KR20160059888A - Method of polyketone with additive - Google Patents

Abstract

The present invention provides a method for producing polyketone having a sufficient effect in preventing oxidation, stabilizing heat resistance, or blocking ultraviolet rays. The method comprises the steps of: adding an organic metal complex catalyst in a mixed solvent consisting of methanol and water, wherein the organic metal complex catalyst consists of a Group 9, Group 10, or Group 11 transition metal compound, a ligand having a Group 15 element, and an anion of acid having pKa of 4 or lower; producing methanol slurry by adding a mixed gas of carbon monoxide and an ethylene unsaturated compound in the mixed solvent including the organic metal complex catalyst; separating polyketone from the methanol slurry; and feeding an additive in the methanol slurry.

Description

[0001] The present invention relates to a method of producing a polyketone containing an additive,

The present invention relates to a polyketone having a sufficient heat resistance, antioxidation property and ultraviolet light shielding property with a small amount of additives in the production of polyketones, and a process for producing the same.

The polyketone having a structure in which repeating units derived from carbon monoxide and repeating units derived from an ethylenically unsaturated compound are substantially alternately linked has excellent mechanical and thermal properties and has high abrasion resistance, chemical resistance and gas barrier property, Expansion is expected. Specifically, polyketone is a useful material as high strength, high heat resistant resin, fiber, and film. Particularly, when a high molecular weight polyketone having an intrinsic viscosity of 2.5 dl / g or more is used as a raw material, a fiber or a film having a very high strength and an elastic modulus can be obtained. Such fibers and films are expected to be widely used for building materials such as belts, rubber reinforcements such as hoses and tire cords, concrete reinforcing materials, and industrial materials.

The polyketone can also be used in various industrial fields by adding additives in addition to the mechanical and chemical properties inherent to the polyketone mentioned above. Conventional methods for producing polyketones include a method in which polyketone is polymerized after solvent polymerization and polymerization is completed. When the polymerization is completed, 3 to 4 kinds of additives in powder form are mixed and pelletized through physical pelletizing, Lt; / RTI >

However, in addition to the problem that a large amount of additive should be used for sufficient antioxidant effect, heat stability stabilization effect or ultraviolet ray shielding effect in the conventional method, the polyketone pellet is formed into a lump of additives The appearance frequency of defective products was high, and it was difficult to exhibit sufficient oxidation prevention, heat stability, or ultraviolet shielding effect.

Accordingly, the inventors of the present invention have solved the above-mentioned problems by improving the manufacturing process of polyketone.

Disclosure of Invention Technical Problem [8] The present invention has been made to solve the above problems in that a large amount of additive is injected into polyketone having antioxidation, heat stability or ultraviolet shielding effect, A stabilizing or ultraviolet shielding effect, and a polyketone produced by the method.

In order to achieve the above object, the present invention provides a process for the preparation of an organometallic complex catalyst comprising an organometallic complex catalyst consisting of a Group 9, a Group 10 or Group 11 transition metal compound, a ligand having an element of Group 15 elements and an anion of an acid having a pKa of 4 or less, To a mixed solvent consisting of water; Preparing a methanol slurry by adding a mixed gas of carbon monoxide and an ethylenically unsaturated compound to a mixed solvent containing the catalyst; And separating the polyketone from the methanol slurry, the method comprising the step of adding an additive to the methanol slurry.

Specifically, the additive is at least one selected from the group consisting of a heat stabilizer, an antioxidant and an ultraviolet screening agent, the additive is in powder form, and the heat stabilizer is tricalcium phosphate. .

Further, the present invention provides a polyketone which is produced by the above production method.

In addition, the present invention provides a polyketone characterized in that the increase in viscosity with time using a rheometer is 1500 Pa * s / 10 min.

According to the method for producing a polyketone of the present invention, it is possible to produce a polyketone having sufficient or excellent antioxidation, heat stability, and ultraviolet shielding effect by the addition of a small amount of an additive in production of the polyketone. Such polyketone can be usefully applied to molded articles such as fibers, automobile engine parts, gears, wheel covers and connectors.

FIG. 1 shows an increase in viscosity using a rheometer as a method of comparing the heat stabilizing effect.

According to the present invention, a mixture of methanol and water in the presence of an organometallic complex catalyst consisting of a Group 9, Group 10 or Group 11 transition metal compound, a ligand having an element of Group 15 and an anion of an acid having a pKa of 4 or less Adding to the solvent; Preparing a methanol slurry by adding a mixed gas of carbon monoxide and an ethylenically unsaturated compound to a mixed solvent containing the catalyst; And separating the polyketone from the methanol slurry, the method comprising the step of adding an additive to the methanol slurry.

Specifically, the additive is at least one selected from the group consisting of a heat stabilizer, an antioxidant, and an ultraviolet screening agent. The additive is in the form of powder, and the heat stabilizer is preferably Tricalcium Phosphate (TCP) Various additives such as lubricants may be used.

When the additive is added in a methanol slurry state after the polymerization, the dispersing power is improved, and the amount of the additive can be reduced to 1/10 of that of the conventional method of adding the additive to the dry powder.

Particularly, TCP used as a heat stabilizer is not dissolved in methanol, which is a polymerization solvent, but is dispersed in a colloid form. In the separation operation between a polyketone powder and methanol, TCP is hardly dispersed into a methanol layer, .

In the case of adding TCP to the conventional method and the manufacturing method of the present invention, when comparing the increase in viscosity with time using a rheometer, the thermal stability against the 5000 ppm level of the existing state was 500 ppm As well as the effect was expressed.

Hereinafter, the constitution and effects of the present invention will be described in more detail with reference to examples and comparative examples. However, these examples are merely intended to clarify the present invention and are not intended to limit the scope of the present invention. In Examples and Comparative Examples, the intrinsic viscosity, catalytic activity and viscosity of the polyketone were measured by the following method.

(1) intrinsic viscosity

The intrinsic viscosity was determined by the following equation.

[Equation 1]

[?] = lim (T-t) / t C (dl / g)

Wherein t and T are the times when a diluted solution of polyketone dissolved in hexafluoroisopropanol and hexafluoroisopropanol having a purity of 98% or more respectively flowed through a viscosity tube at 25 ° C, and C is a time Of solute mass.

(2) Catalytic activity

Weight of the polymerized resin / weight / hour of palladium (g-polyketone / g-Pd · hr).

(3) Measurement of viscosity increment using a rheometer

The vibrational shear rheology was measured using an Anton Paar MCR301 Model rheometer. The test specimens were molded with 30 mils inches (0.762 mm) thick discs using Compression Mouling, and the increase in viscosity was measured for 10 minutes at a rate of 1 rad / s at 275 degrees Celsius with a 25% strain. Chain breaking and crosslinking occur in polyketone due to presence of carbonyl group in high temperature, and viscosity increases with time. Therefore, the thermostable effect of the additives on the polyketone can be judged to be better as the viscosity of the rheometer increases.

(Example 1)

(Bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) was dissolved in 5 L of acetone, and then 2.8061 g Were added and dissolved. At the start of the polymerization, 14.252 g of triploloacetic acid was added and stirred to prepare a catalyst solution. 490 L of methanol, 7.9 L of water and 8.5 kg of polyketone powder for seeds were charged into a 1 m ³ stainless steel reactor, and the solution was subjected to nitrogen purge at 3.5 bar for 3 times to remove air. Propylene was filled in a 40 kg reactor in a fixed amount, and the temperature of the reactor was raised to 78 degrees Celsius. The stirrer was charged with stirring at a ratio of carbon monoxide: ethylene = 1: 1 to 56 bar. Polymerization was initiated by introducing the catalyst solution prepared above into a high pressure pump. The pressure of the polymerization reactor was supplemented with carbon monoxide: ethylene = 1: 1 at 78 ° C for 1 hour and 20 minutes and at 84 ° C for 2 hours and 50 minutes, Respectively. Thereafter, the polymerization was completed by keeping the monomer supply for 25 minutes.

After the polymerization, 500 ppm of TCP was added to the methanol slurry and stirred for 30 minutes. The reaction solution was filtered, washed several times with methanol, and 117.5 kg of polymer was obtained. (Polymerization activity 19.047 kg / g-Pd / hr)

^{From the 13} C-NMR and IR results, it was confirmed that the polymer was substantially a polyketone composed of repeating units derived from carbon monoxide, repeating units derived from ethylene, and repeating units derived from propylene.

The catalytic activity was equivalent to 19.05 kg / g-Pd / hr and the intrinsic viscosity was 1.4 dl / g.

The test specimens of 30 mils inches (0.762 mm) thick were molded with Compression Mouling, and a 25% strain was maintained at a rate of 1 rad / s at 275 degrees Celsius, and the increase in viscosity was measured for 10 minutes and shown in Table 1 and FIG. 1 .

(Comparative Example 1)

The procedure of Example 1 was the same as that of Example 1, except that 250 ppm of TCP was added to the prepared polymer instead of feeding 500 ppm of TCP into the methanol slurry of Example 1.

^{From the 13} C-NMR and IR results, it was confirmed that the polymer was substantially a polyketone composed of repeating units derived from carbon monoxide, repeating units derived from ethylene, and repeating units derived from propylene.

The catalytic activity was equivalent to 19.21 kg / g-Pd / hr and the intrinsic viscosity was 1.4 dl / g.

The test specimens of 30 mils inches (0.762 mm) thick were molded with Compression Mouling, and a 25% strain was maintained at a rate of 1 rad / s at 275 degrees Celsius, and the increase in viscosity was measured for 10 minutes and shown in Table 1 and FIG. 1 .

(Comparative Example 2)

The polymerization process of polyketone was the same as the process of Example 1, and methanol washing, filtration and drying under reduced pressure were carried out without the addition of TCP, and then 5000 ppm of TCP was mixed and extruded using a polyketone polymer and a tumbler under dry conditions.

 The catalytic activity was equivalent to 19.11 kg / g-Pd / hr, and the intrinsic viscosity was 1.4 dl / g.

The test specimens of 30 mils inches (0.762 mm) thick were molded with Compression Mouling, and a 25% strain was maintained at a rate of 1 rad / s at 275 degrees Celsius, and the increase in viscosity was measured for 10 minutes and shown in Table 1 and FIG. 1 .

According to the present invention, in the case of producing polyketone by copolymerizing carbon monoxide and an ethylenically unsaturated compound in a liquid medium, the case of Example 1 in which TCP was put in a methanol slurry state exhibited the most excellent heat stability (Tables 1 and 2 1). Particularly, the polyketone of Example 1 exhibited an increase in viscosity for 10 minutes using a rheometer of 1,500 Pa * s or less, which was superior to the comparative example in heat resistance.

Item TCP content TCP input method Increase in viscosity of Rheometer (10min) Example 500ppm Into MeOH Slurry 1,280 Comparative Example 1 250ppm Into MeOH Slurry 2,330 Comparative Example 2 5000ppm Mixed with dry powder 4,030

Claims (5)

To a mixed solvent consisting of methanol and water in the presence of an organometallic complex catalyst consisting of a Group 9, a Group 10 or Group 11 transition metal compound, a ligand having an element of Group 15 elements and an anion of an acid having a pKa of 4 or less ;
Preparing a methanol slurry by adding a mixed gas of carbon monoxide and an ethylenically unsaturated compound to a mixed solvent containing the catalyst; And
And separating the polyketone from the methanol slurry, the method comprising:
And adding an additive to the methanol slurry.
The method according to claim 1,
Wherein the additive is at least one selected from the group consisting of a heat stabilizer, an antioxidant and an ultraviolet screening agent, and the additive is in powder form.
3. The method of claim 2,
Wherein the heat stabilizer is tricalcium phosphate.
A polyketone produced by the process of any one of claims 1 to 3.
5. The method of claim 4,
Wherein said polyketone is a polyketone having a viscosity increase of not more than 1,500 Pa * s for 10 minutes using a rheometer.

Images