KR101527520B1 - Polyketone blend and Method for Preparing The Same - Google Patents

Abstract

The present invention relates to a polyketone blend comprising a linear alternating polymer of carbon monoxide and at least one ethylenically unsaturated hydrocarbon and certain other polymer materials and more particularly to a polyketone blend comprising a linear alternating polyketone polymer, ≪ / RTI > The polyketone blend produced in the present invention improves the discoloration stability and does not cause excessive MI index change due to crosslinking and decomposition when staying in a medium or long-term injection machine in the process of producing a molded article. Therefore, when the polyketone blend prepared in the present invention is used as a composite product, it can be effectively used as a molded product such as a container or a component for an automobile industry.

Polyketone, blend, crystal nucleating agent, titanium dioxide, color stability, MI, polyketone terpolymer

Description

TECHNICAL FIELD [0001] The present invention relates to a polyketone blend,

The present invention relates to a polyketone blend comprising a linear alternating polymer of carbon monoxide and at least one ethylenically unsaturated hydrocarbon and certain other polymer materials and more particularly to a polyketone blend comprising a linear alternating polyketone polymer, ≪ / RTI >

BACKGROUND OF THE INVENTION [0002] Recently, there has been a growing interest in polyelectrolyte or polyketone polymers, a group of linear alternating 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 terephthalic unsaturated hydrocarbons such as propylene.

The process for preparing the polyketone polymer is generally carried out by reacting a compound of a Group VIII metal selected from among palladium, cobalt or nickel with an anion of a strong halogen-hydrohalogentic acid, , Phosphorus, arsenic, or antimony (Antimon).

U.S. Patent No. 4,843,144 discloses a method for producing a polymer of carbon monoxide and at least one ethylenically unsaturated hydrocarbon using a palladium compound, an anion of a nonhydrohalogen acid having a pKa of less than 6, and a catalyst that is a bidentate ligand Lt; / RTI >

In general, polyketone terpolymers are suitable for automobile fuel parts and molded products because of their excellent chemical resistance and chemical stability. However, since the polyketone itself has poor stability against heat, the color is discolored during processing, It has disadvantages.

The polyketone blend produced in the present invention improves the discoloration stability when staying in a medium or long-term injection machine in the process of producing a molded article, and also has an excessive MI (melt index) change does not occur.

It is an object of the present invention to provide a polyketone polymer as a polymeric material made of an excellent thermoplastic resin which can be used as a molded article such as a food container or a part for automobile industry. And more particularly to a polyketone blend which has improved stability to heat which is poor for polyketone itself, and a process for producing the same.

According to a preferred embodiment of the present invention for solving the above-mentioned problems, there is provided a process for producing a polyolefin composition comprising a linear alternating polyketone polymer composed of carbon monoxide and at least one ethylenically unsaturated hydrocarbon, a titanium dioxide crystal nucleating agent and an alpha -olefin monomer and an ethylenically unsaturated carboxylic acid There is provided a polyketone blend comprising an acidic polymer composed of a copolymer of monomers.

According to another preferred embodiment of the present invention, there is provided a polyketone blend, wherein the crystal nucleating agent is contained in an amount of 0.1 to 10% by weight based on the weight of the entire polyketone blend.

According to another preferred embodiment of the present invention, the polyketone blend is characterized in that the acidic polymer is contained in an amount of 0.05 to 5% by weight based on the total weight of the polyketone blend.

According to another preferred embodiment of the present invention, there is provided a composite product produced by extrusion molding or injection molding the polyketone bell.

According to another preferred embodiment of the present invention, the composite article has a color change value of not more than? 3 and a melt viscosity (MI) change value of not more than? 6.

The polyketone blend of the present invention improves the amount of color change when staying in an injection machine and improves the rate of change of melt index (MI) value due to heat when staying in an injection machine. Also, the polyketone blend prepared in the present invention can be manufactured as a molded article such as a general container or a part for an automobile industry and used stably.

The present invention provides a polyketone blend comprising a linear alternating polyketone polymer, a nucleating agent and an acidic polymer.

The polyketone polymer of the polyketone blend of the present invention is a linear alternating structure and contains substantially carbon monoxide per one molecule of unsaturated hydrocarbon. Ethylenically unsaturated hydrocarbons suitable for use as precursors of polyketone polymers have up to 20, 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 and containing an aryl substituent on an ethylenically unsaturated carbon atom. Examples of aryl aliphatic hydrocarbons in the ethylenically unsaturated hydrocarbon 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, especially alpha-olefins such as propene, It is a terpolymer with olefins.

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).

In the above formula, G is an ethylenically unsaturated hydrocarbon, particularly a portion 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.

In the above, when y is 0, it may be represented by the following general formula (2), and it becomes a copolymer and does not contain the second ethylenic unsaturated hydrocarbon.

And

The units of formula (2) are randomly applied throughout the polymer chain. The preferred y: x ratio is from 0.01 to 0.5. The terminal root, or "cap ", of the polymeric ring is determined depending on what material is present during the preparation of the polymer and how the polymer will be purified or the polymer will be purified.

The number average molecular weight measured by gel permeation chromatography is preferably 100 to 200,000, more preferably 20,000 to 90,000. Depending on the molecular weight, the physical properties of the polymer depend on whether the polymer is a copolymer or a terpolymer, and in the case of a terpolymer, the physical properties of the second hydrocarbon part are determined. Typical melting points of the polymers in the present invention are 175 ° C to 300 ° C, and generally 210 ° C to 270 ° C. The intrinsic viscosity (LVN) of the polymer measured using m-cresol at 60 ° C is from 0.5 dl / g to 10 dl / g, frequently from 0.8 dl / g to 4 dl / g, to be.

A preferred process for producing a polyketone polymer is disclosed in U.S. Patent No. 4,843,144. The carbon monoxide and the hydrocarbon monomer are brought into contact under polymerization conditions in the presence of a catalyst composition suitably produced from a palladium compound, an anion of a hydrohalogenic acid having a pKa of 6 or less, preferably less than pKa 2, and a bidentate two-coordinate ligand, to produce a polyketone polymer.

The second component of the composition of the present invention may be titanium dioxide as a crystal nucleating agent. The crystal nucleating agent improves the resistance to color by increasing the degree of crystallization as an additive, and can improve MI (viscosity change) change at high temperature during processing. The blend of the present invention exhibits improved color stability and MI stability at processing temperatures (250 DEG C) due to the addition of the nucleating agent.

The content of the nucleating agent used in the blend of the present invention is not particularly limited, but it is preferably 0.01% by weight to 20% by weight, more preferably 0.05% by weight to 10% by weight, more preferably 0.1% by weight to 10% % By weight is most preferred. When the content of the crystal nucleating agent is less than 0.1 wt% based on the total blend weight, the effect is insufficient. When the content of the nucleating agent is 10 wt%, the extrusion stability due to the action of the nucleating agent is poor and the processability is poor.

Wherein the acidic polymer is a third polymer component and is present in minor amounts in the overall blend, comprising an alpha-olefin moiety and an alpha, beta-ethylenically unsaturated carboxylic acid moiety and optionally a third non-acidic low molecular weight polymer Containing monomer. In some cases, a part of the carboxylic acid group of the acidic polymer is neutralized with a non-alkali metal.

In this acidic polymer component, the -olefin monomer has up to 10 carbon atoms. As the? -olefin, for example, ethene, propene, 1-butene, isobutene, 1-octene or 1-decene is preferable. The? -olefin is preferably a straight chain? -olefin having up to 4 carbon atoms, and more preferably is ethene. The? -olefin monomer is preferably present in an amount of at least 65 mol%, more preferably at least 80 mol%, based on the weight of the acid polymer.

The ethylenically unsaturated carboxylic acid monomer has up to 10 carbon atoms. ?,? -ethylenically unsaturated carboxylic acid and is represented by acrylic acid, 2-hexenoic acid or 2-octenoic acid. The alpha, beta -ethylenically unsaturated carboxylic acid has up to 4 carbon atoms. These acids are acrylic acid, methacrylic acid and crotonic acid, of which acrylic acid and methacrylic acid are particularly preferred. The?,? - ethylenically unsaturated carboxylic acid of the acid polymer as the third polymer component is preferably 1% by mass to 35% by mass, more preferably 5% by mass to 20% by mole, based on the total acid polymer .

As the third polymer component, the acid polymer is preferably a copolymer of an? -Olefin and an unsaturated carboxylic acid. Optionally, it is possible to optionally include non-acidic low molecular weight polymerizable monomers having up to 8 carbon atoms as the third monomer. Such optional monomers include, but are not limited to, unsaturated halo hydrocarbons (e.g., vinyl fluoride or vinyl chloride), or unsaturated (ethylenically unsaturated) Nitrile (e.g. acrylonitrile). The third monomer is preferably 5 mol% or less, more preferably 3 mol% or less, based on the total weight of the third polymer.

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

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

The blend of the present invention may contain conventionally known additives such as an antioxidant, a stabilizer, a filler, a refractory material, a release agent, a coloring agent, and other materials in order to improve the processability of the polymer or the physical properties of the blend. The additives may be added before or after mixing with the polyketone and the modifier by known methods.

The method for producing the blend of the present invention is not particularly limited as long as the blend or the blend component does not cause excessive disintegration and the blend is uniformly produced. In another embodiment, the polymer component can be blended in a mixing apparatus exhibiting high shear stress . A sheet, a film, a plate and a molded product can be produced by molding the blend by a conventional method, for example, extrusion molding or injection molding. Such application examples can be used for interior parts and exterior parts used in automobiles.

Hereinafter, the constitution and effects of the present invention will be described in detail with reference to specific examples and comparative examples, but these examples are merely for the purpose of understanding the present invention more clearly and do not limit the scope of the present invention. The present invention will be described in detail with reference to the following non-limiting examples.

Comparative Example 1

Linear alternating polyketone terpolymers of carbon monoxide and ethylene and propene were prepared in the presence of a catalyst composition formed from palladium acetate, trifluoroacetic acid and 1,3-bis [bis (2-methoxyphenyl-phosphino] propane . The polyketone terpolymer prepared above had a melting point of 220 DEG C, an LVN of 1.3 dl / g measured with HFIP (hexa-fluoroisopropano) at 25 DEG C and a MI index of 48 g / 10 min. The resulting polyketone terpolymer was loaded with 0.1 wt% of a copolymer of ethene and methacrylic acid (trade name: Nucrel 1183C) and pelletized on an extruder using a twin-screw of 2.5 cm diameter and L / D = 32 operating at 250 rpm. (manufactured by BYK Gardner Co., Ltd.) was used to measure the yellow index of the specimens prepared in the first step, and then the yellow index was measured using a colorimeterThe yellow index was measured by the same method as described above for the molding specimens prepared by injection molding after 10 to 20 minutes retention in the extruder, And then a specimen on a pellet was obtained, and MI (melt viscosity) values were measured for each condition using an MI meter (Model 4002, Alpha Technologies-A Division of Dynico), and the variation was compared.

Comparative Example 2

Linear alternating terpolymers of carbon monoxide and ethylene and propene were prepared in the presence of a catalyst composition resulting from palladium acetate, trifluoroacetic acid and 1,3-bis [bis (2-methoxyphenyl-phosphino] propane. The polyketone polymer used in the present invention had a melting point of 220 DEG C, an LVN of 1.5 dl / g measured with HFIP (hexa-fluoroisopropano) at 25 DEG C and a MI index of 24 g / 10 min. A 0.1 wt.% Copolymer of ethene and methacrylic acid (trade name: Nucrel 1183C) was added to the polymer. The thus prepared sample was extruded using a twin screw having a diameter of 2.5 cm and operating at 250 rpm and L / D = (Manufactured by BYK Gardner Co., Ltd.) was used to prepare a polyketone blend on a pellet basis, and the prepared test piece was injection-molded on a molding machine having a mold clamping force of 80 tons. ), And the molded specimens prepared by injection molding after staying in the injection machine for 10 or 20 minutes respectively were measured for their yellow index by the same method as described above, and their variations were compared. The specimen on the pellet was obtained by freezing and shredding the prepared specimen, and MI (melt viscosity) value was measured for each condition using an MI measuring machine (Model 4002, manufactured by Alpha Technologies-A Division of Dynico) And the variation was compared.

Examples 1 to 4

In addition to the polyketone blend prepared in pellet form in Comparative Example 1, titanium dioxide (manufactured by DuPont), a crystal nucleus additive, was mixed so as to contain 0.1, 1.0, 5.0, and 10 wt%, respectively, relative to the total blend weight, The blend was formulated on an extruder using a twin screw with a diameter of 2.5 cm and L / D = 32. After blending, the blend specimens were injection molded on a molding machine with a mold clamping force of 80 tons. The specimen measurement methods were compared in the same manner as in the comparative example.

The yellow index and MI (melt viscosity) change characteristics of the prepared blend test pieces after initial, 10 and 20 min injection residence were measured and are shown in Table 1. For reference, the higher the yellow index, the more yellowing has occurred.

In the comparative examples and the examples of the present invention, the first 0 min value differs depending on whether titanium dioxide is input or not and the content thereof. This is more important than the initial value of each data because it is important to change the color or melt viscosity after initial and after processing when applied to actual production process.

As shown in Table 1, the yellow index (YI) and the MI drop phenomenon were collectively improved as the nucleating agent was added. However, since the content of the nucleating agent was 5.0% or more, .

It can be seen that the content of the crystal nucleating agent is most preferably 0.1 or more and less than 0.5% with respect to the weight of the entire blend. Titanium dioxide is a white powder of fine color and at the same time has an effect of increasing the crystallinity, so that the polyketone polymer has a reduced amorphous portion, a dense crystal, and an increased opacity of white. As a result, the effect of increasing heat stability and decreasing the amount of color change is obtained. That is, as the titanium dioxide is added, the YI value and the MI drop phenomenon are improved.

In addition, if the titanium dioxide content is 5.0% or more, it is assumed that the misalignment of the two materials slightly decreases. Therefore, the content ratio should be determined according to the required properties of the final application product.

Examples 5 to 8

In addition to the pelletized polyketone terpolymer of Comparative Example 2, which is lower in MI than Comparative Example 1, titanium dioxide (manufacturer: Dupont), which is a crystal nucleus additive, is further mixed and has a diameter of 2.5 cm, operating at 250 rpm, with L / D = 32 The blend was formulated on an extruder using a two-axis screw. Titanium dioxide was prepared so as to contain 0.1, 1.0, 5.0, and 10 wt%, respectively, with respect to the total blend weight. The prepared blend is shown in Table 2. After blending, the blend specimens were injection molded on a molding machine with a mold clamping force of 80 tons. The specimen measurement methods were compared in the same manner as in the comparative example.

As shown in Table 2, when the titanium dioxide, which is a nucleating agent, was used, the YI and MI drop phenomena were improved, and when the content of titanium dioxide was 1.0% or more and 5.0% or less, Showed the same level of results. In the case of polymers with lower MI, the degree of neutralization was improved by the content of only 1.0% since the viscosity was not significantly changed due to deterioration as a midpoint viscosity.

Therefore, it can be seen that even in the polyketone composition system shown in Table 2, the color and MI drop phenomenon is best improved when the content of the crystal nucleating agent is less than 5.0% by weight. More preferably, when the color change is ± 1, 1.0% is most preferable in the present composition system because it is almost impossible to be visually recognized.

The polyketone blend of the present invention was compared using two kinds of polyketone polymers alone according to the MI (melt viscosity), and it was found that the color stability was improved at the processing temperature and the MI drop phenomenon was improved and the processing stability was increased .

Claims (4)

A linear alternating polyketone polymer composed of carbon monoxide and at least one ethylenically unsaturated hydrocarbon, a titanium dioxide crystal nucleating agent, and a copolymer of an alpha -olefin monomer and an ethylenically unsaturated carboxylic acid monomer Wherein the titanium dioxide crystal nucleating agent comprises less than 5.0% by weight based on the weight of the entire polyketone blend, wherein the hue change value produced by the extrusion molding or injection molding of the polyketone blend is not more than? 3 and the melt viscosity (MI) And the value is? 6 or less. delete delete delete