KR20110078383A - Polyketone blend comprising glass fiber and method for preparing the same - Google Patents

Abstract

PURPOSE: A polyketone blend is provided to ensure excellent abrasion resistance and to enable the application to industrial products such as automobile parts. CONSTITUTION: An industrial polyketone blend comprises: a linear alternating polyketone polymer including carbon monoxide and at least one kind of ethylenically unsaturated hydrocarbons; glass-reinforced fibera surface-treated with epoxy or urethane; and a polymer grafted with polytetrafluoroethylene. The content of the glass-reinforced fiber is 90:10-70:30 based on the total of the polyketone polymer. The polymer grafted with polytetrafluoroethylene is included in the amount of 1~20 weight% based on the total weight of the whole blend.

Description

Polyketone blend Comprising Glass Fiber and Method for Preparing The Same}

FIELD OF THE INVENTION The present invention relates to an improved poly ketone polymer blend, in particular a linear alternating polymer of carbon monoxide and at least one ethylene-based unsaturated hydrocarbon, glass fibers and polytetrafluoroethylene polymer resins. For polyketone blends containing

There is a growing interest in a group of linear alternating polymers, known as polyketones or polyketone 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 a olefinic unsaturated hydrocarbon such as propylene. The process for preparing polyketone polymers is usually a compound of Group VIII metal selected from the group consisting of palladium, cobalt or nickel, anions of strong-hydrohalogentic acid, phosphorus Catalyst compositions resulting from the bidentate ligands of arsenic or Antimon are used. US Pat. No. 4,843,144 describes a process for the preparation of polymers of carbon monoxide and at least one ethylenically unsaturated hydrocarbon using a preferred catalyst consisting of a palladium compound, an anion of nonhydrohalogenic acid having a pKa of less than about 6 and a bidentate ligand of phosphorus. It is starting.

An object of the present invention is to provide a polyketone blend having excellent wear resistance that can be used in the manufacture of industrial products such as automotive parts.

In order to solve the above problems, according to a preferred embodiment of the present invention, a glass-reinforced fiber and polytetrafluor surface-treated with a linear alternating polyketone polymer composed of carbon monoxide and at least one ethylenically unsaturated hydrocarbon, epoxy or urethane An industrial polyketone blend is provided that includes a polymer grafted with low ethylene.

According to another suitable embodiment of the present invention, the content of the glass-reinforced fiber provides an industrial polyketone blend, characterized in that 90:10 to 70:30 relative to the weight of the polyketone polymer.

According to another suitable embodiment of the present invention, the polymer grafted with polytetrafluoroethylene provides an industrial polyketone blend, characterized in that 1 to 20% by weight relative to the total blend weight.

According to another suitable embodiment of the present invention, the industrial polyketone blend provides an industrial polyketone blend, characterized in that the coefficient of kinetic friction is 0.4 or less and the wear amount is 2.5 or less.

Polyketone blends comprising polyketones and polytetrafluoroethylene polymer resins reinforced with glass fibers of the present invention have a high frictional coefficient of 0.4 or less and abrasion resistance of 2.5 ³ / kgf / km or less. It can be applied to industrial products.

The present invention provides a blend comprising a linear alternating polymer consisting of carbon monoxide and at least one ethylenically unsaturated hydrocarbon and certain other polymeric materials. Specifically, the present invention provides a blend comprising a linear alternating polymer blend reinforced with glass fibers and a polymer grafted with a fluorine-based polymer. Blends of the invention exhibit improved friction and wear resistance above room temperature.

The linear alternating polymer blend reinforced with the glass fibers of the present invention is a linear alternating structure and substantially contains carbon monoxide for each molecule of unsaturated hydrocarbon. Suitable ethylenically unsaturated hydrocarbons for use as precursors of polyketone polymers have up to 20, preferably up to 10 carbon atoms. In addition, ethylenically unsaturated hydrocarbons are ethene and α-olefins such as propene, 1-butene, isobutene, 1-hexene, 1-octene It is an aryl aliphatic containing an aryl substituent on an aliphatic or other aliphatic molecule such as, in particular an aryl substituent on an ethylenically unsaturated carbon atom. Examples of the aryl aliphatic hydrocarbons in the ethylenically unsaturated hydrocarbons include styrene, p-methyl styrene, p-ethyl styrene, and m-isopropyl styrene. Preferred polyketone polymers are copolymers of carbon monoxide and ethene or second ethylenically unsaturated hydrocarbons having at least three carbon atoms with carbon monoxide and ethene, in particular terpolymers with α-olefins such as propene. terpolymer).

When the polyketone terpolymer is used as the main polymer component of the blend of the present invention, for each unit containing the second hydrocarbon moiety in the terpolymer, there are at least two units containing the ethylene moiety. It is preferable that there are 10-100 units containing a 2nd hydrocarbon part.

The number average molecular weight measured by gel permeation chromatography is preferably 100 to 200,000, particularly preferably a polyketone polymer having 20,000 to 90,000. The physical properties of the polymer are determined by the molecular weight, by the polymer or by the terpolymer, and by the nature of the second hydrocarbon moiety present in the case of the terpolymer. Melting | fusing point of the conversion of a polymer is 175 degreeC-300 degreeC, and is 210 degreeC-270 degreeC generally. The ultimate viscosity number (LVN) of the polymer measured at 60 ° C. using a standard tubular viscosity measuring device and HFIP (Hexafluoroisopropylalcohol) is 0.5 dl / g to 10 dl / g, more preferably 0.8 dl / g to 4 dl / g.

Preferred methods of preparing polyketone polymers are disclosed in US Pat. No. 4,843,144. Polyketone by contacting carbon monoxide and a hydrocarbon monomer under polymerization conditions in the presence of a palladium compound and a catalyst composition suitably produced from anionic non-hydrohaloic acid of less than pKa, preferably less than pKa 2, and a bidentate ligand of phosphorus. Prepare a polymer.

Blends of glass-reinforced fibers and polyketone polymers, also disclosed in US Pat. No. 5,114,992, are incorporated herein by reference. The patent improves mechanical strength characteristics by blending polyketone polymer and glass reinforced fiber. For blending of glass reinforced fiber and polyketone, glass reinforced fiber was blended after surface treatment with epoxy or urethane.

As the second component of the blend of the present invention, glass-reinforced fibers surface-treated with epoxy or urethane are used. The use of glass-reinforced fibers in polyketone polymers improved the mechanical strength of the blend. The content of the glass-reinforced fibers relative to the weight of the polyketone polymer is preferably 90:10 to 70:30. If the content of glass-reinforced fiber is less than 10%, the effect of strengthening the properties is insignificant. If the content of glass-reinforced fiber is more than 30%, the increase of the property reinforcement is slowed down, and carbonization due to cutting of strands and deterioration of flow during the extrusion process Occurrence of workability lowers.

The third component of the composition of the present invention is a polymer grafted with a fluorine-based polymer. Examples of the polymer grafted with the fluorine-based polymer effective in the present invention include polytetrafluoroethylene (hereinafter referred to as "PTFE"), and commercially available teflon or the like can be used. The polymer grafted with a fluorine-based polymer in the present invention is preferably 1 to 20% by weight based on the total weight of the polyketone blend. When the PTFE polymer content is less than 1%, the change in physical properties is insignificant, and when 20% by weight or more is mixed, the increase in physical properties is slowed down.

Teflon is a crystalline polymer having a melting point of 327 ° C. The continuous use temperature is 260 ° C, and it can be stably used from a low temperature of -268 ° C to a high temperature. Its chemical resistance is the best among organic materials. It does not intrude at all in acid, alkali, and various solvents. It is invaded only in harsh conditions under special conditions such as fluorine gas, molten alkali metal, and trifluorochlorine, and is used for gaskets, packing, and various sealing materials. have. In addition, it has excellent non-adhesiveness and is used for coating of frying pans and various steel pipes. However, there is a drawback that the adhesive cannot be used even if it is welded. The electrical characteristics, especially the dielectric characteristics, are the best, and the wide frequency is stable over the temperature range, exhibits low dielectric constant and dielectric loss tangent, and other insulation characteristics.

In addition, the most important feature of mechanical properties of Teflon is its low coefficient of friction, which is reinforced with various fillers and is used for bearings of oil-free sliding materials. Therefore, it is believed that the wear resistance of polyketone is modified with Teflon blend to contribute to wear stability.

It may further comprise a fourth polymer component in the present invention. In the present invention, the fourth polymer component is a small amount present in the entire blend and is an acidic polymer including an α-olefin portion and an α, β-ethylenically unsaturated carboxylic acid portion. The third polymer polymerizes with the fourth monomer and optionally a portion of the carboxylic acid group is neutralized with the non-alkali metal. The alpha -olefin monomer in this optional fourth polymer component has up to 10 carbon atoms. As an alpha olefin, ethene, a propene, 1-butene, isobutene, 1-octene, 1-decene, etc. are preferable, for example. The α-olefin monomer is preferably present at least 65 mol%, and preferably at least 80 mol% based on the total weight of the fourth polymer.

The ethylenically unsaturated carboxylic acid monomer has up to 10 carbon atoms. The α, β-ethylenically unsaturated carboxylic acid of the present invention is one selected from the group consisting of acrylic acid, 2-hexenoic acid, methacrylic acid or crotonic acid, and acrylic acid and methacrylic acid are particularly preferred. It is preferable that it is 1 weight%-35 weight% with respect to the weight of a 4th polymer, and, as for the (alpha), (beta)-ethylenically unsaturated carboxylic acid of arbitrary 4th polymer component, it is still more preferable that it is 5 mol%-20 mol%.

Regardless of whether the fourth polymer in the blend is a copolymer or a terpolymer, in some embodiments a portion of the carboxylic acid groups is neutralized with the non-alkali metal. When partially neutralized, the fourth polymer is polymer in form but at the same time ionic.

In a specific example of partially neutralizing the fourth polymer component, it does not include or include any fourth monomer. In the α-olefin / unsaturated carboxylic acid polymer, the carboxylic acid groups present in the polymer are reacted with a compound source of ionized zinc, aluminum or magnesium to neutralize 10% to 90%, preferably 20% to 80%. Particularly preferably, when neutralizing with zinc, which is a metal, the metal is uniformly dispersed throughout the polymer.

The polyketone blend of the present invention may also include conventionally known additives such as antioxidants, stabilizers, fillers, refractory materials, mold release agents, colorants and other materials in order to improve the processability of the polymer or the physical properties of the blends produced. The additive may be added by conventional methods before or after blending the polyketone with the modifier or after the blend.

The method for producing the blend is not particularly limited as long as the blend or blend component does not produce excessive collapse and a uniform blend is produced. In another embodiment, the polymer component is blended in a mixing device exhibiting high shear stress. Blends are molded by conventional methods such as extrusion and injection molding to produce sheets, films, plates and shaped articles. Examples of such applications include the manufacture of interior parts and exterior parts used in automobiles.

Hereinafter, the configuration and effects of the present invention will be described in more detail with reference to specific examples, but these examples are only intended to more clearly understand the present invention and are not intended to limit the scope of the present invention. The invention is illustrated in detail by the following non-limiting examples.

Preparation Examples 1 to 3

Linear alternating terpolymers of carbon monoxide, ethylene and propene are present in the presence of a catalyst composition produced from palladium acetate, trifluoroacetic acid and 1,3-bis [bis (2-methoxyphenyl)) phosphino] propane Prepared under. The polyketone terpolymer used in the present invention has a melting point of 225 ° C., LVN measured at 25 ° C. with hexa-fluoroisopropanol (HFIP) at 1.53 dl / g, and a melt flow index (MI) of 45 g at 230 ° C. and 2.16 kg. / 10min. Irganox 1010 (manufactured by Ciba-Geigey), 0.2 wt% and 0.2 wt% of calcium hydroxyapatite (Calcium Hydroxyapatite, manufactured by Budenheim) in the polyketone terpolymer prepared above, and commercially available noses consisting of ethene and methacrylic acid 0.1 wt% of the polymer brand name Nucrel 1183C) was added thereto, and a primary pellet was prepared on an extruder by setting the temperature at 245 ° C. using a 32 mm twin screw operating at 180 rpm. Next, 10%, 20%, and 30% of 165A of Dow Corning, a glass-reinforced fiber surface-treated with polyurethane, was blended to prepare secondary pellets using a biaxial screw.

Examples 1-6

The secondary pellet prepared above and a Teflon-based modifier of 3M's Dyneon ^TM PA5953 were mixed, and the temperature was set at 245 ° C. using a 32 mm twin screw to prepare a third pellet. In the above, the Teflon modifier was mixed with 10, 20% by weight relative to the total weight of the third pellet. Using the prepared third pellets, analytical specimens were prepared by an injection molding machine according to the test method of ASTM D3702, and then subjected to a thrust washer test to measure dynamic friction coefficient and wear.

TABLE 1

Polyketone / Glass Fiber (Wt%) Dyneon ^TM PA5953 (Wt%) Dynamic friction coefficient Wear
(Kg / kgf / km) Preparation Example 1 90/10 0 0.45 4.5 Example 1 90/10 10 0.3 1.2 Example 2 90/10 20 0.28 0.8

TABLE 2

Polyketone / Glass Fiber (Wt%) Dyneon ^TM PA5953 (Wt%) Dynamic friction coefficient Wear
(Kg / kgf / km) Production Example 2 80/20 0 0.5 4.6 Example 3 80/20 10 0.41 1.5 Example 4 80/20 20 0.32 0.8

[Table 3]

Polyketone / Glass Fiber (Wt%) Dyneon ^TM PA5953 (Wt%) Dynamic friction coefficient Wear
(Kg / kgf / km) Production Example 3 70/30 0 0.5 4.5 Example 5 70/30 10 0.4 2.5 Example 6 70/30 20 0.4 2.4

The dynamic friction coefficient and wear amount of each sample are shown in Tables 1-3. The dynamic friction coefficient and the amount of wear are measured friction characteristics with polyketone having the same composition ratio. Regardless of the mixing ratio of the polyketone and glass-reinforced fibers, it can be seen that as the content of the fluorine-based polymer increases, the coefficient of kinetic friction and wear decreases. As the content of glass-reinforced fibers increased, the physical properties of the kinetic coefficient and wear decreased even though the fluorinated polymer content increased.

Claims (4)

An industrial polyketone blend comprising a linear alternating polyketone polymer consisting of carbon monoxide and at least one ethylenically unsaturated hydrocarbon, glass-reinforced fibers surface treated with epoxy or urethane, and a polymer grafted with polytetrafluoroethylene. The industrial polyketone blend according to claim 1, wherein the glass fiber is 90:10 to 70:30 based on the weight of the polyketone polymer. The industrial polyketone blend according to claim 1, wherein the polymer grafted with polytetrafluoroethylene is 1 to 20% by weight based on the total blend weight. The industrial polyketone blend of claim 1, wherein the industrial polyketone blend has a coefficient of dynamic friction of 0.4 or less and a wear of 2.5 or less.