KR101664931B1 - Office polyketone parts - Google Patents

Abstract

The present invention is produced by injection molding a linear alternating polyketone comprising carbon monoxide and at least one olefinically unsaturated hydrocarbon and having a molecular weight distribution of 1.5 to 2.5 and a residual amount of palladium catalyst of 20 ppm or less, wherein the impact strength is 8 to 15 kJ / m 2, and more particularly to an office polyketone molded part characterized by excellent abrasion resistance.

Description

Office polyketone parts {Office polyketone parts}

The present invention relates to an office polyketone part characterized by being produced by injection molding polyketone, and more particularly to an office polyketone part having excellent abrasion resistance and impact resistance.

Polyketone (PK) is a low cost raw material and polymerization process ratio compared with general engineering plastic materials such as polyamide polyester and polycarbonate, but it is resistant to heat and chemical. Impact resistance and fuel permeability.

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

The polyketone is included in general purpose high-performance plastics and has an advantage that it has high strength equivalent to conventional engineering plastics and good affinity with rubber. Due to the characteristics of polyketone, polyketone can be used for tire cord or rubber material, which is conventionally used exclusively with paraffin-based aramid fibers. However, polyketone can be used for automobile timing chain guide bearings and door check gears There is a problem that the friction is relatively large and the abrasion resistance is weak compared with the conventional engineering plastics.

Therefore, efforts to improve abrasion resistance, which is a disadvantage of polyketone, continue. 870.133 mentions that polyketone is blended with polytetrafluorethylene to increase the melt strength of the polyketone, but there is no mention of increasing the abrasion resistance of the polyketone.

Also, U.S. Patent No. 5,618,870 mentions that polyketone is blended with a silicone oil (s i 1 i con 0 i 1) to increase the abrasion resistance of the polyketone, but there is no mention of other ingredients. And the price of silicone oil added is very expensive, so it is limited to be used for practical industrial use.

Korean Patent Laid-Open Publication No. 2012-0071814 also mentions that the polyketone manufacturing process is controlled to increase the wear resistance of polyketones, but there is no mention of components related to wear resistance.

Therefore, it is necessary to develop a technique for further improving the abrasion resistance of the polyketone which is poor in abrasion resistance.

Korean Patent No. 1004453540000 Korean Patent No. 1008108650000

In order to solve the above-mentioned problems, the present invention provides a polyketone molded part which is characterized by sufficient wear resistance and impact resistance by using a polyketone in which an anti-wear agent is not blended, but also by blending a wear- It is intended to provide parts.

In order to achieve the above object, the present invention provides a process for producing a polyphenylene ether by the injection molding of a linear alternating polyketone comprising carbon monoxide and at least one olefinically unsaturated hydrocarbon having a molecular weight distribution of 1.5 to 2.5 and a residual amount of palladium catalyst of 20 ppm or less, Is 8 to 15 kJ / m < 2 >.

In addition, the linear alternating polyketone has an abrasion resistance of 1.0 mm < ³ > / kg / km or less in the base state.

Further, the polyketone has an intrinsic viscosity of 1.0 to 2.0 dl / g.

The polyketone molded part according to the present invention can obtain sufficient abrasion resistance and impact resistance, even though a polyketone in which a wear-resistant agent is not blended is used. Accordingly, the polyketone molded part of the present invention is usefully applicable to office polyketone parts.

Below. 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, 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.

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. In the presence of a catalyst composition suitably produced from an anion of a non-hydrohalogenic acid having a pKa of less than 6 or preferably less than pKa < 2 > and a bidentate ligand of phosphorus (measured in water at 18 DEG C), carbon monoxide and a hydrocarbon monomer Is 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, 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).

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 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.

 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 polyketone of the present invention has an intrinsic viscosity of 1 to 20 dl / g, preferably 1 to 2 dl / g. If the intrinsic viscosity is less than 1 dl / g, the strength and fatigue resistance of the polyketone fiber are not sufficient, and if the intrinsic viscosity exceeds 20 dl / g, not only is it time and cost in terms of economy, but also dissolves uniformly It is difficult.

The molecular weight distribution of the polyketone is 1.5 to 3.5, preferably 1.5 to 2.5. If the molecular weight distribution is 1.5 or less, the polymerization efficiency is poor. If the molecular weight distribution is 3.5 or more, the mechanical properties are poor. Therefore, the molecular weight distribution in the present invention is preferably 1.5 to 3.5.

 The content of the Pd element in the polyketone of the present invention is preferably 20 ppm or less. When the content of the Pd element exceeds 20 ppm, thermal denaturation and chemical denaturation due to the residual Pd element are liable to occur, and in the melt molding, a phenomenon such as an increase in the melt viscosity and an increase in the viscosity of the dopant 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.

In the present invention, a phosphine-based bidentate ligand ligand having a catalytic amount of 3 to 20 times the catalytic amount is introduced into the reactor immediately before the completion of the polyketone polymerization reaction so that the catalyst (Pd) remaining after the polymerization reaction is bound to the phosphine ligand, Thereby preventing the polymerization reaction from occurring during the decompression at the end of the reaction, thereby reducing the molecular weight distribution. Further, the bonded compound is washed with a methanol solvent after polymerization to reduce the content of Pd in the polyketone, thereby preventing deterioration of the polyketone or discoloration. When the amount of the ligand of the biphenyl ligand of the phosphine series is less than 3 times the amount of the catalyst, there is a problem that the ligand binding to the catalyst does not bind well and the polymerization reaction is activated. If the amount is 20 times or more, There is a problem that it costs a lot. The amount of the bipyramidal ligand of the phosphine series is preferably 3 to 10 times, more preferably 3 to 5 times.

Examples of phosphine based bidentate ligand ligands include 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) Bis [di (2-methoxyphenyl) phosphino] propane, 1,3-bis [di (2-methoxy- Bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) phosphine ) And the like.

Further, the present invention provides an office polyketone part improved in abrasion resistance by blending an anti-wear agent. As the wear-resistant agent, a commonly used wear-resistant agent may be used, but preferably a silicone wear-resistant agent is used, more preferably a silicone oil or silicone gum is used. If the content of the wear-resistant agent is less than 0.5% by weight, the synergistic effect of the wear resistance obtained by adding the wear-resistant agent is not sufficient. If the content of the wear-resistant agent is less than 2.0% by weight , The impact resistance and formability peculiar to the polyketone other than the abrasion resistance are lowered.

3. Comparative Examples and Examples

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

The linear alternating polyketone terpolymer of carbon monoxide and ethylene and propene is prepared by reacting palladium acetate, trifluoroacetic acid and ((2,2-dimethyl-1,3-dioxane-5,5-diyl) bis (methylene) Bis (2-methoxyphenyl) phosphine). The molar ratio of ethylene to propene in the polyketone terpolymer prepared above was 46 to 4. The melting point of the polyketone terpolymer was 220 占 폚, the LVN measured at 25 占 폚 by HFIP (hexa-fluoroisopropano) was 1.4 dl / g, MI (Melt index) was 48 g / 10 min and the amount of residual palladium catalyst 10 ppm and a molecular weight distribution of 2.0. The polyketone terpolymer prepared above was molded into a pellet on an extruder using a twin screw having a diameter of 2.5 cm and L / D = 32 operating at 250 rpm and injection molded to produce a specimen for office polyketone parts .

Separately from the above specimens, a silicone oil, which is a wear resistant agent, was prepared by preparing the polyketone composition containing the polyketone, and the content of the polyketone composition was 1.0% by weight based on the entire composition to prepare a polyketone composition. To prepare specimens for office polyketone parts.

Comparative Example 1

A polyoxymethylene resin was prepared in the form of a pellet on an extruder using a twin screw having a diameter of 2.5 cm and operated at 250 rpm and having an L / D of 32, and a specimen for an office polyketone part was prepared. Was added to prepare a sample for office polyketone part.

Property evaluation

The abrasion resistance and impact resistance of the office parts specimens prepared in Example 1 and Comparative Example 1, respectively, in the case of adding the base state and the wear resistance agent were evaluated, and the results are shown in Table 1 below.

1. 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. The abrasion resistance was evaluated by evaluating the abrasion resistance. The smaller the amount of non-abrasion obtained, the better the abrasion resistance.

2. Izod Impact Strength: Performed according to ASTM D256.

Grade importance Cycle time (s) Coefficient of friction Wear amount
(mm ³ / kg / km) noise Impact strength
(kJ / m2) Example 1 Base 1.24 17
0.34 0.60 NO (60) 10 Antiwear additive 0.10 0.01 NO (60) Comparative Example 1 Base 1.42 22 0.40 8.10 squeak noise (80) 6.5 Antiwear additive 0.13 0.10 NO (60)

As shown in Table 1, in the polyketone base state, the abrasion resistance and the impact resistance were evaluated to be superior to those in the POM base state, and the abrasion resistance and impact resistance were also excellent when the wear resistance agent was added. , The polyketone component for office use, which has excellent impact resistance and abrasion resistance, is suitable for application as an office polyketone part.

Claims (6)

Which is produced by injection molding a linear alternating polyketone comprising carbon monoxide and at least one olefinically unsaturated hydrocarbon and having a molecular weight distribution of 1.5 to 2.5 and a residual amount of palladium catalyst of 20 ppm or less,
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)
Wherein the extruded molded article has an impact strength of 8 to 15 kJ / m < ² >.

delete The method according to claim 1,
Wherein the linear alternating polyketone has an abrasion resistance of 1.0 mm < ³ > / kg / km or less in the base state.
The method according to claim 1,
Wherein said linear alternating polyketone has an intrinsic viscosity of 1.0 to 2.0 dl / g.
A polyketone composition comprising carbon monoxide and at least one olefinically unsaturated hydrocarbon and having a molecular weight distribution of 1.5 to 2.5 and a balance of a palladium catalyst of 20 ppm or less with a linear alternating polyketone and a wear resistant agent,
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)
Wherein the abrasion resistance of the line-by-line alternating polyketone during polymerization is 0.1 mm ³ / kg / km or less.
6. The method of claim 5,
Wherein the wear-resistant agent is 0.5 to 2.0% by weight of the total polyketone composition, and is a silicone oil or silicone gum.