KR20190087019A - Polyketone resin composition with improved durability - Google Patents

Abstract

The present invention relates to a polyketone resin composition comprising: a linear alternating polyketone copolymer; and at least one of an antioxidant and an inorganic filler, wherein the polyketone resin composition can greatly improve durability, flame resistance, and light resistance in an environment exposed to ultraviolet rays and seawater while maintaining advantageous properties inherent in a polyketone resin such as excellent mechanical rigidity, dimensional stability and the like, and also, can reduce a production cost since the polyketone resin composition can be produced by a simple production process.

Description

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

The present invention relates to a polyketone resin composition which is excellent in physical property retention even when moisture is penetrated and has improved light resistance against ultraviolet rays.

Polyketone can be used for high-end engineering plastics such as interior and exterior materials and fuel system parts in automobile, electric and electronic fields based on excellent impact resistance, chemical resistance and abrasion resistance, and can also be used as a fiber having ultrahigh strength and ultrahigh elasticity . Polyketone is an eco-friendly material made from carbon monoxide, which is the main cause of olefins and air pollution. Abrasion resistance, and chemical resistance, it is widely regarded as a next-generation engineering plastic material to replace existing nylon and plastic in automobile interior and exterior materials, electric and electronic parts, tire cord, and industrial pipe.

The polyketone is a copolymer of carbon monoxide and an ethylenically unsaturated compound, in particular, repeating units derived from carbon monoxide and repeating units derived from an ethylenically unsaturated compound are alternately linked. The polyketone is excellent in mechanical properties and thermal properties and has excellent abrasion resistance, It has high gas barrier properties and is useful for various applications.

Generally, polyketone is a semicrystalline polymer having a glass transition temperature of 15 ° C and a melting temperature of 225 ° C, and its characteristic behavior is very similar to polypropylene. These polyketones show high yield stress and stiffness, but they have fracture toughness characteristics and have been reported as a weak point of deterioration of properties due to long-term heat aging.

Among the polyketones in recent years, there is a growing interest in a series of alternating polyketones wherein 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 ter-polymer in which a ketone group, ethylene, and other olefinically unsaturated hydrocarbons (e.g., propylene) are alternately polymerized and formed. U.S. Patent No. 4,843,144 discloses a process for the production of a catalyst by reacting at least one ethylenically unsaturated hydrocarbon and a ketone compound with a palladium compound catalyst, a nonhydrohalogenic acid catalyst having an acidity (pKa) of less than 6, A method for producing a polyketone in which a systematic unsaturated hydrocarbon is alternately polymerized is disclosed.

However, in order to utilize polyketone as a material for a torsion floor, it is required to develop a polyketone resin composite that maintains the mechanical strength against the ultraviolet rays and the water containing the salt.

The present invention provides a polyketone composition having durability against moisture penetration even when exposed to water such as seawater and having enhanced oxidation resistance against ultraviolet rays.

In order to solve the above problems, the present invention provides a polyketone resin composition comprising at least one of a polyketone resin, an antioxidant, and an inorganic filler.

The polyketone resin composition of the present invention can greatly improve durability, salt resistance and light resistance in an environment exposed to ultraviolet rays and seawater while retaining favorable characteristics inherent in polyketone resins such as excellent mechanical stiffness and dimensional stability, Production costs can also be reduced because production is possible.

Therefore, it is possible to utilize polyketone resin as a tile material for torsion floor, thereby contributing to expansion of utilization of polyketone material.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a linear alternating polyketone copolymer comprising repeating units represented by the following general formulas (1) and (2) and having y / x of 0.03 to 0.3; And a polyketone resin composition comprising at least one of an antioxidant and an inorganic filler, the polyketone composition having improved durability and oxidation resistance against ultraviolet rays.

- [- CH2CH2-CO] x- (1)

- [- CH2 --CH (CH3) - CO] y - (2)

(x and y represent mol% of each of the general formulas (1) and (2) in the polymer).

The polyketone resin used in the present invention is a thermoplastic synthetic resin which is excellent in mechanical properties such as electrical conductivity and rebound resilience and molding properties and thus is usefully used as a material for various molded products and parts. It is synthesized from carbon monoxide as a raw material It has attracted great attention as an eco-friendly material.

In particular, the polyketone resin has lower moisture absorption than nylon (0.45%, 50% RH, 23 ℃), and it is a material that can change various dimensions and physical properties due to moisture absorption.

Hereinafter, the process for producing the polyketone will be described.

The production process of polyketone is carried out in the presence of an organometallic complex catalyst comprising (a) a Group 9, 10 or 11 transition metal compound, and (b) a ligand having an element of Group 15, Wherein the carbon monoxide, ethylene and propylene are subjected to liquid phase polymerization in a mixed solvent of an alcohol (e.g., methanol) and water to produce a linear terpolymer, As the 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.

Wherein the catalyst comprises (a) a Group 9, 10 or 11 transition metal compound of the Periodic Table of the Elements (IUPAC Inorganic Chemical Nomenclature, 1989) and (b) a ligand having an element of Group 15 elements.

Examples of the Group 9 transition metal compound in the ninth, tenth, or eleventh group transition metal compound (a) include complexes of cobalt or ruthenium, carbonates, phosphates, carbamates, and sulfonates, Specific examples thereof include cobalt acetate, cobalt acetylacetate, ruthenium acetate, ruthenium trifluoroacetate, ruthenium acetylacetate, and ruthenium trifluoromethanesulfonate.

Examples of the Group 10 transition metal compounds include complexes of nickel or palladium, carbonates, phosphates, carbamates, sulfonates and the like. Specific examples thereof include nickel acetate, nickel acetylacetate, palladium acetate, palladium trifluoroacetate , Palladium acetylacetate, palladium chloride, bis (N, N-diethylcarbamate) bis (diethylamine) palladium and palladium sulfate.

Examples of Group 11 transition metal compounds include copper or silver complexes, carbonates, phosphates, carbamates, sulfonates and the like, and specific examples thereof include copper acetate, copper trifluoroacetate, copper acetylacetate, Examples of the trifluoroacetic acid include silver acetyl acetate, trifluoromethanesulfonic acid and the like.

Of these, the transition metal compound (a), which is preferable inexpensively and economically, is nickel and copper compounds, and the preferable transition metal compound (a) in terms of the yield of the polyketone and the molecular weight is the palladium compound, It is most preferable to use palladium acetate.

As the polyketone polymerization method, a solution polymerization method using a liquid medium, a suspension polymerization method, a vapor phase polymerization method in which a small amount of a polymer is impregnated with a high concentration catalyst solution, and the like are used. The polymerization may be either batchwise or continuous. The reactor used in the polymerization can be used as it is or in a known manner. The polymerization temperature is not particularly limited, and is generally 40 to 180 占 폚, preferably 50 to 120 占 폚. The pressure at the time of polymerization is not particularly limited, but is generally from normal pressure to 20 MPa, preferably from 4 to 15 MPa.

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

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).

[Chemical Formula 1]

- [CO- (-CH2-CH2-)] x- [CO- (G)] y-

In the general formula (2), G is an ethylenically unsaturated hydrocarbon, particularly a portion obtained from an ethylenically unsaturated hydrocarbon having at least three carbon atoms, and x: y is preferably at least 1: 0.01.

In another embodiment, the polyketone polymer is a copolymer comprising repeating units represented by the general formulas (1) and (2), and y / x is preferably 0.03 to 0.3. When the value of the y / x value is less than 0.03, there is a limit in that the meltability and processability are inferior. When the value of y / x is more than 0.3, the mechanical properties are poor. Further, y / x is more preferably 0.03 to 0.1.

- [- CH2CH2-CO] x- (1)

- [- CH2 --CH (CH3) - CO] y - (2)

In addition, the melting point of the polymer can be controlled by controlling the ratio of ethylene to propylene in the polyketone polymer. For example, when the molar ratio of ethylene: propylene: carbon monoxide is adjusted to 46: 4: 50, the melting point is about 220 ° C, while the melting point is adjusted to 235 ° C when the molar ratio is adjusted to 47.3: 2.7: 50.

The number average molecular weight measured by gel permeation chromatography is preferably in the range of 100 to 200,000, more preferably 20,000 to 90,000. The physical properties of the polymer are determined according to the molecular weight, depending on whether the polymer is a copolymer or a terpolymer and, in the case of a terpolymer, the properties of the second hydrocarbon part. The melting point of the total of the polymers used in the present invention is 175 ° C to 300 ° C, and generally 210 ° C to 270 ° C. The intrinsic viscosity (LVN) of the polymer measured by HFIP (hexafluoroisopropyl alcohol) at 60 DEG C using a standard tubular viscosity measuring apparatus is 0.5 dl / g to 10 dl / g, preferably 0.8 dl / g to 4 dl / g, And more preferably 1.0 dl / g to 2.0 dl / g. If the intrinsic viscosity is less than 0.5 dl / g, the mechanical properties are deteriorated. If the intrinsic viscosity exceeds 10 dl / g, the workability is deteriorated.

On the other hand, the molecular weight distribution of the polyketone is preferably 1.5 to 2.5, more preferably 1.8 to 2.2. When the ratio is less than 1.5, the polymerization yield decreases. When the ratio is 2.5 or more, the moldability is poor. In order to control the molecular weight distribution, it is possible to adjust proportionally according to the amount of the palladium catalyst and the polymerization temperature. That is, when the amount of the palladium catalyst is increased or when the polymerization temperature is 100 ° C or higher, the molecular weight distribution becomes larger.

Meanwhile, the polyketone resin composition of the present invention comprises at least one carbon black-based antioxidant selected from the group consisting of carbon nanotubes, carbon black, acetylene black, ketjen black, channel black, furnace black, .

The physical properties of the carbon black preferably have an average particle size of 40 to 60 nm and an average surface area of 15 to 30 mg / g. When the average particle size and surface area are within the above range, compatibility with polyketone is improved and performance as an antioxidant is improved.

In addition, the polyketone resin composition of the present invention can also be used in a wide range of applications including, but not limited to, silica (such as natural silica, synthetic silica, fused silica, etc.), silica nitride, magnesium carbonate, talc, magnesium hydroxide, aluminum hydroxide, aluminum silicide, Barium, kaolin, alumina, and clay.

Such an inorganic filler is a component for improving the mechanical strength of the composition of the present invention and the molded article thereof, and also performs a function of lowering the moisture absorption amount.

The content of the carbon black-based antioxidant is preferably 0.5 to 2% by weight. If it is less than 0.5% by weight, it may be difficult to expect improvement in durability and light resistance. If it exceeds 2.0% by weight, Mechanical properties (e.g., impact strength), dimensional stability, and molding properties (e.g., extrudability) may not be exhibited.

If the content of the inorganic filler is less than 1% by weight, it may be difficult to expect an improvement in mechanical strength (for example, impact strength). If the content is more than 5% by weight, the viscosity may increase and the flowability may deteriorate, .

The specimen made of the polyketone resin composition of the present invention was precipitated in water and exposed to ultraviolet light (QUV) at 340 nm. After 4 weeks, the retention ratio of the strength (MPa) and the retention ratio of the modulus of elasticity (MPa) It can be applied as tile material for tile floor.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Reference will now be made in detail to the preferred embodiments of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited by the examples.

≪ Example 1 >

An ISO specimen was prepared from a composition containing 99.5% by weight of a polyketone resin and 0.5% by weight of carbon black.

Specifically, a polyketone terpolymer (PK) polymerized from ethylene, carbon monoxide and propylene was directly introduced into a 40 mm biaxial screw operated at 200 rpm to prepare a carbon black (product of Orion) having a particle size of 58 nm and a surface area of 23 mg / And the extruder barrel was set at a temperature of 240 DEG C to prepare a pellet. The test specimens were prepared in accordance with the ISO standard, exposed to ultraviolet light having a wavelength of 340 nm, left for 7 days, and the impact strength was measured. The results are shown in Table 1.

The impact strength (MPa), the modulus of elasticity (MPa), and the elongation (%) of the specimens were measured after 1 day, 4 weeks and 8 weeks after exposure to 340 nm QUV, ) Were evaluated, and the results are shown in Table 2 below.

≪ Example 2 >

A test piece was prepared and tested in the same manner as in Example 1, except that a composition containing 99.0% by weight of polyketone resin and 1.0% by weight of carbon black was prepared.

≪ Example 3 >

A test piece was prepared and tested in the same manner as in Example 1, except that a composition containing 98.6% by weight of polyketone resin and 1.4% by weight of carbon black was prepared.

<Example 4>

A test piece was prepared in the same manner as in Example 1 except that a composition containing 98.2% by weight of polyketone resin and 1.8% by weight of carbon black was prepared.

<Comparative Example>

Except that only the polyketone terpolymer (PK) polymerized from ethylene, carbon monoxide and propylene was used and carbon black and inorganic filler were not added. The specimens of comparative examples prepared without carbon black showed very poor impact strength.

Table 1 summarizes the results of the evaluation test when the specimens of Examples and Comparative Examples were exposed only to 340 nm QUV without impregnating the jars.

Example 1 Example 2 Example 3 Example 4 Comparative Example Carbon black
content 0.5 1.0 1.4 1.8 - Impact Strength - Initial
(kJ / m 2) 16.6 16.4 16.3 16.5 16.1 Impact strength -3 days
(kJ / m 2) 9.8 10.4 11.4 12.5 9.1 Impact strength - 5 days
(kJ / m 2) 8.9 9.2 10.8 11.0 8.1 Impact strength-7 days
(kJ / m 2) 5.8 6.1 7.2 10.1 4.2 Impact strength
Retention rate (%) 35 37 44 61 26

Table 2 below summarizes the data obtained by measuring the mechanical properties of the specimens prepared in Example 1 over time after exposure to 340 nm of ultraviolet rays.

Example 1 Comparative Example
The tensile strength
burglar
(MPa)
Day 1
59
52
4 parking
56
42
Property retention rate
(%)
95%
81%
Modulus of elasticity
(MPa)
Day 1
1877
1785
4 parking
1577
1188
Property retention rate
(%)
82%
67%
Elongation
(%)
Day 1
194
158
4 parking
145
107
Flexural strength
burglar
(MPa)
Day 1
58
51
4 parking
57
40
Property retention rate
(%)
98%
78%
Modulus of elasticity
(MPa)
Day 1
1675
1498
4 parking
1409
1106
Property retention rate
(%)
84%
74%
Impact test
Impact strength
(kJ / m 2)
Day 1
16.5
16.1
4 parking
20
14.8

As can be seen from the above results, when a suitable amount (0.5 to 2% by weight) of antioxidant such as carbon black is contained in the polyketone, resistance to salt water, durability and light fastness to ultraviolet rays are strengthened, And mechanical properties such as impact strength were maintained at a certain level or more.

On the other hand, in the case of the impact strength, the physical properties were strengthened after 4 weeks even though it was impregnated with the wastewater and exposed to the UV. This result shows that the influence of the ultraviolet rays is reduced by the wastewater, It was predicted that the strength was increased rather than being immersed in the wastewater.

That is, when a specimen prepared from a composite composition obtained by adding an oxidizing agent such as carbon black to a polyketone resin as in the present invention is impregnated into a wastewater and exposed to QUV, the impact strength and the elastic modulus are 90% , And the elongation was maintained at 70% or more.

As a result, it was confirmed that the strength (MPa) retention ratio and the modulus of elasticity (MPa) retention ratio after 80 days were more than 80% after 4 weeks, and it was confirmed that the polyketone resin composition of the present invention had strong resistance to water and ultraviolet rays.

Claims (5)

A polyketone resin composition comprising a linear alternating polyketone copolymer comprising repeating units represented by the following general formulas (1) and (2) and having y / x of 0.03 to 0.3 and an antioxidant.
- [- CH2CH2-CO] x- (1)
- [- CH2 --CH (CH3) - CO] y - (2)
(x and y represent mol% of each of the general formulas (1) and (2) in the polymer). The method according to claim 1,
Wherein the antioxidant is at least one selected from the group consisting of carbon nanotubes, carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black and thermoplastic black. The method according to claim 1,
And the antioxidant is 0.5 to 2% by weight. 3. The method of claim 2,
The physical properties of the carbon black include an average particle size of 40 to 60 nm and an average surface area of 15 to 30 mg / g. 5. The method according to any one of claims 1 to 4,
The polyketone resin composition according to any one of claims 1 to 3, wherein the polyketone resin composition has a tensile strength (MPa) retention ratio and a resilience (MPa) retention ratio of 80% or more even after 4 weeks under the condition that the test piece is precipitated in water and exposed to ultraviolet light (QUV) at 340 nm.