasion resistance is 1.0 mm < 3 > / kg / km or less in US CAR CLASS III.
The method according to claim 1,
Wherein the step of forming a polyketone connector is omitted.
delete delete