KR20140097719A - Composition of polyketone with high tribological properties - Google Patents

Abstract

The present invention relates to a polyketone composition with high wear resistance and a use thereof. By adding wear resistance material of a specific material to polyketone with excellent heat-resistance, chemical resistance, fuel permeate resistance, and impact resistance and improving wear resistance of polyketone, parts of vehicles such as a timing chain guide, a bearing, a door check gear, a power steering warm gear, a door regulator gear, and the like which existing expensive wear resistance polyamide-based materials are applied to can be replaced, thereby significantly improving wear resistance of polyketone and saving manufacturing costs.

Description

[0001] The present invention relates to a polyketone composition having high abrasion resistance,

TECHNICAL FIELD The present invention relates to a polyketone composition having excellent abrasion resistance and a use thereof, and more particularly, to a polyketone composition which is improved in abrasion resistance of a polyketone composition by including a wear resistant material of polyketone and a specific substance, A polyketone composition excellent in abrasion resistance that can improve abrasion resistance and economical efficiency by replacing automobile parts and the like to which a polyamide-based material such as polyamide-based material is applied, and use thereof.

Polyketone (PK) is an inexpensive raw material and polymerization process ratio compared to general engineering plastic materials such as polyamide, polyester and polycarbonate, and is excellent in heat resistance, chemical resistance, impact resistance and fuel permeability.

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

The polyketone is included in a general purpose high-performance plastic, and has an advantage in that it has a strength equivalent to that of conventional engineering plastics and has good affinity with rubber. Due to the characteristics of polyketone, polyketone can be used for tire cords and rubber materials which are conventionally used exclusively for paraffin-based aramid fibers.

However, polyketone is used in automotive timing chain guides, bearings, and door check gears, and has a disadvantage in that it has a relatively large friction and relatively low abrasion resistance compared to engineering plastics.

Accordingly, efforts to improve abrasion resistance, which is a disadvantage of polyketone, have been continuing. U.S. Patent No. 4,870,133 discloses a method of blending polytetrafluoroethylene with polyketone to improve melt strength of polyketone, , There is no mention of increasing the abrasion resistance of polyketones.

In addition, U.S. Patent No. 5,618,870 mentions that polyketone is blended with silicone oil to increase the abrasion resistance of polyketones, 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 abrasion resistance of the polyketone, but there is no mention of components related to abrasion resistance.

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

It is an object of the present invention to overcome the above-mentioned problems by providing a polyketone and an abrasion-resistant material of a specific material to significantly improve the abrasion resistance of polyketone to replace an automobile part to which a conventional expensive polyamide- A polyketone composition excellent in abrasion resistance, which has an effect of improving the wear resistance of automobiles and lowering the manufacturing cost, and use thereof.

In order to achieve the above object, And at least one abrasion resistant material selected from the group consisting of silicon, polytetrafluoroethylene, calcium carbonate, maleic acid, molybdenum and magnesium stearate.

At this time, it is preferable that the content of the polyketone is 80 to 99.9% by weight and the content of the abrasion-resistant material is 0.1 to 20% by weight based on the total weight of the composition.

Particularly, the wear resistant material is preferably silicon, polytetrafluoroethylene or magnesium stearate.

Further, it is preferable that 97 wt% of the polyketone and 3 wt% of silicon are based on the total weight of the composition.

The polyketone is preferably a terpolymer obtained by polymerizing monomers such as carbon monoxide, ethylene and propylene.

Meanwhile, the polyketone composition is preferably applied to an automotive timing chain guide, a bearing, a door check gear, a power steering worm gear, and a door regulator gear.

The effects of the present invention having the above-described structure are as follows: polyketone; And abrasion resistant materials of specific materials including at least one selected from the group consisting of silicon, polytetrafluoroethylene, calcium carbonate, maleic acid, molybdenum, and magnesium stearate, thereby improving the abrasion resistance of the polyketone It is effective.

In addition, the present invention has an advantage in that the abrasion resistance of parts can be improved by replacing a part to which a high-priced polyamide-based material is applied, and the manufacturing cost can be lowered.

Hereinafter, the present invention will be described in detail with reference to the drawings and tables.

1. Composition

The polyketone composition having excellent abrasion resistance according to the present invention is a polyketone excellent in heat resistance, chemical resistance, fuel permeability and impact resistance, and the like; And abrasion resistance of a specific material which reduces abrasion, it is possible to remarkably improve the abrasion resistance of the polyketone due to the abrasion resistance of a specific material dispersed in the polyketone, particularly abrasion resistance of a specific material dispersed on the surface have.

Here, the polyketone is a terpolymer in which carbon monoxide, ethylene and propylene are polymerized with monomers.

The abrasion resistant material of the specific material added to improve the abrasion resistance and abrasion resistance of the composition is silicon, polytetrafluorethylene (PTFE), calcium carbonate (CaCO ₃ ), maleic acid, Molybdenum, molybdenum, magnesium stearate and the like, more preferably silicon, polytetrafluoroethylene or magnesium stearate, and most preferably silicon.

More specifically, the silicon may be provided in the form of a gum (product of the liquid type silicon produced by the POM master batch) or powder, added to the polyketone, and then blended or the like Lt; RTI ID = 0.0 > polyketone.

The polytetrafluorethylene (PTFE) may be provided in a powder form, added to a polyketone, and then dispersed in a polyketone through blending or the like.

The calcium carbonate (CaCO ₃ ) may be provided in the form of a powder of a product used as a lubricant for engineering plastics, and may be added to polyketones and then dispersed in polyketones through blending or the like.

The maleic acid may be provided in the form of an MA-g-ethylene copolymer substituted with maleic acid by graft polymerization of maleic acid to the ethylene copolymer, Added to the ketone, and then dispersed in the polyketone through blending or the like.

The molybdenum (Mo) may be provided in a powder form of molybdenum disulfide (MoS ₂ ), may be added to the polyketone, and then may be dispersed in the polyketone through blending or the like.

The magnesium stearate may be provided in the form of a powder of a lubricant product, added to a polyketone, and then dispersed in a polyketone through blending or the like.

2. Content of composition

In the polyketone composition having excellent abrasion resistance according to the present invention, it is preferable that the polyketone content is 80 to 99.9% by weight based on the total composition weight and the abrasion-resistant content of the specific material is 0.1 to 20% by weight.

When the content of the polyketone is less than 80% by weight, the mechanical properties, thermal stability and fluidity of the composition may be reduced. When the content of the polyketone is more than 99.9% by weight, The effect of improving the abrasion resistance of the polyketone composition may be insignificant.

If the abrasion resistance of the specific material is less than 0.1% by weight, the effect of improving the abrasion resistance of the composition may be insignificant. If the abrasion resistance is more than 20% by weight, the mechanical properties and thermal stability of the composition are decreased, Can happen.

In a more preferred embodiment, the polyketone content is 97% by weight based on the total composition weight, and the abrasion-resistant material content of the specific material is 3% by weight.

On the other hand, a polyketone composition having excellent abrasion resistance according to the present invention can be suitably produced by those skilled in the art with reference to known techniques.

3. Usage

The polyketone composition having excellent wear resistance according to the present invention is preferably applied to automobile timing chain guides, bearings, door check gears, power steering worm gears, door regulator gears, and the like, to which conventional wear resistant polyamide materials have been applied.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are merely illustrative of the present invention and that the scope of the present invention is not construed as being limited by these embodiments.

Comparative Examples 1 to 5, which are conventional engineering plastics, and the specimens of Examples 1 to 12, which are polyketone compositions having excellent abrasion resistance according to the present invention, were prepared by the following procedure.

The wear resistant material of the polyketone and the specific material was melt-blended by using a co-rotating twin-screw extruder at 230 ° C to make a pellet, The specimens were prepared by injection molding.

The results of the test of the coefficient of kinetic friction and the wear property according to the composition and content of the conventional engineering plastic specimen prepared through the above process and the polyketone composition specimen having excellent wear resistance according to the present invention are shown in .

division Components (% by weight) Evaluation results Base resin Abrasion resistance agent PK PA
66 PA
46 PA
6 POM silicone
powder CaCO ₃ PTFE MoS ₂ PM-12 VA-
1803 Exercise
friction
Coefficient Abrasion
(Rmax) Comparative Example 1 100 - - - - - - - - - - 0.35 88 Comparative Example 2 - 100 - - - - - - - - - 0.28 50 Comparative Example 3 - - 100 - - - - - - - - 0.24 45 Comparative Example 4 - - - 100 - - - - - - - 0.32 70 Comparative Example 5 - - - - 100 - - - - - - 0.24 40 Example 1 99.9 - - - - 0.1 - - - - - 0.20 34 Example 2 97.0 - - - - 3 - - - - - 0.10 9 Example 3 95.0 - - - - - 5 - - - - 0.22 30 Example 4 80.0 - - - - - 20 - - - - 0.16 20 Example 5 95.0 - - - - - - 5 - - - 0.22 20 Example 6 80.0 - - - - - - 20 - - - 0.11 12 Example 7 99.9 - - - - - - - 0.1 - - 0.20 34 Example 8 97.0 - - - - - - - 3 - - 0.12 15 Example 9 99.9 - - - - - - - - 0.1 - 0.18 33 Example 10 97.0 - - - - - - - - 3 - 0.11 13 Example 11 99.9 - - - - - - - - - 0.1 0.20 23 Example 12 97.0 - - - - - - - - - 3 0.12 13 PK: Polyketone (polyketone)
PA66: Polyamide 66 (polyamide 66)
■ PA46: Polyamide 46 (polyamide46)
■ PA6: Polyamide 6 (polyamide 6)
■ POM: Acetal polymer (polyacetal)
■ silicone powder: silicone powder, EP-5500 from Dow Corning
■ CaCO ₃ : Calcium carbonate, SN7000 from RexM
■ PTFE: Polytetrafluorethylene, manufactured by Solvay Co., Ltd.
XPP-511 product
■ MoS ₂ : Molybdenum disulfide, MD-40 product of hypersensitivity
PM-12: Magnesium hydroxystearate (Hydroxy Magnesium Stearate),
PM-12 products of Tohse Polymer
VA-180: amorphous ethylene copolymer (MA-g-ethylene copolymer) substituted with maleic acid,
The Exxelor VA-1803 from ExxonMobil

Table 1 above is a table comparing the coefficient of dynamic friction and abrasion according to the constituents of the Comparative Examples and Examples and their contents.

The kinetic friction coefficient in the above table is a value capable of indicating the degree of kinetic friction. The greater the kinetic friction coefficient, the greater the frictional force. On the contrary, the smaller the kinetic frictional coefficient, the smaller the frictional force.

In addition, the wear property is a value indicating the degree of abrasion. The abrasion resistance means that the abrasion resistance is more easily generated when the abrasion resistance is larger, and the abrasion resistance is smaller. On the other hand, the smaller the abrasion resistance is, This means it is big. Also, the abrasion test was performed using a pin-on-disc type under a load of 1 kg, a linear velocity of 7 Hz and a test time of 30 minutes.

Hereinafter, comparative examples and examples of the above table will be described in detail.

Comparative Example 1 The coefficient of dynamic friction and wear of Comparative Example 1 including polyketone (PK) were 0.35 and 88, respectively. Therefore, it can be understood that the friction coefficient and the abrasion resistance of Comparative Example 1 are larger than those of the Comparative Examples 1 and 2, respectively, as compared with the average wear friction coefficient and the average wear resistance of Examples 16 and 21. Therefore, Comparative Example 1 has a large frictional force and a small wear resistance.

Comparative Example 2 The dynamic friction coefficient and the wear rate of Comparative Example 2 including Polyamide 66 (PolyAmide 66, PA66) as a material for a timing chain guide of DuPont currently in use are 0.28 and 50, respectively. Therefore, in comparison with the average kinetic friction coefficient and the average wear rate of the examples of 0.16 and 21, respectively, the dynamic friction coefficient and the wear resistance of the comparative example 2 are large, so that the comparative example 2 has a large frictional force and a small wear resistance.

COMPARATIVE EXAMPLE 3 Timing of Current DSM Company The coefficient of dynamic friction and wear of Comparative Example 3 including Polyamide 46 (PA46) as a material for guide chains were 0.24 and 45, respectively. Therefore, in comparison with the average kinetic friction coefficient and the average wear rate of the examples of 0.16 and 21, the friction coefficient and abrasion resistance of the comparative example 3 are large, so that the comparative example 3 has a large frictional force and a small wear resistance.

Comparative Example 4: The coefficient of dynamic friction and wear of Comparative Example 4 including polyamide 6 (PA6) were 0.32 and 70, respectively. Therefore, in comparison with the average kinetic friction coefficient and the average wear rate of the examples of 0.16 and 21, respectively, the friction coefficient and the wear resistance of the comparative example 4 are large, so that the comparative example 4 has a large frictional force and a small wear resistance.

Comparative Example 5 The friction coefficient and the wear of Comparative Example 5 including polyoxymethylene (POM) were 0.24 and 40, respectively. Therefore, in comparison with the average kinetic friction coefficient and the average wear rate of the examples of 0.16 and 21, respectively, since the kinetic friction coefficient and abrasion resistance of the comparative example 5 are large, the comparative example 5 has a large frictional force and a small wear resistance.

Example 1 The coefficient of dynamic friction and wear of Example 1 including 99.9 wt% of polyketone and 0.1 wt% of silicone powder based on the total composition weight were 0.20 and 34, respectively. Therefore, it can be seen that the friction coefficient and abrasion resistance of Example 1 are smaller than those of the comparative example average friction coefficient and the average wear rate of 0.29 and 58.6, respectively, so that Example 1 has a small frictional force and a high wear resistance.

Example 2 Including the same components as in Example 1 but containing 97.0 wt% of polyketone and 3.0 wt% of silicon powder based on the total composition weight, the friction coefficient and the abrasiveness are smaller than those of Example 1, It can be seen that Example 2 has a smaller friction force and greater wear resistance than Example 1.

Example 3: The coefficient of dynamic friction and wear of Example 3 including 95.0 wt% of polyketone and 5.0 wt% of calcium carbonate (CaCO ₃ ) based on the total composition weight were 0.22 and 30, respectively. Therefore, it can be seen that the friction coefficient and the abrasion resistance of the third embodiment are smaller than those of the comparative example average wear friction coefficient and the average wear degree of 0.29 and 58.6, respectively, so that the third embodiment has a small frictional force and a high wear resistance.

Example 4: Including the same components as in Example 3 above, but comprising 80.0 wt.% Polyketone and 20.0 wt.% Calcium carbonate based on the total composition weight, from the fact that the coefficient of friction and abrasion are smaller than those of Example 3 , Example 4 is smaller in frictional force and more abrasion resistance than Example 3.

Example 5 The coefficient of dynamic friction and wear of Example 5 including 95.0% by weight of polyketone and 5.0% by weight of polytetrafluorethylene (PTFE) based on the total composition weight were 0.22 and 20, respectively. Therefore, it can be seen that the friction coefficient and the abrasion resistance of Example 5 are smaller than those of the Comparative Examples having an average wear coefficient of 0.29 and an average wear rate of 58.6, respectively, so that Example 5 has a small frictional force and a high wear resistance.

Example 6 Contains the same components as in Example 5 but contains 80.0% by weight of polyketone and 20.0% by weight of polytetrafluoroethylene with respect to the total composition weight, which is smaller in friction coefficient and abrasion than Example 5 It can be seen that the friction force is smaller and the abrasion resistance is higher in Example 6 than in Example 5. [

Example 7: The coefficient of dynamic friction and wear of Example 7 including 99.9% by weight of polyketone and 0.1% by weight of molybdenum disulfide (MoS ₂ ) based on the total composition weight were 0.20 and 34, respectively. Therefore, it can be seen that the friction coefficient and abrasion resistance of Example 7 are smaller than those of the Comparative Examples having an average wear coefficient of 0.29 and an average wear rate of 58.6, respectively, so that Example 7 has a small frictional force and a high wear resistance.

Example 8: Including the same components as in Example 7 above but containing 97.0 wt.% Polyketone and 3.0 wt.% Molybdenum disulfide, based on the total composition weight, which has a lower coefficient of friction and less abrasion than Example 7 It can be seen that Example 8 is smaller in frictional force and more abrasion resistance than Example 7.

Example 9: The kinetic friction coefficient and wear resistance of Example 9 including 99.9% by weight of polyketone and 0.1% by weight of magnesium hydroxystearate (hydroxy magnesium stearate) based on the total composition weight were 0.18 and 33, respectively. Therefore, it can be seen that the friction coefficient and the wear resistance of Example 9 are smaller than those of Comparative Example 10 and Comparative Example 10, which are 0.29 and 58.6, respectively, so that Example 9 has low frictional force and high abrasion resistance.

Example 10: Containing the same components as in Example 9 above but containing 97.0 wt.% Polyketone and 3.0 wt.% Magnesium hydroxystearate, based on the total weight of the composition, which has a lower coefficient of friction and less abrasion than Example 9 It can be seen that Example 10 is smaller in friction force and more abrasion resistance than Example 9.

Example 11: The dynamic friction coefficient and the abrasion resistance of Example 11 including 99.9% by weight of a polyketone and 0.1% by weight of an MA-g-ethylene copolymer substituted with maleic acid based on the total composition weight were 0.20 23. Therefore, it can be seen that the friction coefficient and abrasion resistance of Example 11 are smaller than those of the comparative example having an average coefficient of dynamic friction and an average wear rate of 0.29 and 58.6, respectively, so that Example 11 has low frictional force and great wear resistance.

Example 12: Containing the same components as in Example 11 above but containing 97.0 wt.% Polyketone and 3.0 wt.% Maleic acid, based on the total weight of the composition, from the fact that the coefficient of friction and abrasion are smaller than those of Example 11 , Example 12 is smaller in friction force and more abrasion resistance than Example 11.

Therefore, Examples 1 to 12 according to the present invention show that the friction coefficient of the Comparative Examples 1 to 5 was reduced by an average of 55% and the abrasion was reduced by an average of 36% And the abrasion resistance was improved.

Also, as can be seen from Examples 1 to 12, the friction was small and the abrasion resistance was excellent when the composition contained more abrasion-resistant material than that of the abrasion-resistant material.

Further, Examples 1 to 2 each containing silicone, polytetrafluoroethylene and magnesium stearate; Examples 5 to 6; And Examples 9 to 10 are relatively small in friction coefficient and abrasion resistance, so that friction is small and abrasion resistance is great. Therefore, the wear resistant material is preferably silicon, polytetrafluoroethylene and magnesium stearate.

Particularly, in Example 2 including silicon, friction and modulus of abrasion are the smallest in all Comparative Examples and Examples, so that friction is the smallest and wear resistance is greatest. Therefore, the wear resistant material is most preferably silicon.

With reference to Example 2 above, it is most preferred that the polyketone content is 97% by weight and the silicone powder is 3% by weight based on the total composition weight.

Although the present invention has been described in connection with the specific embodiments of the present invention, it is to be understood that the present invention is not limited thereto. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents. Various modifications and variations are possible.

Claims (6)

Polyketone; And at least one abrasion resistant material selected from the group consisting of silicon, polytetrafluoroethylene, calcium carbonate, maleic acid, molybdenum, and magnesium stearate.
The method according to claim 1,
Wherein the content of the polyketone is 80 to 99.9% by weight and the content of the abrasion resistant material is 0.1 to 20% by weight based on the total weight of the composition.
3. The method of claim 2,
Wherein the abrasion resistant material is silicone, polytetrafluoroethylene or magnesium stearate.
The method of claim 3,
Wherein the polyketone composition is 97 wt% of the polyketone and 3 wt% of silicon based on the total weight of the composition.
The method according to claim 1,
Wherein the polyketone is a terpolymer in which carbon monoxide, ethylene and propylene are polymerized with monomers.
6. The method according to any one of claims 1 to 5,
Wherein the polyketone composition is applied to an automotive timing chain guide, a bearing, a door check gear, a power steering worm gear, and a door regulator gear.