KR20110026769A - Blend comprising polyketone and poylamide and method for preparing the same - Google Patents

Abstract

PURPOSE: A blend comprising polyketone and poylamide is provided to ensure low linear expansion coefficient and excellent dimensional stability, thereby enabling the application to molded products such as food containers or automobile parts. CONSTITUTION: An industrial polyketone blend comprises: a linear alternate polyketone polymer consisting of carbon monoxide and at least one kind of ethylenic unsaturated hydrocarbon; polyamide formed by caprolactame ring opening polymerization; and acidic polymer. The linear expansion coefficient of the polyketone blend is 10.0-11.0.

Description

Blend Comprising Polyketone and Poylamide and Method for Preparing the Same

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to polyketone polymer compositions, comprising: industrial polyketone blends comprising linear alternating polymers, polyamides, and acidic polymers of carbon monoxide and at least one ethylene-based unsaturated hydrocarbon Regarding

There is a growing interest in a group of linear alternating polymers consisting of carbon monoxide and at least one ethylenically unsaturated hydrocarbon, known as polyketones or polyketone polymers. U. S. Patent No. 4,880, 903 discloses a linear alternating polyketone terpolymer consisting of carbon monoxide and ethylene and other olefinically unsaturated hydrocarbons such as propylene. The process for preparing polyketone polymers is usually a compound of Group VIII metal selected from palladium, cobalt or nickel, and anions of non-hydro halogen strong-hydrohalogentic acid. Catalyst compositions produced from bidentate ligands of phosphorus, arsenic or antimones are used. U.S. Patent 4,843,144 describes a process for preparing polymers of carbon monoxide and at least one ethylenically unsaturated hydrocarbon using a palladium compound, an anion of nonhydrohalogenic acid with a pKa of less than 6, and a catalyst that is a bidentate ligand of phosphorus. It is starting.

An object of the present invention is to provide a polyketone blend excellent in dimensional stability as a thermoplastic resin in the manufacture of molded articles such as food containers and automobile parts.

In order to solve the above problems, according to a preferred embodiment of the present invention, a linear alternating polyketone polymer consisting of carbon monoxide, at least one ethylene-based unsaturated and a hydrocarbon, a polyamide consisting of a caprolactam ring-opening polymerization and an acidic polymer Provides industrial polyketone blends.

According to another suitable embodiment of the present invention, the polyketone blend comprises 60 to 95 weight percent of linear alternating polyketone polymer, 5 to 40 weight percent of polyamide, and 0.05 to 5 weight percent of acidic polymer relative to the total weight of the blend. It provides an industrial polyketone blend.

According to another suitable embodiment of the present invention, the polyketone blend provides an industrial polyketone blend, characterized in that the coefficient of linear expansion is 10.0 to 11.0.

According to another suitable embodiment of the present invention, the acidic polymer is one type of α-olefin and acrylic acid, 2-, selected from the group consisting of ethene, propene, 1-butene, isobutene, 1-octene and 1-decene. It provides an industrial polyketone blend, characterized in that it comprises one kind of α, β-ethylenically unsaturated carboxylic acid selected from the group consisting of hexenic acid, methacrylic acid and crotonic acid.

Since the polyketone and polyamide blend of the present invention have a linear expansion coefficient of 10.0 to 11.0, the polyketone and polyamide blend have superior dimensional stability than resins composed of conventional polyketones.

The present invention provides a blend of linear alternating polymers consisting of carbon monoxide and at least one ethylenically unsaturated hydrocarbon and certain other polymeric materials.

In particular, the present invention provides an industrial polyketone blend comprising (1) linear alternating polymers, (2) polyamides, and (3) acidic polymers. The blend of the present invention is characterized by showing improved dimensional stability at room temperature or above.

The polyketone polymer of the blend 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 also have up to 20 carbon atoms, preferably up to 10 carbon atoms, and ethene and α-olefins (e.g. propene, 1-butene) ), Containing an aryl substituent on an aliphatic or other aliphatic molecule such as isobutene, 1-hexene, 1-octene, and especially an ethylenically unsaturated carbon source. Examples of aryl aliphatic hydrocarbons in ethylenically unsaturated hydrocarbons include styrene, p-methyl styrene, p-ethyl styrene and m-isopropyl. Styrene (isopropyl styrene) Preferred polyketone polymers are copolymers of carbon monoxide and ethene or a second ethylene-based unsaturated carbon having at least three carbon atoms with carbon monoxide and ethene. Terpolymers with α-olefins such as hydrocarbons (especially propene).

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 polymer ring of the preferred polyketone polymer in the present invention may be represented by the following formula (1).

In the above formula, G is an ethylenically unsaturated hydrocarbon, in particular, a part obtained from an ethylenically unsaturated hydrocarbon having at least three carbon atoms, and the y: x ratio is preferably 1: 0.01 to 0.5.

Particularly advantageous are polyketone polymers having a number average molecular weight of 100 to 200,000, particularly 20,000 to 90,000, as measured by gel permeation chromatography. The physical properties of the polymer depend on the molecular weight, on whether the polymer is a copolymer or terpolymer, and on the nature of the second hydrocarbon moiety present in the case of a 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. Polymerization conditions of carbon monoxide and hydrocarbon monomer in the presence of a palladium compound and a catalyst composition suitably produced from pKa less than 6, preferably less than 2, anion of nonhydrohaloacid and a bidentate ligand of phosphorus. Under contact.

The second component of the composition of the present invention is a polyamide which is a caprolactam ring-opening polymer, and is a compound represented by the following formula (2).

HN- (CH ₂ ) ₅ -COOH

In the present invention, the polyamide is preferably a nylon (Nylon) resin, for example, nylon 6 (Nylon 6), nylon 66 (Nylon 66) is particularly preferred. It is widely known and commercially available.

The nylon polymers described in US Pat. No. 5,486,594, which form part of this specification, are particularly particularly referred to in the present invention. Nylon can be used as an impact reinforcing material, but dimensional stability of precision mechanical parts is also an important factor. Mold shrinkage of polyketones is about 0.5 times higher than that of nylon, which can be a weak point in the injection properties of the mechanical field. Therefore, blending and modifying nylon to polyketone is expected to contribute to the dimensional stability of precision parts.

In the present invention, the nylon 6 or nylon 66 polymer is preferably 1 to 40% by weight based on the total weight of the polyketone. If the nylon 6 polymer content is less than 1%, the mold shrinkage does not reach the expected level, and if it is 40% by weight or more, there is a problem in that the blending workability is lowered, such as foaming.

In the present invention, the third 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 third monomer and optionally a portion of the carboxylic acid group is neutralized with the non-alkali metal. The alpha -olefin monomer in this optional third 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 third 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 3rd polymer, and, as for the (alpha), (beta)-ethylenically unsaturated carboxylic acid of an arbitrary 3rd polymer component, it is still more preferable that it is 5 mol%-20 mol%.

Regardless of whether the third 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. The third polymer, when partially neutralized, is a polymer but at the same time ionic.

In the specific example of partially neutralizing the third polymer component, it does not include or include any third 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. Injecting the acidic polymer in the present invention may generate a release effect on the molding flowability of the polyketone to enable smooth transfer, and also increase the gas barrier property of the produced chip.

Blends of the present invention may include additives known in the art, such as antioxidants, stabilizers, fillers, refractory materials, mold release agents, colorants and other materials to improve the processability of the polymer or the physical properties of the blend. The additives may be added by known methods before, during or after mixing with the polyketone and the modifier.

The blend production method of the present invention is not particularly limited, provided that the blend or blend component is uniformly made without creating excessive collapse. The polymer component can be blended in a mixing device exhibiting high shear stress as another embodiment. . Blends may be molded by conventional methods, such as extrusion or injection molding, to produce sheets, films, plates and shaped articles. Such application examples may be used for interior parts and exterior parts used in automobiles.

Hereinafter, the configuration and effects of the present invention will be described in more detail with 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 present invention is described in detail by the following non-limiting examples.

Preparation Example 1

Linear alternating terpolymers of carbon monoxide, ethylene and propene were prepared in the presence of a catalyst composition produced from palladium acetate, trifluoroacetic acid and 1,3-bis [bis (2-methoxyphenyl-phosphino] propane The polyketone terpolymer used in the present invention has a melting point of 220 ° C., LVN measured at 25 ° C. with hexa-fluoroisopropanol (HFIP) at 1.25 dl / g, and a melt flow index of MI at 230 ° C. and 2.16 kg. ) Was 60 g / 10 min.0.2% by weight of Irganox 1010 (manufactured by Ciba-Geigey), 0.3% by weight of calcium hydroxyapatite (manufactured by Budenheim), and ethene and methacryl to the polyketone terpolymer prepared above. An acid copolymer (trade name Nucrel 1183C) was prepared in pellet form on an extruder by using a 32 mm twin screw operating at 250 rpm using 0.1 wt% of the acid-containing copolymer (brand name Nucrel 1183C). Was a type. Were stored over desiccant until use molded test specimens were subjected to mechanical testing on a test piece after.

Examples 1-4

The polyketone pellets prepared in Preparation Example 1 and 10, 20, 30, and 40% by weight of nylon 6 (KN3311, KOLON) were each set at a temperature of 240 ° C. using a 32 mm twin screw to bond T-dies. Into sheets on an extruder. The sheet was 1 mm thick, cut into 2 cm long and 4 mm wide. Specimens and measurement conditions were tested according to KS M ISO 11359-2 and measured by TMA. The measurement range was measured at a rate of 3 ° C. per minute at 20 ° C. to 100 ° C., and the clamping force was 30 mN.

Comparative Example 1

The polyketone pellets prepared in Preparation Example 1 were prepared in sheets on an extruder in which a T-die was bonded by setting the temperature at 240 ° C. using a 32 mm twin screw. The sheet was 1 mm thick, cut into 2 cm long and 4 mm wide. Specimens and measurement conditions were tested according to KS M ISO 11359-2 and measured by TMA. The measurement range was measured at a rate of 3 ° C. per minute at 20 ° C. to 100 ° C., and the clamping force was 30 mN. Then, the tensile strength and the sharpness (sharpy) impact rate were measured and shown in Table 1.

Comparative Example 2

Nylon 6 (KN3311, KOLON) was prepared in a sheet on an extruder with a T-die attached by setting the temperature to 240 ° C. using a 32 mm twin screw. The sheet was 1 mm thick, cut into 2 cm long and 4 mm wide. Specimens and measurement conditions were tested according to KS M ISO 11359-2 and measured by TMA. The measurement range was measured at a rate of 3 ° C. per minute at 20 ° C. to 100 ° C., and the clamping force was 30 mN.

Polyketone (wt%) Nylon 6 (wt%) Coefficient of linear expansion (X 10 ^-5 ) Example 1 90 10 11.0 Example 2 80 20 10.8 Example 3 70 30 10.5 Example 4 60 40 10.6 Comparative Example 1 100 0 11.5 Comparative Example 2 0 100 8.5

Table 1 shows the coefficients of linear expansion of each sample. The coefficient of linear expansion at 100% polyketone was 11.5, but the coefficient of linear expansion decreased with increasing nylon modifier content. However, the coefficient of linear expansion did not increase any more from 30% to 40% by weight. The lower the coefficient of linear expansion (CTE), the greater the dimensional safety.

Claims (4)

An industrial polyketone blend comprising a linear alternating polyketone polymer consisting of carbon monoxide and at least one ethylenically unsaturated hydrocarbon, a polyamide consisting of caprolactam ring-opening polymerization, and an acidic polymer. The method of claim 1, wherein the polyketone blend is 60 to 95% by weight of the alternating polyketone polymer, 5 to 40% by weight polyamide, and 0.05 to 5% by weight of the acidic polymer relative to the total weight of the blend Polyketone blends. The industrial polyketone blend of claim 1, wherein the polyketone blend has a coefficient of linear expansion of 10.0 to 11.0. According to claim 1, wherein the acidic polymer is ethene, propene, 1-butene, isobutene, 1-octene and 1-decene selected from the group consisting of acrylic acid, 2-hexenoic acid, methacrylic Industrial polyketone blend, characterized in that it comprises one type of α, β-ethylenically unsaturated carboxylic acid selected from the group consisting of acid and crotonic acid.