KR20160059889A - Method of low melting polyketone - Google Patents

Abstract

The present invention provides a method for producing low melting point polyketone. When low melting point polyketone is produced, a hydride anion provider is fed in the produced polyketone so as to solve a problem in which a polymerization speed is reduced and productivity is reduced when the low melting point polyketone is polymerized by increasing a content of propylene.

Description

TECHNICAL FIELD The present invention relates to a low melting polyketone

The present invention relates to a process for producing a low melting point polyketone and a low melting point polyketone produced therefrom characterized by the step of introducing a hydride anion carrier in the production of a low melting point polyketone.

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 properties, 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 most basic polyketone structure is a copolymer for fibers consisting of a copolymer of carbon monoxide (CO) and ethylene. It has a melting point of 250 to 260 캜 and can not be molded by heat processing. Therefore, when polymerization is carried out by addition of carbon monoxide (CO), ethylene as well as propylene as a monomer in the polymerization, the melting point is linearly decreased according to the content of propylene.

Based on this, general polyketone for extrusion injection uses mainly a polymer having a melting point of about 220 ° C. by adding about 4 mol% of propylene. However, it is difficult to ensure processability stability with polyketones having a melting point of 220 ° C when used in low flow extrusion applications such as Film / Pipe / Stock Shape. This is a phenomenon due to the rapid crystallization rate of polyketones, and further reduction of the melting point is required. Polyketone having a melting point of about 200 ° C is sufficiently capable of polymerization but requires a higher content of propylene, and the polymerization rate is slow due to the competitive reaction between propylene and ethylene in polymerization and the bulky properties of propylene relative to ethylene Resulting in very low productivity. The lowering of the polymerization rate leads to a decrease in the productivity and an increase in the residual amount of the metal catalyst in the polymer, which has a side effect of accelerating the crosslinking in thermal processing.

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

Korean Patent No. 10-0652074

The present invention aims to solve the problem of lowering the polymerization rate and lowering the productivity, which occurs when the propylene content is increased and the low melting point polyketone is polymerized, by the improved low melting point polyketone manufacturing method of the present invention.

In order to accomplish the above object, the present invention provides a process for producing an organometallic complex catalyst comprising a Group 9, a 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 To a mixed solvent composed of methanol and water, and a method for producing a polyketone by adding a mixed gas of carbon monoxide and an ethylenically unsaturated compound to a mixed solvent containing the catalyst, the method comprising: And a step of adding a ridged anion donor to the low-melting point polyketone.

Specifically, the hydride anion donor is lithium aluminum hydride or sodium borohydride, and the hydride anion donor is added in an amount of 0.01% to 3% based on the total weight of the polyketone slurry.

Further, the present invention provides a low melting point polyketone which is produced by the above-mentioned production method.

In addition, the low melting point polyketone has a melting point of 190 to 215 degrees and a ketone / hydroxyl group ratio of 95: 5 to 99.99: 0.01.

According to the method for producing a polyketone of the present invention, the production of a low-melting polyketone which can improve the productivity while maintaining or improving the polymerization rate relative to the high-melting-point polyketone polymerization rate by the addition of the hydride anion- And a low-melting point polyketone prepared therefrom.

Further, such polyketone can be usefully applied to molded articles due to processing at a low temperature of 215 DEG C or less for products for compression or film use.

Hereinafter, the present invention will be described in detail.

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 A method for producing a polyketone by adding a mixed gas of carbon monoxide and an ethylenically unsaturated compound to a mixed solvent comprising the catalyst and a method for producing the polyketone by adding a hydride anion donor in a methanol solvent Wherein the low-melting point polyketone is obtained by reacting a low-melting polyketone with a low-melting polyketone.

Specifically, the hydride anion donor is lithium aluminum hydride or sodium borohydride, and the hydride anion donor is added in an amount of 0.01% to 3% by weight. The high-dry anion provider used in the present invention is applicable to all of the conventional hydride anion providers that provide the hydride anions. For example, sodium cyanoborohydride (NaCNBH3) or sodium hydride (NaH) may be used in addition to the above-mentioned lithium aluminum hydride (LAH) and sodium borohydride (NaBH4) It will be apparent to those skilled in the art that the scope of the present invention is not limited thereto.

Further, the present invention provides a low melting point polyketone which is produced by the above-mentioned production method.

Hereinafter, the present invention will be described more specifically.

 The process for producing a polyketone according to the present invention comprises the steps of: (a) dissolving palladium acetate as a Group 9, Group 10 or Group 11 transition metal compound, (b) (2,2-dimethyl- Bis (methylene)) bis (bis (2-methoxyphenyl) phosphine) as a liquid medium was mixed with carbon monoxide and ethylenic unsaturation The compounds are copolymerized.

Examples of phosphine based bidentate ligand ligands include 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) Bis [di (2-methoxyphenyl) phosphino] propane, 1,3-bis [di (2-methoxy- Sodium 4-sulfonate-phenyl) phosphino] propane, and the like.

Examples of the ethylenically unsaturated compound copolymerized with carbon monoxide in the present invention include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, -Olefins such as tetradecene, 1-hexadecene, and vinylcyclohexane; Alkenyl aromatic compounds such as styrene and? -Methylstyrene; But are not limited to, cyclopentene, norbornene, 5-methylnorbornene, 5-phenylnorbornene, tetracyclododecene, tricyclododecene, tricyclo undecene, pentacyclopentadecene, pentacyclohexadecene, Cyclic olefins such as cyclododecene; Vinyl halides such as vinyl chloride; Ethyl acrylate, and acrylates such as methyl acrylate. These ethylenically unsaturated compounds are used singly or as a mixture of plural kinds. Of these, preferred ethylenically unsaturated compounds are? -Olefins, more preferably? -Olefins having 2 to 4 carbon atoms, and most preferably ethylene.

The molar ratio of the carbon monoxide / ethylenically unsaturated compound to the ethylenically unsaturated compound in the reaction vessel is preferably 1/1 to 1 / 2.5 from the viewpoints of polymerization activity and recovery cost. The method of adding the carbon monoxide and the ethylenically unsaturated compound is not particularly limited and may be added after mixing them in advance, or they may be added in separate feed lines. In the present invention, a mixed gas having a molar ratio of carbon monoxide and an ethylenic unsaturated compound of 1 / 2.5 and 1/1 was mixed in advance, and then a certain amount of monomer was continuously added to increase the polymerization activity

In carrying out the present invention, the polymerization method includes 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. The polymerization may be either batchwise or continuous. As the reactor used for the polymerization, known ones can be used as they are or by processing. 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.

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 above formula (1), G is an ethylenically unsaturated hydrocarbon, particularly 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.

Particularly preferred are polyketone polymers having a number average molecular weight of from 100 to 200,000, especially from 20,000 to 90,000, as measured by gel permeation chromatography. 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 260 ° C, and generally 180 ° C to 215 ° C. The intrinsic viscosity (LVN) of the polymer measured by HFIP (Hexafluoroisopropylalcohol) at 25 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.

The production of polyketone polymers for low melting point extrusion / films requires an initial propylene charge of 2 to 3 times higher than that of a conventional injection / extrusion polymer at a melting point of 220 degrees. Polymerization of polyketone is a complete alternating copolymerization of carbon monoxide and olefin, so that the insertion reaction of ethylene and propylene occurs competitively. Injection of non-bulky ethylene is more likely to occur than propylene. In order to increase the insertion probability of propylene, propylene is excessively injected. Therefore, the polymerization rate is reduced to half the level of ordinary injection / extrudate, and the secondary polymerization rate is a secondary problem in that a large amount of fouling occurs in the polymerization reactor.

The melting point of the polyketone prepared by the above-mentioned production method is 190 degrees, and the polymerization activity is 9 kg / g-Pd / hr. This is accompanied by a drastic decrease in productivity compared to the 220 ° C melting point for general extrusion and 17 kg / g-Pd / hr polymerization activity. Therefore, it is a key point of the present invention to lower the melting point of the polyketone by simple post-polymerization preparation without deterioration of the polymerization activity.

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. The intrinsic viscosity and catalytic activity of the polyketone in Examples and Comparative Examples were evaluated by the following methods.

(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) The amount of the polyketone

Pd, P, and Fe were measured using ICP-AES.

(4) Measurement of melting point Tm

5 mg of the sample was measured under the following conditions using a differential scanning calorimeter (DSC) in a nitrogen atmosphere.

Atmosphere: nitrogen flow rate = 200 ml / min

Temperature conditions: (1) Maintain at 20 DEG C for 1 minute, (2) 20 DEG C to 250 DEG C (temperature rise rate = 20 DEG C / minute)

The peak top temperature of the maximum endothermic peak in (2) was taken as the melting point

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 45 kg reactor in a fixed amount, and the temperature of the reactor was increased by 72 degrees centigrade. The stirrer was charged with stirring at a ratio of carbon monoxide: ethylene = 1: 1 to 56 bar. The polymerization was started while the catalyst solution prepared above was introduced into a high pressure pump. The pressure of the polymerization reactor was supplemented with carbon monoxide: ethylene = 1: 1 for 2 hours and 40 minutes at 72 ° C. and 3 hours and 10 minutes at 78 ° C., Respectively. Thereafter, the polymerization was completed by keeping the monomer supply for 25 minutes.

^{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 16.9 kg / g-Pd / hr and the intrinsic viscosity was 1.91 dl / g. To the obtained polyketone polymer slurry, 0.01% of NaBH ₄ was added and stirred for 1 hour. The methanol was washed and then dried under reduced pressure to obtain a low melting point polyketone polymer. The melting point and the amount of Pd remaining are shown in Table 1.

Example 2

A low melting point polyketone was prepared in the same manner as in Example 1 except that 0.05% NaBH ₄ was added to the resulting polyketone polymer slurry. The melting point and the amount of Pd residue are shown in Table 1.

Example 3

A low melting point polyketone was prepared in the same manner as in Example 1 except that 0.10% NaBH ₄ was added to the resulting polyketone polymer slurry. The melting point and the amount of Pd remnant are shown in Table 1.

Example 4

A low melting point polyketone was prepared in the same manner as in Example 1 except that 0.25% of NaBH ₄ was added to the resulting polyketone polymer slurry. The melting point and the amount of Pd residue are shown in Table 1.

Example 5

A low melting point polyketone was prepared in the same manner as in Example 1 except that 0.30% of NaBH ₄ was added to the obtained polyketone polymer slurry. The melting point and the amount of Pd remnant are shown in Table 1.

Comparative 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 150 kg reactor in a fixed amount, and the temperature of the reactor was raised to 62 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 for 2 hours and 40 minutes at 62 ° C. and 3 hours and 10 minutes at 68 ° C., Respectively. Thereafter, the polymerization was completed by keeping the monomer supply for 25 minutes.

^{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 8.41 kg / g-Pd / hr, and the intrinsic viscosity was 1.93 dl / g. At this time, the melting temperature (Tm) of the polyketone polymer was 190 degrees (see Table 1).

Item Polymerization catalyst activity NaBH ₄ charge Melting point Pd remaining amount Example 1 16.6 kg / g-Pd / hr 0.01% 215 2.1 ppm Example 2 16.9 kg / g-Pd / hr 0.05% 206 2.3 ppm Example 3 16.0 kg / g-Pd / hr 0.10% 199 2.0 ppm Example 4 16.4 kg / g-Pd / hr 0.25% 193 2.5 ppm Example 5 15.8 kg / g-Pd / hr 0.30% 192 1.9 ppm Comparative Example 1 8.41 0.00% 190 5.8ppm

According to the present invention, when polyketone is produced by copolymerizing carbon monoxide and an ethylenically unsaturated compound in a liquid medium, the productivity of the polymerized product in which the NaBH ₄ is added in the form of a methanol slurry (added in an amount of 0.01% to 3% The productivity was about twice as high as that of the polymer prepared by the addition of the propylene overload (Comparative Example 1), and the residual amount of Pd as the metal catalyst in the polymer was less than half. Further, as a result of IR and NMR, the ratio of the ketone group to the hydroxyl group in the low melting point polyketone prepared in Examples 1 to 5 was 95: 5 to 99.99: 0.01.

The low melting point polyketone prepared through the above process has been found to be suitable for application to bar extrusion products or films having excellent productivity and low Pd residue.

Claims (7)

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 ; And a method for producing a polyketone by adding a mixed gas of carbon monoxide and an ethylenically unsaturated compound to a mixed solvent comprising the catalyst,
And a step of adding the hydride anion provider to the polyketone produced in a methanol solvent.
The method according to claim 1,
Wherein the hydride anion donor is lithium aluminum hydride or sodium borohydride.
The method according to claim 1,
Wherein the hydride anion donor is added in an amount of 0.01% to 3% based on the total weight of the polyketone polymer slurry.
A low melting point polyketone produced by the process of any one of claims 1 to 3.
5. The method of claim 4,
Wherein the low melting point polyketone has a melting point of 190 to 215 degrees.
5. The method of claim 4,
Wherein the low melting point polyketone has a ratio of ketone group and hydroxyl group of 95: 5 to 99.99: 0.01.
5. The method of claim 4,
Wherein the low melting point polyketone is applied to a product or film for extrusion.