KR20150108602A - Polyketone resin composition and method for preparing the same - Google Patents

Abstract

The present invention relates to a polyketone resin composition, and a method for preparing the same. More specifically, the present invention relates to a polyketone resin composition, capable of greatly improving impact resistance, flexibility and durability by manufacturing a cable tie and an industrial band cable by using a polyketone resin and a toluene sulfonamide-based plasticizer composition, and to a molded article of the polyketone resin composition and a method for preparing the polyketone resin composition and the molded article.

Description

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

More particularly, the present invention relates to a polyketone resin composition and a method for producing the same, and more particularly, to a polyketone resin composition and a method for producing the same, A polyketone resin composition, a molded article thereof, and a process for producing the same.

Cable ties for automobiles are used as harness fixation straps for automobiles. They are manufactured using NYLON 6,6 high temperature materials. Industrial band cables are used as straps for fixing cable outdoor. Cable materials for automotive and industrial applications require flexibility, heat resistance and impact strength.

A typical material used in cable ties for automobiles in the past is polyamide 66 (PA66).

However, since the impact resistance and the assembling property of the PA66 are low, there is a problem that the product is broken after the cable is mounted. Therefore, the product is supplied to the end user after containing the moisture by about 2% through the process of forced wet after the injection molding.

Accordingly, development of new materials excellent in mechanical properties, impact resistance and durability is required.

U.S. Patent No. 4,843,144 U.S. Patent No. 4,880,903

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made in view of the above problems, and it is an object of the present invention to provide a polyketone resin composition capable of suitably applying flexibility and impact resistance as well as mechanical properties basically required for industrial materials .

In order to accomplish the above object, the present invention provides a polyketone resin composition comprising: a polyketone resin; And a toluene sulfonamide based plasticizer, and a molded product thereof (particularly, an automobile cable tie and an industrial band cable).

According to another aspect of the present invention, there is also provided a process for preparing a catalyst composition, comprising: preparing a catalyst composition comprising a palladium compound, an acid having a pKa value of 6 or less, and a bidentate compound of phosphorus; Preparing a mixed solvent comprising an alcohol and water; Conducting the polymerization in the presence of the catalyst composition and the mixed solvent to prepare a linear terpolymer of carbon monoxide, ethylene and propylene; Removing the remaining catalyst composition from the linear terpolymer with a solvent to obtain a polyketone resin; And a step of mixing and extruding the polyketone resin with a toluene sulfonamide-based plasticizer to prepare a polyketone resin composition.

According to still another aspect of the present invention, there is provided a method of manufacturing a cable tie for an automobile or an industrial band cable by injecting a polyketone resin composition produced by the above method.

By using a polyketone resin and a plasticizer, the composition of the present invention can greatly improve flexibility and impact resistance while ensuring mechanical rigidity, thereby achieving harmonious physical properties, and can be applied to various industrial materials (in particular, automobile cable ties, industrial bands Cable material).

Further, according to the manufacturing method of the present invention, the injection molding cycle time is shortened by 20%, and the productivity is significantly improved as compared with the existing material.

Hereinafter, the present invention will be described in detail.

Polyketone resin composition and molded article thereof

The polyketone resin composition of the present invention comprises a polyketone resin; And a toluene sulfoamide-based plasticizer, and more particularly, to a composition comprising 100 parts by weight of a polyketone resin; And 10 parts by weight of a toluene sulfonamide-based plasticizer.

The polyketone resin, which is the subject of the composition of the present invention, is a newly developed thermoplastic resin which is excellent in mechanical properties such as impact strength and molding properties and is thus useful as a molded article such as a food container or a material for various parts. The mechanical properties of the polyketone resin belong to the category of high performance plastics. Polyketone resins having other desirable properties such as conductivity while retaining inherent physical properties such as mechanical properties and molding properties are widely used for various purposes. In addition, polyketone resin is a polymer material synthesized from carbon monoxide as a raw material, and has attracted great attention as an environmentally friendly material.

Generally, the polyketone resin is synthesized from carbon monoxide and olefins. For example, U.S. Patent No. 4,843,144 discloses line alternating polymers synthesized from olefins such as ethylene and propylene and carbon monoxide. The polyketone resin produced in this patent has been shown to have excellent impact resistance, high rebound resilience at room temperature and low temperature, and excellent creep properties.

In recent years, among polyketones, there is a growing interest in a series of alternating polyketones in which ketone groups and at least one ethylenically unsaturated hydrocarbon are alternately polymerized and improved in mechanical properties and molding characteristics. For example, U.S. Patent No. 4,880,903 discloses a polyketone terpolymer in which ketone groups, ethylene, and other olefinically unsaturated hydrocarbons (e.g., propylene) are alternately polymerized to form.

The contents of the aforementioned U.S. Patent Nos. 4,843,144 and 4,880,903 are incorporated herein by reference.

Specifically, the linear alternating polyketone as a main component of the polyketone resin composition of the present invention is a linear alternating structure composed of a ketone group and at least one ethylenically unsaturated hydrocarbon, and substantially one carbon monoxide (or ketone group ), And is excellent in physical properties, appearance characteristics and molding properties.

The polyketone resin may contain a repeating unit represented by the following formula (1).

[Chemical Formula 1]

- {- CO - (- CH 2 -CH 2 -) -} x - {CO- (G) -} y -

Wherein G is derived from monomers of at least three ethylenically unsaturated hydrocarbons polymerized through ethylenic unsaturation, wherein x: y is at least 2: 1.

Ethylenically unsaturated hydrocarbons suitable for use as the precursor of the polyketone are selected from the group consisting of ethene having up to 20 carbon atoms, preferably up to 10 carbon atoms, alpha -olefins (e.g., propene, 1-butene, ), Aliphatic hydrocarbons such as isobutene, 1-hexene and 1-octene, or aryl aliphatic hydrocarbons having an aryl substituent on the aliphatic molecule, in particular ethylenically unsaturated carbon atoms Lt; / RTI > is an aryl aliphatic hydrocarbon in which an aryl substituent is formed. Examples of the aryl aliphatic hydrocarbon in the ethylenic unsaturated hydrocarbon include styrene, p-methylstyrene, p-ethylstyrene, and m-isopropyl styrene.

Such ethylenically unsaturated hydrocarbons and ketone compounds are copolymerized to form a linear alternating polyketone. Among them, a linear alternating polyketone formed by copolymerization of ethene and a ketone compound, or a mixture of at least three Linear alternating polyketone formed by copolymerization of an ethylenically unsaturated hydrocarbon having a carbon atom is preferable in view of the fact that the copolymerization reaction is easy and the molecular weight of the copolymerized linear alternating polyketone is relatively uniform. In short, the preferred polyketone resin is a copolymer of carbon monoxide and ethene, more preferably a second ethylenically unsaturated hydrocarbon having carbon monoxide, ethene and at least three carbon atoms (especially propene) is a linear terpolymer with an a-olefin.

The polyketone resin preferably has an intrinsic viscosity (LVN) of 0.5 to 10 dl / g, more preferably 0.8 to 4 dl / g, and most preferably 1 to 1.5 dl / g. If the intrinsic viscosity of the polyketone resin is less than 0.5 dl / g, the mechanical properties may be deteriorated. If the intrinsic viscosity exceeds 10 dl / g, the workability may be deteriorated.

The polyketone resin has a number-average molecular weight, as measured by gel permeation chromatography, of preferably 100 to 200,000, more preferably 20,000 to 90,000. The physical properties of the polymer depend on the molecular weight, whether the polymer is a copolymer or a terpolymer, and in the case of a terpolymer, the physical properties of the second hydrocarbon moiety are determined.

The melting point of the polyketone resin is usually in the range of 175 ° C to 300 ° C, specifically 210 ° C to 270 ° C.

The plasticizer is a clear yellowish liquid phase having a density of 1.2 g / cm < 3 > as a mixture of 60 parts by weight of N-ethyl-p-toluenesulphonamide and 40 parts by weight of N-ethyl-o-toluenesulphonamide.

The plasticizer is preferably contained in an amount of 10 parts by weight per 100 parts by weight of the polyketone resin. If the content of the plasticizer is less than 10 parts by weight, the flexibility may be deteriorated. If the amount is more than 10 parts by weight, the mechanical strength may be deteriorated.

The polyketone resin composition of the present invention may additionally contain additives commonly used in the art within the scope not deviating from the object.

In one preferred embodiment, antioxidants, heat stabilizers, lubricants, processing aids and weathering stabilizers may be added to the polyketone resin composition of the present invention, alone or in combination.

As the antioxidant, a phenolic oxamide antioxidant may be used, which has a deactivation effect of the metal catalyst used in the polymerization. The antioxidant is preferably contained in an amount of 0.1 to 0.5 parts by weight based on 100 parts by weight of the polyketone resin. If the content of the antioxidant is less than 0.1 parts by weight, the deactivation function of the metal catalyst may be deteriorated. If the amount is more than 0.5 parts by weight, the physical properties of the product may be deteriorated.

Examples of the heat stabilizer include phosphorus thermal stabilizers, particularly hydroxy apatite represented by M ₁₀ (PO ₄ ) ₆ (OH) ₂ (wherein M is barium, strontium or calcium), preferably calcium hydroxyapatite Can be used, which suppresses the problem of an increase in viscosity during processing. The heat-resistant stabilizer is preferably contained in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the polyketone resin. If the content of the heat-resistant stabilizer is less than 0.1 parts by weight, the viscosity-increasing inhibiting function may be deteriorated. If the content is more than 2 parts by weight, the physical properties of the product may be deteriorated.

As the activator, an ethylene-methacrylic acid ester and / or a polyethylene-based synthetic lubricant such as ethylene bisstearamide, which is an acrylic lubricant, may be used. These lubricants are preferably contained in an amount of 0.1 to 1 part by weight per 100 parts by weight of the polyketone resin. If the content of the lubricant is less than 0.1 part by weight, the appearance quality may be deteriorated, and if it exceeds 1 part by weight, the mechanical properties may be deteriorated.

As the processing aid, ethylene methacrylic acid may be used. As the weather stabilizer, a benzotriazole-based material, a triazine-based material, a hindered amine-based material, and the like may be used, but the present invention is not limited thereto.

As described above, the polyketone resin composition of the present invention can be molded into a variety of products by extrusion, injection molding, or the like.

Specifically, the polyketone resin composition of the present invention is injection-molded or extruded to produce polyketone sheets, films, plates, OA appliances, electric / electronic parts, housing parts, automobile parts, Various industrial materials can be produced, and these industrial materials have excellent mechanical properties and molding properties.

In particular, the polyketone resin composition of the present invention is excellent in impact resistance, flexibility, and mechanical rigidity suitable for a cable tie, and is therefore very suitable as an automobile cable tie material.

POLYKETONE RESIN COMPOSITION AND METHOD FOR MANUFACTURING CABLE TIE BY CAR

According to another aspect of the present invention, there is provided a method of manufacturing the polyketone resin composition of the present invention and a method of manufacturing a cable tie using the same.

A method for producing a polyketone resin composition of the present invention comprises: preparing a catalyst composition comprising a palladium compound, an acid having a pKa value of 6 or less, and a bidentate compound of phosphorus; Preparing a mixed solvent (polymerization solvent) containing an alcohol (for example, methanol) and water; Conducting the polymerization in the presence of the catalyst composition and the mixed solvent to prepare a linear terpolymer of carbon monoxide, ethylene and propylene; Removing the remaining catalyst composition from the linear terpolymer with a solvent (e.g., alcohol and acetone) to obtain a polyketone resin; And mixing and extruding the polyketone resin with a toluene sulfonamide based plasticizer.

As the palladium compound constituting the catalyst composition, palladium acetate can be used, and the amount of the palladium compound to be used is preferably 10 ^-3 to 10 ^-1 mole.

As the acid having a pKa value of 6 or less constituting the catalyst composition, at least one selected from the group consisting of trifluoroacetic acid, p-toluenesulfonic acid, sulfuric acid and sulfonic acid, preferably trifluoroacetic acid, may be used. 6 to 20 (mol) equivalents relative to the compound is appropriate.

Examples of the bidentate ligand compound constituting the catalyst composition include 1,3-bis [diphenylphosphino] propane (e.g., 1,3-bis [di (2-methoxyphenylphosphino) propane) Bis [bis [anisyl] phosphinomethyl] -1,5-dioxaspiro [5,5] undecane, the amount of which is 1 to 1.2 ) Equivalent.

The carbon monoxide, ethylene and propylene are liquid phase polymerized in a mixed solvent of alcohol (e.g. methanol) and water to produce a linear terpolymer. As the mixed 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.

The polymerization temperature is preferably in the range of 50 to 100 ° C and the reaction pressure in the range of 40 to 60 bar. The resulting polymer is recovered through filtration and purification processes after polymerization, and the remaining catalyst composition is removed with a solvent such as alcohol or acetone.

In the present invention, the obtained polyketone resin is mixed with a toluene sulfonamide plasticizer and then extruded by an extruder to finally obtain a polyketone resin composition.

In one specific example, the polyketone resin is used in an amount of 100 parts by weight, the toluene sulfonamide plasticizer particle diameter of 10 parts by weight, the phenolic oxamide antioxidant in an amount of 0.1 to 0.5 part by weight, the phosphorus thermal stabilizer in an amount of 0.1 to 2 parts by weight, 0.1 to 1 part by weight of the polyethylene-based synthetic lubricant is added to a twin-screw extruder having L / D of 32 to 40 and 40 to 65, followed by melt-kneading and extruding to produce the polyketone resin composition of the present invention.

In this case, the extrusion temperature is preferably 230 to 260 ° C, and the screw rotation speed is preferably in the range of 100 to 300 rpm. If the extrusion temperature is less than 230 캜, kneading may not occur properly, and if the extrusion temperature exceeds 260 캜, problems related to the heat resistance of the resin may occur. If the screw rotational speed is less than 100 rpm, smooth kneading may not occur. If the screw rotation speed is more than 300 rpm, the plasticizer may volatilize and the required flexibility may be lowered.

Hereinafter, the present invention will be described more specifically by way of examples. However, these examples are provided only for the understanding of the present invention, and the scope of the present invention is not limited to these examples in any sense.

Example 1

A linear terpolymer of carbon monoxide, ethylene and propylene was added to 100 parts by weight of methanol in the presence of a catalyst composition consisting of palladium acetate, anion of trifluoroacetic acid and 1,3-bis [diphenylphosphino] The polymerization was carried out in a solvent of 70 to 90 DEG C in which water was added. The melting point of the prepared terpolymer was 220 DEG C and the intrinsic viscosity (LVN) measured on 1,1,1,3,3,3-HFIP was 1.5 dl / g.

0.2 parts by weight of XL-1 (manufactured by Chemtura), 0.3 part by weight of calcium hydroxyapatite (manufactured by Budenheim), and 10 parts by weight of a copolymer comprising ethene and methacrylic acid (trade name: Nucrel 1183C) was put into a pellet on an extruder at a temperature of 240 DEG C using a 40 mm biaxial screw operated at 200 rpm.

100 parts by weight of the polyketone resin prepared above was introduced into a main body of an extruder through a metering pump on the side of an extruder and 10 parts by weight of a toluene sulfonamide plasticizer was extruded through a melt pump at a temperature of 240 캜 at a screw rotation speed of 250 rpm.

The physical properties of the final polyketone resin were as shown in Table 1 below.

Test Items Test Methods unit Measure Physical properties
importance
Contraction ratio
Absorption rate 23 ° C, Equilibrium 60% RH
ASTM D792
ASTM D955
ASTM D570
-
%
%
1.10
2.0
0.45 Thermal property
Melting point
Melt index 240 DEG C, 2.16 kg
Heat distortion temperature
HDT 0.45 MPa (4.6 Kg / cm2)
HDT 1.82 MPa (18.6 Kg / cm2)
combustibility
ASTM D1525
ASTM D1238
ASTM D648


UL94
℃
g / 10 min
℃
℃

-
190
50

190

HB Mechanical property
Tensile strength 23 ℃
Elongation at break 23 ℃
Flexural strength 23 ℃
Flexural modulus 23 ℃
Notched Izod impact strength 23 ° C
Rockwell hardness R scale
ASTM D638
ASTM D638
ASTM D790
ASTM D790
ASTM D256
ASTM D785
MPa
%
MPa
MPa
KJ / m ²
-
48
100
40
900
15
80

Comparative Example 2

Rhodia PA66 B230 product was used.

Property evaluation

The polyketone resin composition pellets of the above examples were (injection molded) molded to evaluate physical properties in comparison with the products of the comparative examples, and the results are shown in Table 2 below.

1. Tensile strength: ASTM D638.

2. Flexural strength: ASTM D790.

3. Flexural modulus: It was conducted according to ASTM D790.

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

5. Heat distortion temperature: ASTM D648.

Test Items Test Methods unit PK B230 B230
Forced wetting
(2.0%) Physical properties
importance
Contraction ratio
Absorption rate 23 ° C, Equilibrium 60% RH
ASTM D792
ASTM D955
ASTM D570
-
%
%
1.10
2.0
0.45
1.12
0.16
3.25
1.12
0.16
2.0 Thermal property
Melting point
Melt index 240 DEG C, 2.16 kg
Heat distortion temperature
HDT 0.45 MPa (4.6 Kg / cm ² )
HDT 1.82 MPa (18.6 Kg / cm ² )
ASTM D1525
ASTM D1238
ASTM D648


℃
g / 10 min
℃
℃
190
50

190
250
20

220
250
20

220 Mechanical property
Tensile strength 23 ℃
Elongation at break 23 ℃
Flexural strength 23 ℃
Flexural modulus 23 ℃
Notched Izod impact strength 23 ° C
ASTM D638
ASTM D638
ASTM D790
ASTM D790
ASTM D256
MPa
%
MPa
MPa
KJ / m2
48
100
40
900
15
61
16
83
2000
5
48
70
42
860
8

As shown in the above Table 2, in the case of Examples, even though the PA66 exhibited mechanical stiffness equal to that of wet PA66 even in the non-wet state, the specific impact resistance was evaluated to be excellent. It is believed that a product similar to the rubber phase was formed at the impact evaluation temperature due to the low glass transition temperature of the polyketone.

Claims (9)

Polyketone resin; And a toluene sulfonamide-based plasticizer. The method according to claim 1,
100 parts by weight of a polyketone resin; And 10 parts by weight of a toluene sulfonamide-based plasticizer. The method according to claim 1,
The polyketone resin is a linear terpolymer of carbon monoxide, ethylene and propylene,
Wherein the plasticizer is a toluene sulfonamide-based resin. The method according to claim 1,
An antioxidant, a heat-resistant stabilizer and a lubricant. 5. The method of claim 4,
The antioxidant is a phenolic oxamide antioxidant, which is contained in an amount of 0.1 to 0.5 parts by weight based on 100 parts by weight of the polyketone resin,
The heat-resistant stabilizer is a hydroxyapatite, which is contained in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the polyketone resin,
Wherein the lubricant is an ethylene-methacrylic acid ester as an acrylic lubricant and an ethylene bisstearamide as a polyethylene-based synthetic lubricant, each of which is contained in an amount of 0.1 to 1 part by weight based on 100 parts by weight of the polyketone resin. A molded article of the polyketone resin composition according to any one of claims 1 to 5. Preparing a catalyst composition comprising a palladium compound, an acid having a pKa value of 6 or less, and a bidentate compound of phosphorus;
Preparing a mixed solvent comprising an alcohol and water;
Conducting the polymerization in the presence of the catalyst composition and the mixed solvent to prepare a linear terpolymer of carbon monoxide, ethylene and propylene;
Removing the remaining catalyst composition from the linear terpolymer with a solvent to obtain a polyketone resin; And
And mixing and extruding the polyketone resin with a toluene sulfonamide-based plasticizer to form a polyketone resin composition. 8. The method of claim 7,
As the palladium compound is palladium acetate, and the amount of use thereof is 10 ^-3 to 10 ^-1 molar,
The acid having a pKa value of 6 or less is at least one selected from the group consisting of trifluoroacetic acid, p-toluenesulfonic acid, sulfuric acid and sulfonic acid, the amount of which is 6 to 20 equivalents relative to the palladium compound,
The phosphorus bidentate compound may be prepared by reacting 1,3-bis [diphenylphosphino] propane and 1,3-bis [bis [anisyl] phosphinomethyl] -1,5-dioxaspiro [5,5] Wherein the amount of the palladium compound to be used is 1 to 1.2 equivalents based on the palladium compound. 8. The method of claim 7,
Wherein the mixed solvent comprises 100 parts by weight of methanol and 2 to 10 parts by weight of water.